Synthetic methods for compounds having CF3-S units on carbon by trifluoromethylation, trifluoromethylthiolation, triflylation, and related reactions.

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Synthetic Methods for Compounds Having CF3−S Units on Carbon by Trifluoromethylation, Trifluoromethylthiolation, Triflylation, and Related Reactions Xiu-Hua Xu, Kohei Matsuzaki, and Norio Shibata* Department of Nanopharmaceutical Science and Department of Frontier Materials, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555, Japan Biographies Acknowledgments References

1. INTRODUCTION Fluorine is the most abundant halogen in the Earth’s crust.1 However, only a dozen fluorinated organic compounds have been identified in nature.2 Most of the organofluorine compounds are synthesized by organic chemists. From this point of view, fluorine-containing groups play an important role in fluorine chemistry. The incorporation of fluorine-containing groups into an organic molecule often drastically perturbs the chemical, physical, and biological properties of the parent compound, so organofluorine compounds are receiving increasing attention in the medicinal, pharmaceutical, agricultural, and material sciences.3−14 To date, the trifluoromethyl group is the most widely used fluorine-containing group owing to its strong electron-withdrawing power and high lipophilicity.15−20 In recent years, there has been growing interest in the association of the trifluoromethyl group with heteroatoms such as trifluoromethoxy (OCF3) or trifluoromethanesulfenyl (SCF3). These functional groups have similar properties as the trifluoromethyl (CF3) group.21−23 As shown in Table 1, among these functional groups, SCF3 shows

CONTENTS 1. Introduction 2. Synthesis of C-SCF3 Compounds 2.1. Synthesis of C-SCF3 (sp3) Compounds 2.1.1. Synthesis of Alkyl Trifluoromethyl Sulfides 2.1.2. Synthesis of Benzyl or Allyl Trifluoromethyl Sulfides 2.1.3. Synthesis of α-Trifluoromethanesulfenyl Carbonyl Compounds 2.2. Synthesis of C-SCF3 (sp2) Compounds 2.2.1. Synthesis of Aryl Trifluoromethyl Sulfides 2.2.2. Synthesis of Heteroaryl Trifluoromethyl Sulfides 2.2.3. Synthesis of Vinyl Trifluoromethyl Sulfides 2.2.4. Synthesis of Other C-SCF3 (sp2) Compounds 2.3. Synthesis of C-SCF3 (sp) Compounds 3. Synthesis of C-SOCF3 Compounds 4. Synthesis of C−SO2CF3 Compounds 4.1. Synthesis of C−SO2CF3 (sp3) Compounds 4.1.1. Synthesis of Alkyl Trifluoromethanesulfones (Triflones) 4.1.2. Synthesis of Benzyl, Allyl, and Propargyl Triflones 4.1.3. Synthesis of Bis(triflyl) and Tris(triflyl)alkanes 4.1.4. Synthesis of α-Triflyl Carbonyl and Sulfonyl Compounds 4.2. Synthesis of C−SO2CF3 (sp2) Compounds 4.2.1. Synthesis of Aryl Triflones 4.2.2. Synthesis of Heteroaryl Triflones 4.2.3. Synthesis of Vinyl and Allenyl Triflones 4.3. Synthesis of C−SO2CF3 (sp) Compounds 5. Synthesis of C−S(O)x(NR)CF3 Compounds 6. Conclusion Author Information Corresponding Author Notes © 2014 American Chemical Society

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Table 1. “Aromatic” Substituent Constants of Selected Fluorine-Containing Groups Π σm σp

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CF3

OCF3

SCF3

SOCF3

SO2CF3

0.88 0.43 0.54

1.04 0.38 0.35

1.44 0.40 0.50

0.63 0.69

0.55 0.79 0.93

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extremely high lipophilicity (π = 1.44) and trifluoromethanesulfonyl (SO2CF3) has the strongest electron-withdrawing power (σm = 0.79, σp = 0.93), while trifluoromethanesulfinyl (SOCF3) exists between two. Compounds containing SCF3, as well as the analogous groups, are frequently found in many pharmaceutical and agrochemical products. Representative examples are shown in Scheme 1. Toltrazuril is a coccidiostatic drug24,25 while Tiflorex is an anorectic drug.26,27 Cefazaflur is a parenteral cephalospor-

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Special Issue: 2015 Fluorine Chemistry Received: April 6, 2014 Published: August 14, 2014 731

dx.doi.org/10.1021/cr500193b | Chem. Rev. 2015, 115, 731−764

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2. SYNTHESIS OF C-SCF3 COMPOUNDS

Scheme 1. Examples of SOnCF3-Containing Biologically Active Compounds

2.1. Synthesis of C-SCF3 (sp3) Compounds

2.1.1. Synthesis of Alkyl Trifluoromethyl Sulfides. Different synthetic methods of alkyl trifluoromethyl sulfides are summarized in Scheme 3. For both trifluoromethanesulfenylation and trifluoromethylation reactions, electrophilic, nucleophilic, and radical approaches have been developed. Other methods, such as functionalization, fluorination, and decomposition, are important complements. The content of direct trifluoromethanesulfenylation is shown in Schemes 4−9. Two key aspects are summarized: (1) free radical, electrophilic, and nucleophilic reactions of alkanes; (2) radical and electrophilic addition to olefins. The free radical chain reaction of trifluoromethanesulfenyl chloride (CF3SCl) with saturated hydrocarbons was first reported by Harris (Scheme 4).54,55 The desired products were obtained in moderate yields, along with other byproducts. Depending on the structure of the alkane precursor, different isomers of the products might be produced (eqs a and b, Scheme 4). Electrophilic trifluoromethanesulfenylation with different electrophilic reagents was examined by different research groups (Scheme 5).56−58 Among these electrophilic trifluoromethanesulfenylation reagents, easily available trifluoromethanesulfanamide (CF3SNMePh) showed efficient reactivity (eq b, Scheme 5).57 The reaction of alkyl halides with different nucleophilic trifluoromethylthiol metal compounds provides another route to alkyl trifluoromethyl sulfides (Scheme 6).59−65 Various nucleophilic SCF3 transfer reagents, such as Hg(SCF3)2,59,60 AgSCF 3 , 61 CuSCF 3 , 62,63 CsSCF 3 , 64 Me 4 NSCF 3 , 64 and HSCF3,65 were widely applied in this substitution reaction. The free radical addition of trifluoromethanethiol (CF3SH) or CF3SCl to olefins resulted in the formation of various alkyl trifluoromethyl sulfides (Scheme 7).54,60,66−71 The direction of attack can be attributed to the stability of the intermediate radical. For example, the addition of CF3SH to isobutylene gave isobutyl(trifluoromethyl)sulfane as a major product, which could be predicted by radical stability theory.66 Another type of addition reaction to olefins is electrophilic addition (Scheme 8).72−75 The first example of the trifluoroacetic acid (TFA)-catalyzed electrophilic addition to olefins using CF3SCl was reported by Zhang in 1985.72 Electrophilic addition with other active trifluoromethanesulfenylation reagents, trifluoromethanesulfenyl fluoride (CF3SF)73 and trifluoromethanesulfenyl acetate or trifluoroacetate (CF3SOCOR),74 was also developed. It is noteworthy that the addition to cyclohexene gave the trans adducts, which were thermodynamically stable. Recently, three-component addition reactions were developed by Langlois76 and Qing77 to provide double-functionalized products (Scheme 9). In both cases, the trans configuration of the products supports an anti addition, in which the intermolecular (eq a, Scheme 9) or intramolecular (eq b, Scheme 9) opening of an episulfonium intermediate might be involved. Methods for the trifluoromethylation of sulfur-containing substrates are shown in Schemes 10−13. Electrophilic, nucleophilic, and particularly radical trifluoromethylation are widely applied in the synthesis of alkyl trifluoromethyl sulfides. Normally trifluoromethylation of thiolates (RS−) with an electrophilic reagent (CF 3 I) (eq a, Scheme 10) 78 or

in 28,29 and Fipronil is a widely used phenylpyrazole insecticide.30,31 The analogues of Losartan and Nifedipin have been developed as potential hypotensive agents.32 Trifluoromethionine, a trifluorinated analogue of the amino acid methionine, has emerged as a promising lead for amebiasis.33−35 5′-Trifluoromethyladenosine shows good inhibitory activity against P. falciparum (FBC1).36 Some previous excellent reviews partly focused on SOnCF3containing compounds.37−53 This present work, however, is the first comprehensive review on various synthetic methods of SOnCF3-containing compounds as well as their typical applications. This review includes all the reported methods in the literature until the end of 2013. Different strategies applied to SOnCF3-containing compounds are summarized in Scheme 2. The two major approaches for the formation of these compounds are direct C−S bond formation, including intermolecular or intramolecular trifluoromethanesulfenylation or trifluoromethanesulfonylation, and direct trifluoromethylation of sulfur-containing compounds. The three remaining methods, functionalization, transformation, and fluorination, are occasionally used depending on the substrate. Scheme 2. Different Strategies Applied to SOnCF3Containing Compounds

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Scheme 3. Different Methods for the Preparation of Alkyl Trifluoromethyl Sulfides

Scheme 4. Free Radical Reaction with CF3SCl

Scheme 7. Addition of Free Radical to Olefins

Scheme 5. Electrophilic Trifluoromethanesulfenylation

Scheme 8. Electrophilic Addition to Olefins

Scheme 6. Nucleophilic Trifluoromethanesulfenylation Scheme 9. Three-Component Addition Reaction

Umemoto’s reagent (eq b, Scheme 10)79,80 affords the corresponding trifluoromethyl sulfides. A breakthrough of this type of reaction was reported by Togni in 2007.81 Using his reagent, various thiols were smoothly converted to the

trifluoromethylated products directly without the addition of a base (eq c, Scheme 10).81−85 733


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Scheme 10. Electrophilic Trifluoromethylation Methods

Scheme 13. Radical Trifluoromethylation of Disulfides

The reactions of disulfides or thiocyanates with different nucleophilic trifluoromethylation systems are summarized in Scheme 11.86−93 Except for the system in eq a of Scheme 11,86

tems.97−105,107−111 Langlois reported the generation of a trifluoromethyl radical from his reagent (CF3SO2Na) while preparing SCF3-containing α-amino acids.112 Another type of trifluoromethylation reagent used in radical reactions is Ntrifluoromethyl-N-nitrososulfonamide, developed by Umemoto.106,113 The radical addition of trifluoromethyl to thiones is another approach to produce trifluoromethyl sulfides (eq a, Scheme 14).114 Similarly, the nucleophilic addition of aromatic thiones

Scheme 11. Nucleophilic Trifluoromethylation Methods

Scheme 14. Radical and Nucleophilic Trifluoromethylation of Thiones

all of the remaining four systems were developed by the Langlois group.87−93 Various alkyl sulfides were produced by their methods. Unlike the electrophilic trifluoromethylation reaction, these nucleophilic trifluoromethylation reactions always need two-component systems. This generated CF3−in situ probably because this anion is very unstable and collapses easily into a fluoride anion and difluorocarbene.94−96 Radical trifluoromethylation is widely applied to different substrates, such as thiols and thiolates (Scheme 12),97−106 as well as disulfides (Scheme 13).107−113 The trifluoromethyl radical is normally prepared from trifluoromethyl halides (CF3Br or CF3I) irradiated under different reported sys-

was reported under a TMSCF3/TBAF condition (eq a, Scheme 14).115,116 In both cases, yields were average because of the side reactions. In 1952, the photolysis of bistrifluoromethyl disulfide (CF3SSCF3) reportedly afforded bistrifluoromethyl sulfide (CF3SCF3) in 66% yield (eq a, Scheme 15).117 After about half a century, the Langlois group developed the photolysis of trifluoromethanethiosulfonates (CF3SO2SR) or trifluorothioacetates (CF3COSR) in the presence of corresponding disulfides (eq b and eq c, Scheme 15).90,118,119 The decarbonylated or

Scheme 12. Radical Trifluoromethylation of Thiols and Thiolates

Scheme 15. Photolysis Reactions for the Preparation of Trilfuoromethyl Sulfides

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desulfonylated product was obtained, and the added disulfide (or diselenide) was recovered after the reaction. Starting from trifluoromethyl vinyl sulfide, different addition products were prepared (Scheme 16).60,120 The reactions could be divided into three types: common addition (eq a, Scheme 16),60 Diels−Alder addition (eq b, Scheme 16),54 and cyclopropanation (eq c, Scheme 16).120

Scheme 18. Electrophilic Allylic Trifluoromethanesulfenylation

Scheme 16. Transformation from Trifluoromethyl Vinyl Sulfide

Scheme 19. Nucleophilic Allylic Trifluoromethanesulfenylation

The last method for the preparation of trifluoromethyl sulfides is fluorination from corresponding trichloromethyl sulfides (Scheme 17).90,121 Through a chlorine-fluorine Scheme 17. Fluorination of Trichloromethyl Sulfides

In 1994, the Kolomeitsev group developed a two-step procedure for the synthesis of trifluoromethyl sulfides (Scheme 20).130 By phosphitylation of alcohols followed by the reaction of CF3SSCF3, the trifluoromethanesulfenylated products were obtained in excellent yields.

exchange with (HF)10-pyridine, the desired products were obtained in moderate to good yields. This halogen-fluorine exchange method, although very old,122 is still commercially significant. 2.1.2. Synthesis of Benzyl or Allyl Trifluoromethyl Sulfides. The first electrophilic allylic trifluoromethanesulfenylation was reported by Mokrosz in 1986 (eq a, Scheme 18).123 The alkylidenemalononitrile dimers reacted smoothly with CF3SCl giving allylic SCF3 compounds in good yields. Recently, Billard and Langlois reported a new method for the preparation of allylic SCF3 compound by the reaction of hindered olefin reacted with CF3SNMePh (eq b, Scheme 18).76 Soon after, Qing developed a modified procedure with allylsilanes as the substrates, in which the pendant trimethylsilyl group could enhance the nucleophilicity of olefins and control regioselectivity via the β-silyl effect (eq c, Scheme 18).124 Compared to electrophilic allylic trifluoromethanesulfenylation, the nucleophilic process has received more attention (Scheme 19).54,59,64,120,125−129 Different nucleophilic trifluoromethanesulfenylation reagents were widely used in the substitution reaction of benzyl halides (eqs a−d, Scheme 19),54,64,125,126 allyl halides (eq e, Scheme 19),59,120,127 and propargyl bromide (eq f, Scheme 19).128,129 In all cases, good yields of the desired products were obtained.

Scheme 20. Preparation of Trifluoromethyl Sulfides from Alcohols

The other methods for preparation of benzyl trifluoromethyl sulfides are the same as those used for alkyl trifluoromethyl sulfides. Nucleophilic trifluoromethylation of benzyl thiocyanate is described in Scheme 11,86−88 and fluorination from trichloromethyl sulfide is described in Scheme 17.90,121 2.1.3. Synthesis of α-Trifluoromethanesulfenyl Carbonyl Compounds. The reactions of various carbonyl compounds with CF3SCl were reported in the last century (eq a, Scheme 21).131−139 Under the conditions with or without a base, the corresponding α-SCF3 carbonyl compounds were obtained in good yields. Sometimes the bis(trifluoromethylthio)-substituted products were produced. 131, 133,134, 139 In 2000, Munavalli utilized N(trifluoromethylthio)phthalimide as the trifluoromethanesulfe735


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Scheme 21. Electrophilic Trifluoromethanesulfenylation

Scheme 23. Nucleophilic Trifluoromethanesulfenylation

pyridinone derivative. Li and Zard reported a metal-free reagent O-octadecyl-S-trifluorothiolcarbonate for the conversion of αbromoketones and -esters into the corresponding trifluoromethyl sulfides in good yields (eq b, Scheme 23).147 Radical trifluoromethylation of thiols (Scheme 12)103 and disulfides (Scheme 13)108 were also applied in the synthesis of different α-trifluoromethanesulfenyl carbonyl compounds.

nylation reagent for the preparation of α-SCF3 carbonyl compounds (eq b, Scheme 21).140 Recently, Lu and Shen developed a novel hypervalent iodine reagent A for the trifluoromethylthiolation of β-keto esters (eq c, Scheme 21).141 Buchwald and co-workers reported a revised structure for this electrophilic trifluoromethylthiolation reagent as thioperoxy compound B.142 Our group also developed a unique trifluoromethanesulfonyl hypervalent iodonium ylide as the electrophilic-type trifluoromethanesulfenylation reagent (eq d, Scheme 21).143 The asymmetric electrophilic trifluoromethanesulfenylation of β-keto esters was simultaneously reported by Rueping and Shen (Scheme 22).144,145 They chose almost the same

2.2. Synthesis of C-SCF3 (sp2) Compounds

2.2.1. Synthesis of Aryl Trifluoromethyl Sulfides. Most of the strategies for the synthesis of alkyl trifluoromethyl sulfides in Scheme 3 can also be applied for the synthesis of aryl trifluoromethyl sulfides. Direct trifluoromethanesulfenylation and trifluoromethylation of sulfur-containing compounds are the two major approaches to various aryl trifluoromethyl sulfides. The most convenient synthesis of aryl trifluoromethyl sulfides is the condensation of electron-rich aromatic compounds with electrophilic trifluoromethanesulfenylation reagents (Scheme 24).54,74,148−152 Normally the substitution

Scheme 22. Asymmetric Electrophilic Trifluoromethanesulfenylation

Scheme 24. Electrophilic Trifluoromethanesulfenylation of Electron-Rich Aromatic Compounds

substrates and similar cinchona alkaloid catalysts, with different trifluoromethanesulfenylation reagents. In both cases, excellent enantioselectivities were obtained. Those studies provided rare examples of the synthesis of optically pure SCF3-containing compounds. Nucleophilic trifluoromethanesulfenylation for the preparation of α-SCF3 ketone was reported by Abdulla in 1979 (eq a, Scheme 23).146 This substitution step afforded an intermediate, which was then used to prepare the 3,5-disubstituted-4(1H)-

occurs in the para position for electron-donating substituents. Compared to gaseous CF3SCl, trifluoromethanesulfenyl trifluoroacetate (CF3CO2SCF3) is more stable and easier to handle.74 Langlois reported that trifluoromethanesulfanylamide (PhNMeSCF3) could also be used in electrophilic aromatic substitution under the activation of protic acid (eq c, Scheme 24).152 In 2012, Daugulis and co-workers reported the first example of copper-promoted direct trifluoromethanesulfenylation of aromatic C−H bonds with CF3SSCF3 as the electrophilic reagent (Scheme 25).153 8-Aminoquinoline auxiliary was introduced as the directing group for ortho-trifluoromethanesulfenylation of benzoic acid derivatives. The difunctionalization products were obtained in moderate yields. 736


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Scheme 25. Copper-Promoted C−H Bond Trifluoromethanesulfenylation

Scheme 27. Trifluoromethanesulfenylation of Aryl Halides

The conversion of aryl halides to aryl trifluoromethyl sulfides has been widely investigated. Trifluoromethylthiocopper (CuSCF3) was the first convenient reagent for reactions with aryl halides (eq a, Scheme 26).154−159 Alternatively, CuSCF3

Scheme 28. Transition-Metal-Catalyzed Trifluoromethanesulfenylation of Aryl Halides

Scheme 26. Trifluoromethanesulfenylation of Aryl Halides

temperature using the less expensive Me4NSCF3 (eq b, Scheme 28).171 Both of these protocols represent significant advances of the yields to previous methods used to prepare aryl trifluoromethyl sulfides. In 2000, Clark and co-workers reported a new synthetic route to aryl trifluoromethyl sulfides from the corresponding diazonium tetrafluoroborates in the presence of CuSCF3 (eq a, Scheme 29).172 When electron-donating groups were present, could be formed in situ from Hg(SCF3)2/Cu and the condensation product was obtained in comparable yield (eq b, Scheme 26).160,161 In order to improve yields and the purification of products, other versions of the copper salt were also developed (eqs c and d, Scheme 26).162,163 Recently, the Weng group developed a ligated copper trifluoromethylthiolate species [(bpy)CuSCF3] as an efficient reagent for the trifluoromethanesulfenylation of aryl halides (eq e, Scheme 26).164 The reaction of silver(I) trifluoromethanethiolate (AgSCF3) with KI led to the formation of another nucleophilic source of trifluoromethanethiolate, which was capable of converting aryl halides into the corresponding trifluoromethyl sulfides (eq a, Scheme 27).165 Other sources of trifluoromethanethiolate, such as CsSCF3, Me4NSCF3, and (TDAE)2+[SCF3]2−, were also reported by different groups (eq b and c, Scheme 27).64,125,166 Trifluoromethanethiolate can be generated in situ by the reaction of thiophosgene with fluorides (eq d, Scheme 27)167,168 or methyl fluorosulfonyldifluoroacetate and sulfur (eq e, Scheme 27).169 Transition-metal-catalyzed trifluoromethanesulfenylation of aryl halides has been developed only recently (Scheme 28).170,171 In 2011, Buchwald and co-workers reported a palladium-catalyzed process employing the hindered BrettPhos ligand using AgSCF3 as the nucleophilic partner (eq a, Scheme 28).170 Soon after, Vicic and co-workers developed a nickelcatalyzed trifluoromethanesulfenylation of aryl halides at room

Scheme 29. Trifluoromethanesulfenylation of Aryl Diazonium Tetrafluoroborates

product yield was generally low. To avoid isolation of the diazonium intermediate, a one-pot conversion of aryl amines to trifluoromethyl aryl sulfides was also developed (eq b, Scheme 29), although yields were lower than when the diazonium intermediate was isolated. Transition-metal-mediated or catalyzed trifluoromethanesulfenylation of aryl boronic acids has also been developed only recently (Scheme 30).141,173,174 Vicic and Zhang reported the copper-mediated oxidative trifluoromethanesulfenylation of aryl boronic acids using Me4NSCF3 with air as the oxidant (eq a, Scheme 30).173 Lu and Shen developed the copper-catalyzed trifluoromethanesulfenylation of aryl boronic acids using their electrophilic hypervalent iodine reagent (eq b, Scheme 30),141 737


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Scheme 30. Trifluoromethanesulfenylation of Aryl Boronic Acid

Scheme 32. Electrophilic Trifluoromethylation of Aromatic Thiolates or Thiols

Scheme 33. Nucleophilic Trifluoromethylation of Diary Disufides while Qing reported copper-catalyzed oxidative trifluoromethanesulfenylation using TMSCF3 and S8 (eq c, Scheme 30).174 All these different strategies provide efficient synthesis of aryl trifluoromethyl sulfides from aryl boronic acids. The reaction of aryl metallic species and electrophilic trifluoromethanesulfenylation reagents is a common and convenient method for the preparation of aryl trifluoromethyl sulfides (Scheme 31).57,175,176 However, the yields are normally Scheme 31. Trifluoromethanesulfenylation of Aryl Metallic Species

of diaryl disulfides leads to the formation of corresponding aryl trifluoromethyl sulfides (eq b, Scheme 33).181−183 The most widely used trifluoromethylating agent, TMSCF3, has also been used for the synthesis of aryl trifluoromethyl sulfides in the presence of TBAF (eq c, Scheme 33).87 In 2003, Prakash and co-workers reported that t-BuOK induced nucleophilic trifluoromethylation of diphenyl disulfides using phenyl trifluoromethyl sulfone (PhSO2CF3) (eq d, Scheme 33).184 At the beginning of this century, Langlois’s group developed two types of trifluoromethylating agents: hemiaminals of trifluoroacetaldehyde (eq e, Scheme 33)92 and trifluoromethanesulfinamides (eq f, Scheme 33),93 both of which have been used in nucleophilic trifluoromethylation reactions. Recently, a new trifluoromethylating reagent, an amidinate salt of hexafluoroacetone hydrate, was developed by Colby and coworkers (eq g, Scheme 33).185 The activity of this salt is nearly identical to that of PhSO2CF3. The last reagent applied in this type of reaction is diethyl trifluoromethylphosphonate (eq h, Scheme 33).186 It expands the array of available trifluoromethylating reagents with a new phosphorus-containing member. Besides diaryl disulfides, other compounds, such as sulfenyl chlorides, thiocyanates, and thiosulfonates, can also be used as substrates in nucleophilic trifluoromethylation reactions (Scheme 34).88,179,187 These compounds can be easily converted to the corresponding trifluoromethyl sulfides when treated with TMSCF3/fluoride (eq a, Scheme 34)88,187 or

low (9−62%) when CF3SCl is used as the electrophilic reagent. There was an important breakthrough when Billard applied their reagent in this type of reaction (eq b, Scheme 31).57 Yields increased when CF3SNMePh was used as the electrophilic reagent. Another important approach to aryl trifluoromethyl sulfides is the trifluoromethylation of sulfur-containing aromatic compounds. Electrophilic trifluoromethylation of aromatic thiolates or thiols have been applied in the synthesis of various aryl trifluoromethyl sulfides (Scheme 32).79,81,177,178 Umemoto’s reagents (eq a, Scheme 32)79,177,178 and Togni’s reagents (eq b, Scheme 32)81 are the major trilfuoromethylating agents used in this type of reaction. In both cases, the desired products were obtained in good yields. Unlike electrophilic trifluoromethylation, nucleophilic reactions have been reported with different CF3 anion sources. As shown in Scheme 33, eight methods have been developed for the conversion of diaryl disulfides to aryl trifluoromethyl sulfides by anion trifluoromethylation. The most simple source is trifluoromethane (fluoroform) deprotonated by strong bases, such as t-BuOK or phosphazene bases (eq a, Scheme 33).91,179,180 Heating potassium trifluoroacetate in the presence 738


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Scheme 34. Nucleophilic Trifluoromethylation

Scheme 36. Radical Trifluoromethylation of Diaryl Disulfides

HCF3/t-BuOK (eq b, Scheme 34)179 in moderate to good yields. Radical trifluoromethylation of aryl thiolates have received much attention (Scheme 35).78,79,188−197 This type of reaction

Scheme 37. Synthesis of Aryl Trifluoromethyl Sulfide by Halogen-Fluorine Exchange

Scheme 35. Radical Trifluoromethylation of Aryl Thiolates

conditions can be used for this conversion. Even using silver tetrafluoroborate (AgBF4) under mild conditions, aryl trifluoromethyl sulfides can be prepared by a bromine−fluorine exchange (eq b, Scheme 37).204 The last method for the preparation of aryl trifluoromethyl sulfide is the reduction of trifluoromethanesulfoxides (Scheme 38).206,207 Self-immolative reduction of trifluoromethanesulfoxides promoted by trifluoromethanesulfonic anhydride (Tf2O) was reported by Blazejewski and Magnier. In the absence of any added nucleophilic species, trifluoromethylsulfenyl sulfonium salts were produced in moderate yields (eq a, Scheme 38).206 The reaction of trifluoromethanesulfoxides with nitriles under the activation of Tf2O led to the formation of different aromatic

involves nucleophilic radical substitution (SRN1). Different types of reaction conditions have been reported for the generation of a trifluoromethyl radical. Wakselman and coworkers developed SRN1 substitutions by CF3Br under slight pressure (eq a, Scheme 35).188−190 Photochemical stimulation was widely used in the synthesis of different aryl trifluoromethyl sulfides (eq b and c, Scheme 35).79,191 In 1992, Koshechko and co-workers reported a convenient method under mild conditions, based on the catalytical action of methylviologen (MV2+) additions (eq d, Scheme 35).192,193 Later, the same group developed electrochemical trifluoromethylation by CF3Br with SO2 as an efficient catalyst (eq e, Scheme 35).194,195 The system of Bi(CF3)3/Cu(OAc)2 opens a new approach to obtaining aryl trifluoromethyl sulfide (eq f, Scheme 35).196 The reactions of aryl thiolates and CF3I without any initiators were also investigated (eq g, Scheme 35).78,197 Diaryl disulfides may also be used as substrates in radical trifluoromethylation reactions (Scheme 36).108−110,190,198−200 Different reaction systems, such as CF3Br/NaO2SCH2OH (eq a, Scheme 36),108,190,198 CF3I/TDAE (eq b, Scheme 36),109,110 CF3CO2H/XeF2 (eq c, Scheme 36),199 and F3CNNSO2Ar (eq d, Scheme 35),200 could accomplish this transformation. The desired aryl trifluoromethyl sulfides were obtained in good to excellent yields. Substitution of halogen atoms by fluorine in aryl polyhalogenalkyl sulfides provides another synthetic route to aryl trifluoromethyl sulfides (Scheme 37).201−205 SbF3 or triethylamine trihydrofluoride (TREAT-HF) under microwave

Scheme 38. Synthesis of Aryl Trifluoromethyl Sulfide from Trifluoromethanesulfoxides

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(eq b, Scheme 38)207 or benzylic (eq c, Scheme 38)207 C−H bond functionalized products in low yields, respectively. 2.2.2. Synthesis of Heteroaryl Trifluoromethyl Sulfides. Most of the methods for the preparation of aryl trifluoromethyl sulfides can be used in the synthesis of heteroaromatic compounds. Due to the unique property of heteroatoms, some heteroaromatic compounds are synthesized by different methods. Among different heteroaromatic compounds, the reactions of pyrroles have been most carefully studied by Haas and coworkers (eq a, Scheme 39).208−210 Pyrroles readily reacted with

Scheme 40. Electrophilic Trifluoromethanesulfenylation of Indoles and Indolizines

Scheme 39. Electrophilic Trifluoromethanesulfenylation of Pyrroles, Furans, Thiophene, Selenophene, and Pyridine

Scheme 41. Electrophilic Trifluoromethanesulfenylation of Pyrrole Derivatives

CF3SCl, giving various trifluoromethanesulfenylated compounds. This reaction could be applied for N-protected and unprotected substrates. An excess of reagents sometimes gave bis(SCF3)-pyrrole derivatives. Tri- and tetra-(SCF3)-pyrrole derivatives could be further synthesized with a catalyst.209,210 Unlike pyrroles, the reactions of furan with CF3SCl needed pyridine for the activation. Only 2-SCF3 derivatives were obtained in moderate yields (eq b, Scheme 39).211 Thiophene and selenophene reacted with CF3SCl in the presence of SnCl4, affording the corresponding trifluoromethanesulfenylated products in moderate yields (eq c, Scheme 39).74,212 Pyridine is also deactivated for trifluoromethanesulfenylation under classic conditions. To accomplish this substitution, two steps are needed: the reduction with LiAlH4 to obtain an anionic hydride σ-complex intermediate and then the reaction with CF3SCl (eq d, Scheme 39).213 The reaction of indole and CF3SCl gave the 3-SCF3 derivative (eq a, Scheme 40).208 Langlois’s system (eq b, Scheme 40)77,152 and Shibata’s system (eq c, Scheme 40)143 could also be used to prepare the same products. The 2-SCF3 indole derivatives were obtained when the 3-position was already substituted (eq d, Scheme 40).77,152 The reaction of indolizines and CF3SCl gave bis(SCF3)-substituted products in quantitative yields (eq e, Scheme 40).214 The reactions of pyrrole derivatives, bearing a novel tricyclic system, with CF3SCl in the presence of pyridine gave the trifluoromethanesulfenylated products (Scheme 41).215,216 These products have potential biological activities. It is interesting to note that only the 3-position in the 5,6unsaturated substrate was reactive in this electrophilic

substitution reaction (eq b, Scheme 41),216 while the other 5,6-saturated substrate was converted to two products (eq a, Scheme 41).215 Another type of electrophilic trifluoromethanesulfenylation reaction of heteroaromatic compounds is shown in Scheme 42. Two steps are needed in this method: the treatment with metallic reagents (organolithium or Grignard reagents) and the reaction of electrophilic trifluoromethanesulfenylation reagents (CF3SSCF3, CF3SCl, or CF3SNMePh). This method is applied for the synthesis of different SCF3-substituted imidazoles,217 thiazoles,218 or pyridines.57 The nucleophilic substitution reaction is another important method for the preparation of heteroaryl trifluoromethyl compounds. Reactions of pentafluoropyridine and the trifluoromethylthiolate anion gave a 4-substituted product in good yields (eq a-d, Scheme 43).64,125,168,219 Tetrafluoropyridazine and tetrafluoropyrimidine could also be converted to the trifluoromethanesulfenylated compounds by the reaction of CF2S/CsF (eqs e and f, Scheme 43).220 740


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(Scheme 45).141,170,171 These recently developed methodologies afford convenient methods for the synthesis of various trifluoromethanesulfenylated heteroaromatic compounds.

Scheme 42. Metallic Reagents Induced Trifluoromethanesulfenylation

Scheme 45. Transition-Metal-Catalyzed Trifluoromethanesulfenylation

Scheme 43. Nucleophilic Trifluoromethanesulfenylation

Both electrophilic and nucleophilic trifluoromethylation of sulfur-containing heteroaromatic compounds were reported for the preparation of corresponding trifluoromethyl sulfides (Scheme 46). Important electrophilic trifluoromethylating Scheme 46. Electrophilic and Nucleophilic Trifluoromethylation Heteroaryl iodines reacted with CuSCF3 or the CF3SCucomplex afforded the corresponding trifluoromethyl sulfides in good yields (Scheme 44).154,160,164 The reactivity was the same as the trifluoromethanesulfenylation of aryl iodines. This method is applied in the synthesis of different SCF3-substituted pyridines, quinoline, or thiophene. Transition-metal-catalyzed trifluoromethanesulfenylation of heteroaryl halides or heteroaryl boronic acid was also applied in the synthesis of different heteroaryl trifluoromethyl sulfides Scheme 44. Reaction of Heteroaryl Iodines with CuSCF3

reagent (Togni’s reagent, eq a, Scheme 46)81 and nucleophilic trifluoromethylating reagent (Ruppert-Prakash’s reagent, eq b, Scheme 46)88 were applied in these transformations. The radical trifluoromethylation of heteroaryl thiols is shown in Scheme 47. The reaction of 2-mercapto-6-(trifluoromethyl)pyrimidin-4-ol and CF3I in liquid ammonia under hv initiation Scheme 47. Radical Trifluoromethylation of Heteroaryl Thiols

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reaction of 1-hydroxypyridine-2(1H)-thione and (CF3CO2)2O in the presence of DMAP gave the corresponding ester, which was not isolated, but when irradiated in situ with a tungsten lamp, the product was afforded in excellent yield. The last method for the preparation of heteroaryl trifluoromethyl sulfides is the transformation from SCF3containing building blocks. As shown in Schemes 51−53,

afforded the corresponding product in moderate yield (eq a, Scheme 47).78 The radical reaction of pyridine-2-thiol proceeded well even without the use of UV irradiation (eq b, Scheme 47).221 The radical trifluoromethylation of diheteroaryl disulfides was also reported by different groups (Scheme 48).110,222−225 Trifluoromethanesulfenylated heteroaromatic compounds, such as indoles and pyrazoles, were conveniently synthesized by this method.

Scheme 51. Preparation of SCF3-Substituted Pyridine and Pyrazoles

Scheme 48. Radical Trifluoromethylation of Diheteroaryl Disulfides

various heteroaryl trifluoromethyl sulfides were prepared by construction of a heterocycle. This method has been rarely applied for the synthesis of aryl trifluoromethyl sulfides. Ponticello and co-workers reported the synthesis of 2bromo-3-(trifluoromethylthio)pyridine (eq a, Scheme 51).229 Condensation of 2-(trifluoromethylthio)acetonitrile with 1,1,3,3-tetramethoxypropane in the presence of Ac2O containing a catalytic amount of ZnC12 followed by cyclization with HBr-AcOH gave the desired product in low yield. Different 3SCF3-substituted pyrazoles were synthesized in moderate yields by Haas after condensing 3-(trifluoromethylthio)pentane-2,4dione with phenylhydrazines (eq b, Scheme 51).133 Another synthetic route for the preparation of SCF3-substituted pyrazoles was also developed by Haas through the 1,3-dipolar cycloaddition of 1,2-bis(trifluoromethylthio)ethyne and hydrazonoyl chloride (eq c, Scheme 51).129 The cyclized product was obtained in 81% yield. 3-SCF3-substituted 2(1H)- and 4(1H)-quinolinones were obtained by a cyclization reaction in concentrated sulfuric acid in moderate yields (eq a and b, respectively, Scheme 52).230

Reduction of the insecticide fipronil could produce fipronil sulfide, one of several active metabolites identified from fipronil (Scheme 49). The reported reduction systems ((CF3CO2)2O/ Scheme 49. Preparation of Fipronil Sulfide

Scheme 52. Synthesis of SCF3-Substituted Heteroaromatic Compounds NaI, eq a, Scheme 49226 and Me2H2NOTs/AcCl, eq b, Scheme 49)227 are similar to that used for the reduction of aryl trifluoromethanesulfoxides ((CF3SO2)2O, Scheme 38). In 1986, Barton and co-workers reported an unusual method for the synthesis of 2-SCF3-pyridine (Scheme 50).228 The Scheme 50. Preparation of 2-SCF3-Pyridine

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fluoride activation, afforded unprecedented S-CF3 ketene dithioacetals (eq a and b, Scheme 55).235,236 These reactions

Recently, Wu and co-workers reported an efficient synthesis of 4-SCF3-2H-benzo[e][1,2]thiazine 1,1-dioxides through the reaction of 2-(2-alkynyl)benzenesulfonamide with CF3SNHPh in the presence of BiCl3 (eq c, Scheme 52).231 The reaction of 2-amino-3-(trifluoromethylthio)benzoic acid and CF3COCl led to the formation of a cyclized product in quantitative yield (eq a, Scheme 53).232 SCF3-substituted

Scheme 55. Synthesis of Vinyl Trifluoromethyl Sulfides by Trifluoromethylation Reactions

Scheme 53. Synthesis of SCF3-Substituted Heteroaromatic Compounds

proceeded via a two-step process: thiophilic trifluoromethylation and β-elimination. The nucleofugal group could be fluorine (eq a, Scheme 55)235 or carbamoyloxy (eq b, Scheme 55).236 Electrophilic trifluoromethylation of Michler’s thioketone provides a new type of vinyl trifluoromethyl sulfide, which could be used as a dye (eq a, Scheme 55).177 Condensation of SCF3-containing building blocks, such as 2(trifluoromethylthio)acetonitrile (eq a, Scheme 56)229 and ethyl 2-(trifluoromethylthio)acetate (eq b, Scheme 56),237 with aldehydes gave different vinyl trifluoromethyl sulfides.

benzothiazole N-oxide was obtained through the reaction of 1chloro-2,6-dinitrobenzene with ethyl thioglycolate in the presence of NEt3 (eq b, Scheme 53).199 Condensation of 4(trifluoromethylthio)aniline with Meldrum’s acid trimethylortho-formate produced SCF3-substituted 4-hydroxyquinoline (eq c, Scheme 53).233 2.2.3. Synthesis of Vinyl Trifluoromethyl Sulfides. Vinyl trifluoromethyl sulfide can be prepared by the trifluoromethanesulfenylation of different substrates. The reaction of vinyl bromide with CuSCF3 gave the corresponding trifluoromethyl sulfides (eqs a and b, Scheme 54).129,234 For the

Scheme 56. Synthesis of Vinyl Trifluoromethyl Sulfides by Condensation Reactions

Scheme 54. Synthesis of Vinyl Trifluoromethyl Sulfides by Trifluoromethanesulfenylation Reactions

The last method for the preparation of vinyl trifluoromethyl sulfides is the transformation from other SCF3-containing compounds. Elimination of HCl from alkyl trifluoromethyl sulfides afforded the desired compound in moderate yields (eq a, Scheme 57).105,120 Haas and co-workers reported the synthesis of bis(trifluoromethylthio)ketene by dehydratization of the corresponding acetic acid (eq b, Scheme 57).238−241 2.2.4. Synthesis of Other C-SCF3 (sp2) Compounds. The reported synthetic methods of SCF3-enols are shown in Scheme 58. Orthoacetate reacted with two equiv of CF3SCl and afforded l,l-diethoxy-2,2-bis(trifluoromethylthio)ethane (eq a, Scheme 58).134 Billard and co-workers reported the reaction of alkyne, with CF3SNMePh, and TsONa under the activation of BF3·Et2O to produce SCF3-enols with different regioisomers (eq b, Scheme 58).76

gem-dibromovinyl substrate, both monosubstituted and bisubstituted products were obtained (eq b, Scheme 54).234 Coppercatalyzed trifluoromethanesulfenylation of vinyl boronic acids with nucleophilic or electrophilic trifluoromethanesulfenylating reagents was reported by Vicic (eq c, Scheme 54)173 and Shen (eq d, Scheme 54),141 respectively. Nucleophilic trifluoromethylation of dithioesters bearing a nucleofugal group in the α-position, using CF3TMS under 743


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reviewed the synthesis and application of these reagents.44 Herein, we simply summarized the synthetic methods in Schemes 61−63.

Scheme 57. Synthesis of Vinyl Trifluoromethyl Sulfides by Transformation Reactions

Scheme 61. Synthesis of S-Trifluoromethyl Diarylsulfonium Salts

Scheme 58. Synthesis of SCF3-Enols

In 1984, Yagupolskii and co-workers reported the first synthesis of S-trifluoromethyl diarylsulfonium salts by treating aryl trifluoromethyl sulfoxide with SF3+ SbF6− and subsequent reaction with electron-enriched arenes (eq a, Scheme 61).250 In 1998, Shreeve and co-workers developed a simpler synthetic method by treating phenyl trifluoromethyl sulfoxide with benzene or its derivatives in triflic anhydride (eq b, Scheme 61).251 In 2006, Blazejewski and Magnier presented a one-pot synthesis of Shreeve’s reagents, by reacting an aromatic compound with potassium triflinate in triflic anhydride (eq c, Scheme 61).252 The advantage of this method is the in situ formation of aryl trifluoromethyl sulfoxide. The synthetic methods of (trifluoromethyl)dibenzoheterocyclic salts are shown in Scheme 62. In 1993,

The reaction of amines and CF3SCl led to the formation of bis-SCF3-substituted enamines (eq a, Scheme 59).242−244 Scheme 59. Synthesis of SCF3-Enamines

Scheme 62. Synthesis of Cyclic S-Trifluoromethyl Sulfonium Salts

Triethylamine was converted to the corresponding product in 26% yield, while 42% yield was obtained starting from N,Ndicyclohexyl-N-ethylamine. SCF3-substituted enamines could also be prepared from enamines by the reaction of CF3SCl (eq b, Scheme 59)245,246 or in Shibata’s electrophilic trifluoromethanesulfenylation system (eq c, Scheme 59).143 S-Trifluoromethyl thioates (eq a, Scheme 60),166,247 as well as their analogues N-hydroxyimidothioates (eq b, Scheme Scheme 60. Synthesis of S-Trifluoromethyl Thioates, NHydroxyimidothioates, and Dithioates

Umemoto and co-workers developed these new electrophilic trifluoromethylating reagents.79,253,254 They could be synthesized either by fluorination of the corresponding sulfides with 10% F2/N2 in the presence of one equivalent of triflic acid (eq a, Scheme 62) or HBF4, or by cyclization of the corresponding sulfoxides with triflic anhydride (eq b, Scheme 62). Blazejewski and Magnier also reported a one-pot synthesis of Umemoto’s type reagents, by reacting the biphenyls with potassium triflinate in triflic anhydride (eq c, Scheme 62) in low yields.255

60)248 and dithioates (eq c, Scheme 59),114,249 respectively, could be prepared by halide substitution reactions of the corresponding chlorides in moderate yields. S-Trifluoromethyl diarylsulfonium salts are important electrophilic trifluoromethylating reagents. Our group has already 744


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In 2010, our group reported the synthesis of a new type of S(trifluoromethyl)sulfonium salts by cyclization of orthoethynylaryl trifluoromethyl sulfides with triflic acid in high yields (eq d, Scheme 62).256 Recently, Yagupolskii and co-workers proposed a new route for the synthesis of S-(trifluoromethyl)diarylsulfonium salts by transformation of the nucleophilic trifluoromethylating reagent, TMSCF3, into an electrophilic one (Scheme 63).177

Scheme 65. Synthesis of Trifluoromethanesulfoxides by Oxidation

Scheme 63. Synthesis of S-Trifluoromethyl Diarylsulfonium Salts

2.3. Synthesis of C-SCF3 (sp) Compounds

Alkynyl trifluoromethyl sulfides can be prepared either from alkynyl bromide or terminal alkynes (Scheme 64). The reaction

66).187,262,263 Nucleophilic trifluoromethylation of these substrates with TMSCF3 under the activation of different fluoride sources gave the desired products in good yields.

Scheme 64. Synthesis of Alkynyl Trifluoromethyl Sulfides

Scheme 66. Synthesis of Trifluoromethanesulfoxides by Trifluoromethylation

In 2001, Wakeselman and co-workers reported the synthesis of aryl trifluoromethyl sulfoxides by the reaction of simple aromatic compounds with triflinates salts in triflic acid medium (eq a, Scheme 67).264 Two years later, the same group reported

of alkynyl bromide and CuSCF3 gave the trifluoromethanesulfenylated products in low yields (eq a, Scheme 64).127 In 2012, Billard and co-workers reported the synthesis of alkynyl trifluoromethyl sulfides from terminal alkynes by deprotonation with butyllithium and then a reaction with their reagent (eq b, Scheme 64).55 One year later, they reported a modified method by base-catalyzed electrophilic trifluoromethylthiolation of terminal alkynes using their reagent.257 Shen’s group applied their trifluoromethylthiolated hypervalent iodine reagent to copper-mediated coupling reactions with terminal alkynes under basic conditions (eq c, Scheme 64).141 Qing’s group performed the oxidative trifluoromethylthiolation of terminal alkynes using their CF3TMS/S8 system (eq d, Scheme 64).258

Scheme 67. Synthesis of Aryl Trifluoromethanesulfoxides

3. SYNTHESIS OF C-SOCF3 COMPOUNDS Alkyl, aryl, and heteroaryl trifluoromethanesulfoxides can be prepared by oxidation of corresponding trifluoromethyl sulfides (Scheme65). Different oxidation systems, such as H2O2,105,223,259 MCPBA,79,104,159,227 CF3CO3H,105 Oxone,105 NaIO 4 , 260 trichloroisocyanuric acid (TCCA), 198 and MoO2Cl2(OPPh3)2,261 have been successfully applied in these transformations. Another widely used method for the preparation of alkyl and heteroaryl trifluoromethanesulfoxides is trifluoromethylation of the corresponding sulfinyl halides or sulfinic esters (Scheme

another synthetic method for aryl trifluoromethyl sulfoxides by the rearrangement of aryl triflinates in the presence of AlCl3 (eq b, Scheme 67).265 The ortho-trifluoromethanesulfinyl phenols and/or para-trifluoromethanesulfinyl phenols were obtained by this thia-Fries rearrangement process. Larock and Liu reported an intermolecular S−N addition of trifluoromethanesulfinamides to arynes for the preparation of ortho-trifluoromethanesulfinyl anilines (eq c, Scheme 67).266 745


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The trifluoromethanesulfinylation of N-methylpyrrole using Langlois’ CF3SO2Na/POCl3 system (eq a, Scheme 68)267 or

Scheme 70. Synthesis of Alkyl Triflones by Electrophilic triflylation

Scheme 68. Synthesis of Heteroaryl Trifluoromethanesulfoxides

The rearrangement of trifluoromethanesulfinates gave the corresponding triflones in good yields (Scheme 71).301,310 A polar solvent, such as hexamethylphosphoramide, is necessary for this rearrangement reaction.

with 1-(trifluoromethylsulfinyl)pyrrolidine-2,5-dione (eq b, Scheme 68)268 gave 1-methyl-2-(trifluoromethylsulfinyl)-1Hpyrrole in good yields. Trifluoromethanesulfinyl-substituted furans could be prepared by a cyclization reaction of alkynyl amines and alkynyl trifluoromethanesulfones (eq c, Scheme 68).269

Scheme 71. Synthesis of Alkyl Triflones by Rearrangement Reaction

4. SYNTHESIS OF C−SO2CF3 COMPOUNDS The trifluoromethanesulfonyl (SO2CF3, triflyl, Tf) group exhibits unique properties. 23,270−274 In particular, it is considered to be the strongest electron-withdrawing group with high lipophilicity. A number of methodologies have been developed for the synthesis of SO2CF3-containing compounds, which are frequently used as structural units in bioactive compounds,183,193,275−282 catalysts or ligands,283−291 and advanced functional materials.292−299

The addition reaction of olefins with triflone-containing reagents, such as CF3SO2F, CF3SO2SPh, and CF3SO2SePh, provides an efficient method for the preparation of various alkyl triflones (eq a, Scheme 72).311,312 Petrov and co-workers reported the reaction of quadricyclane and CF3SO2Cl leading to a mixture of isomeric nortricyclanes in good yields (eq b, Scheme 72).313

4.1. Synthesis of C−SO2CF3 (sp3) Compounds

4.1.1. Synthesis of Alkyl Trifluoromethanesulfones (Triflones). Alkyl triflones may be formed by nucleophilic substitution of primary halides or tosylates by a triflinate salt, such as CF 3 SO 2 Na, 276,300 CF 3 SO 2 K, 271,301−303 and nBu4NSO2CF3304 (Scheme 69). Because of the low nucleophil-

Scheme 72. Synthesis of Alkyl Triflones by Addition Reaction

Scheme 69. Synthesis of Alkyl Triflones by Nucleophilic Triflylation

Triflone-containing building blocks can be transformed for the preparation of alkyl triflones (Scheme 73). The Diels− Alder reaction of vinyl triflones was used for the preparation of different cyclic adducts (eq a-c, Scheme 73).128,314,315 In 2009, the Deng group reported the catalytic enantioselective conjugate additions of a wide range of Michael donors to α,β-unsaturated triflones (eq d, Scheme 73).316 The desired products were obtained in excellent enantioselectivities/ diastereoselectivities and high yields. Alkyl triflones could be prepared from the corresponding sulfides by an oxidation reaction in good yields (Scheme 74).

icity of a rather stable triflinate anion, the reaction is normally performed at high temperature and sometimes iodide ion catalysis is needed to accelerate the reaction rate. The reaction of alkyl metallic species (organolithium or Grignard reagent) and electrophilic triflylation reagents, such as CF3SO2F, (CF3SO2)2O and PhN(SO2CF3)2, provides another convenient method for the preparation of alkyl triflones (eqs a and b, Scheme 70).305−308 Trifluoromethyl triflone could be prepared in a similar way by the reaction of triflyl chloride or phenyl triflate and TMSCF3 under the activation of the fluoride anion (eq c, Scheme 70).262,309 746


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Scheme 73. Synthesis of Alkyl Triflones by SO2CF3Containing Building Blocks

Scheme 76. Synthesis of Benzyl, Allyl, and Propargyl Triflones by Nucleophilic Triflylation

Scheme 77. Synthesis of Allyl and Benzyl Triflones by Electrophilic Triflylation

Different oxidation systems, such as CrO3,60 KMnO4,86 H2O2,90,317 and H2O2/H2WO4,303 were applied in this type of reaction.

Scheme 78. Synthesis of Allyl Triflone by Addition Reaction

Scheme 74. Synthesis of Alkyl Triflones by Oxidation Reaction

triflones was reported by Billard and Langlois in 1999 (eq b, Scheme 78).312 The 1,4-addition of 2,3-dimethy-l,3-butadiene with CF3SO2SePh gave the adducts in good yields. The rearrangement of trifluoromethanesulfinates could also be used to prepare benzyl and allyl triflones (Scheme 79). Scheme 79. Synthesis of Benzyl and Allyl Triflones by Rearrangement Reaction

The last method for the preparation of alkyl triflone is fluorination (Scheme 75).318 Lagow reported the reaction of elemental fluorine with dimethyl Sulphone, giving the fluorinated product in 34% yield. Scheme 75. Synthesis of Alkyl Triflones by Fluorination Reaction

Benzyl trifluoromethanesulfinate could be conveniently converted to benzyl triflone (eq a, Scheme 79).327 Braverman and co-workers reported the [2,3]-sigmatropic rearrangement of propargyl trifluoromethanesulfinates, followed by the nucleophilic addition of EtOH, and for the preparation of allyl triflones (eq b, Scheme 79).328 Soon after, the same group investigated the [2,3]-sigmatropic rearrangement of allyl trifluoromethanesulfinates, which strongly depended on substitution (eq c, Scheme 79).329 Another type of rearrangement reaction is anion triflyl rearrangement starting from aryl or heteroaryl triflates (Scheme 80). Beccalli and co-worker reported the 1,5-migration of triflyl group for the synthesis of allyl triflones (eq a, Scheme 80).330 The Ortar group recently reported a base-catalyzed rearrangement for the preparation of benzyl triflone (eq b, Scheme 80).331

4.1.2. Synthesis of Benzyl, Allyl, and Propargyl Triflones. Nucleophilic triflylation was widely used for the preparation of different benzyl triflones,284,286,319−324 allyl triflones,304 as well as propargyl triflones128 (Scheme 76). Besides the common triflinate salts, the combination of triflates with amines could be used to generate the triflinate anion (eq b, Scheme 76).323,324 The reaction of allyl or benzyl magnesium chlorides with (CF3SO2)2O gave the corresponding products in good yields (Scheme 77).303,308,325 In 1995, the Fuchs group reported the facile synthesis of allyl triflones via the radical-mediated atom-transfer addition of iodomethyl triflone to acetylenes (eq a, Scheme 78).326 Another type of addition reaction for the preparation of allyl 747


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diastereoselectivities and in excellent enantioselectivities (eq c, Scheme 82).335,336 4.1.3. Synthesis of Bis(triflyl) and Tris(triflyl)alkanes. Bis(triflyl)alkanes can be prepared by two-step triflylation reactions (eq a, Scheme 83).307,337 Nuclophilic triflylation followed by electrophilic triflylation was also applied for the synthesis of bis(triflyl)alkanes (eq b, Scheme 83).284,286,310,322

Scheme 80. Synthesis of Allyl and Benzyl Triflones by Anion Triflyl Rearrangement

Scheme 83. Synthesis of Bis(triflyl)alkanes

Allyl triflones can be prepared by the transformation of other triflone-containing compounds (Scheme 81). The Fuchs group Scheme 81. Synthesis of Allyl Triflones by Transformation from Other SO2CF3-Containing Compounds

Another important synthetic method is the transformation from bis(triflyl)-containing building blocks (Scheme 84). Scheme 84. Synthesis of Bis(triflyl)alkanes

reported the synthesis of allyl triflones from γ-iodo triflones (eq a, Scheme 81).326 Under oxidative conditions, the iodide moiety was converted into a putative iodoso intermediate, which underwent 1,2-elimination affording the desired compound. The addition reaction of triflone-containing l,3butadiene could give the cyclic allylic triflones in good yields (eq b, Scheme 81).332 Simple benzyl triflones are normally used as building blocks for the preparation of complex compounds (Scheme 82). 1-

Taguchi and co-workers reported the reaction of electron-rich arenes with 1,1,3,3-tetrakis(triflyl)propane giving the bis(triflyl)ethylated products in good to excellent yields (eq a, Scheme 84).290 The reaction proceeded via the active intermediate Tf2CCH2, which was generated in situ. The same group also reported the three component reaction of Tf2CH2, aldehydes, and 1,3-dienes for the preparation of gembis(triflyl)cyclohexenes in good to excellent yields (eq b, Scheme 84).338 The addition reactions of bis(triflyl)alkadienes were applied for the synthesis of bis(triflyl)alkadienes (eq c, Scheme 84).339,340 In 1993, Zhu reported the synthesis of aryl bis(triflyl)methanes by the pyrolysis of arenediazonium bis(triflyl)methides in high yields (eq a, Scheme 85).341 Surprisingly, Yamamoto and co-workers could not repeat this reaction. An oxygen phenylation product, and not a carbon phenylation product, was obtained (eq b, Scheme 85).342 Halonium ylides could be prepared from bis(triflyl)methane (Scheme 86). Chen and Zhu reported the synthesis of phenyliodonium bis(triflyl)methide by the reaction of bis(triflyl)methane and diacetoxyiodobenzene in good yield (eq a, Scheme 86).343,344 Ochiai and co-workers developed rhodiumcatalyzed transylidation of aryliodonium ylides (eq b, Scheme 86).345 The reaction of phenyliodonium bis(triflyl)methide with a large amount of a substituted iodobenzene under the catalysis of rhodium(II) acetate afforded a substituted aryliodonium ylide in a good yield. Bromonium ylides were synthesized by the Ochiai group following the reaction of

Scheme 82. Transformation Reactions of Simple Benzyl Triflones

Phenyl-1-triflyl cyclopropane was prepared by Zhu from benzyl triflone and 1,2-dibromoethane (eq a, Scheme 82).333 Reactions of the potassium salts of triflyl stabilized carbanions with benzhydrylium tetrafluoroborates were reported by the Mayr group (eq b, Scheme 82).334 Nakamura and co-workers developed the catalytic asymmetric reactions of lithiated benzyl trifluoromethyl sulfones with various aldehydes in good 748


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Scheme 85. Transformation from Arenediazonium Bis(triflyl)methides

Scheme 88. Synthesis of Pyridinium and Triphenylphosphonium Ylides As Well As Other Ammonium Salts

Scheme 86. Synthesis of Halonium Ylides

Scheme 89. Synthesis of Bis(triflyl)alkide salts

Na,352 K,353 Zr,354 Ru,355 Os,356 Ir,357,358 Pt,359−362 Sb,363 and Bi,364 were involved in this type of reaction. Naumann and coworkers reported an unusual [Xe(2,6-F2C6H3)]CH(SO2CF3)2 complex, which was unstable and was only characterized by 19F NMR spectroscopy.365 The synthesis of tris(triflyl)methane and tris(triflyl)methide salts is shown in Scheme 90. Double deprotonation of

3

bis(triflyl)methane and p-trifluoromethylphenyl(difluoro)-λ bromane (eq c, Scheme 86).346 The same group also reported the synthesis of chloronium ylides by the reaction of bromonium ylide and chlobenzenes in low yields (eq d, Scheme 86).347,348 Zhu and Li reported the synthesis of sulfonium ylide from phenyliodonium bis(triflyl)methide and dimethyl sulfide under irradiation in good yield (eq a, Scheme 87).349 After storage for two months in a flask at room temperature, sulfonium ylide was completely oxidized to the sulfoxonium yilde (eq b, Scheme 87).350

Scheme 90. Synthesis of Tris(triflyl)methane and Tris(triflyl)methide salts

Scheme 87. Synthesis of Sulfonium and Sulfoxonium Yildes

bis(triflyl)methane with tert-butyllithium followed by the addition of triflic anhydride gave lithium tris(triflyl)methide, which could be converted to other derivatives.353,366−369 4.1.4. Synthesis of α-Triflyl Carbonyl and Sulfonyl Compounds. α-Triflyl carbonyl compounds can be synthesized by electrophilic triflylation reactions (Scheme 91). Different electrophilic triflylation reagents, such as CF3SO2F, CF3SO2Cl, (CF3SO2)2O, and PhN(SO2CF3)2 were applied for the synthesis of various α-triflyl carbonyl compounds (eq a and b, Scheme 91).139,370−372 In 1979, Kobayashi and co-workers reported the reaction of enamine with CF3SO2OCF3 providing the products in low yields (eq c, Scheme 91).373,374 Nucleophilic triflylation reactions were also applied in the synthesis of α-triflyl carbonyl compounds (Scheme 92).319,375−377 The reaction of α-halo carbonyl compounds with CF3SO2Na gave the desired compounds in good yields.

Zhu and Li also reported the irradiation of phenyliodonium bis(triflyl)methide with pyridine or triphenylphosphine giving the corresponding pyridinium or triphenylphosphonium ylides in good yields (eq a and b, Scheme 88).349 1-Aryl-2,2bis(triflyl)ethylenes reacted with pyridine gave the corresponding pyridinium salts in good yields (eq c, Scheme 88).339 Recently, Yanai and Taguchi reported the reaction of Nalkylated anilines with Tf2CHCH2CHTf2 affording corresponding bis(triflyl)ethylated products in a para-selective manner (eq d, Scheme 88).291 The obtained products form a unique zwitterion structure. Other bis(triflyl)alkide salts were also synthesized from bis(triflyl)alkanes (Scheme 89). Various metals, such as Li,351 749


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Scheme 91. Electrophilic Synthesis of α-Triflyl Carbonyl Compounds

three-component condensation reaction of 1,2-dimethyl-1Hindole, 2-(triflyl)-1-phenylethanone, and paraformaldehyde giving the indole derivative (eq b, Scheme 94).381 Recently, our group reported the reaction of α-triflyl phenyl ketone and phenyliodine(III) diacetate (PIDA) for the synthesis of a triflyl hypervalent iodonium ylide, which was used as a novel electrophilic-type trifluoromethylthiolation reagent (eq c, Scheme 94).143 Bis-metalation of phenylsulfonylmethyl triflone produced a geminal dianion which could be dialkylated affording different α-phenylsulfonyl triflones (eq a, Scheme 95).302 Hendrickson

Sometimes catalytic iodides were added to accelerate the reaction rate.

Scheme 95. Synthesis of α-Sulfonyl Triflones

Scheme 92. Nucleophilic Synthesis of α-Triflyl Carbonyl Compounds

and co-workers developed α-triflyldimethylsulfone as a nucleophilic synthon reagent. The polyalkylation of the two carbons were clean and regiospecific, often amenable to a onepot operation (eq b, Scheme 95).382−384

Another widely used method for the synthesis of α-triflyl ketones is the transformation from alkynyl triflones (Scheme 93).378,379 The triple bond in alkynyl triflones shows

4.2. Synthesis of C−SO2CF3 (sp2) Compounds

4.2.1. Synthesis of Aryl Triflones. Various synthetic methods for the synthesis of aryl triflones are summarized in Scheme 96. For both trifluoromethanesulfonylation and trifluoromethylation reactions, electrophilic and nucleophilic approaches have been developed. Other methods, such as functionalization, fluorination, oxidation, rearrangement, and decomposition are also applied for the synthesis of aryl triflones. The Friedel−Crafts triflylation of aromatic substrates with (CF3SO2)2O under the activation of AlCl3 was reported by Hendrickson (eq a, Scheme 97).305 Only a narrow range of mildly activated aromatic substrates could be used for Friedel− Crafts triflylation. Aryl Grignard reagents reacted with (CF3SO2)2O gave corresponding triflones in low yields (eq b, Scheme 97).308 Nucleophilic triflylation reactions were developed recently (Scheme 98). The reaction of N-arylsulfonyl-1,4-benzoquinone monoimines with CF3SO2Na gave the 1,4-addition products in good yields (eq a, Scheme 98).385 Shekhar and co-workers reported a convenient method for the preparation of aryl triflones from the reactions of diaryliodonium salts with CF3SO2Na in the presence of copper catalysts (eq b, Scheme 98).386 Nucleophilic trifluoromethylation of arenesulfonyl halides or arenesulfonates gave the corresponding aryl triflones in high yields (Scheme 99). Different reaction systems such as TMSCF3/TASF (eq a, Scheme 99),187,387 TMSCF3/CsF (eq b, Scheme 99),263 and CF3CO2Na/CuI (eq c, Scheme 99)388 were applied for these transformations. Electrophilic trifluoromethylation of arenesulfinate sodium salt with diaryltrifluoromethylsulfonium salts produced the corresponding triflones (eq a, Scheme 100).177 Wen and coworkers reported a copper-catalyzed method for the trifluoromethylation of arenesulfinates with Togni’s reagent affording aryltriflones in moderate to good yields (eq b, Scheme 100).389

Scheme 93. Synthesis of α-Triflyl Ketones

pronounced reactivity toward nucleophiles. The α-triflyl ketones were conveniently prepared by the reaction of alkynyl triflones with acetone and water in high yields. α-Triflyl ketones are useful building blocks for the synthesis of other derivatives (Scheme 94). A series of stable arsonium ylides and sulfur ylides were simply synthesized from triflyl diazocarbonyl compounds in the presence of rhodium catalyst (eq a, Scheme 94).380 Zhu and co-workers reported a one-pot Scheme 94. Transformation of α-Triflyl Ketones

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Scheme 96. Various Methods for the Synthesis of Aryl Triflones

Scheme 97. Electrophilic Aromatic Triflylation

Scheme 100. Synthesis of Aryl Triflones by Electrophilic Trifluoromethyaltion

Scheme 98. Nucleophilic Aromatic Triflylation

Scheme 101. Synthesis of Aryl Triflones by Rearrangement Reaction

Scheme 99. Synthesis of Aryl Triflones by Nucleophilic Trifluoromethyaltion

CsF afforded the rearrangement product in low yield (eq b, Scheme 101).398,399 In 1982, Umemoto and Sekiya reported an interesting reaction for the preparation of aryl triflones (Scheme 102).200 Trifluoromethylazosulfonylarenes decomposed under thermal conditions with the release of nitrogen to produce the corresponding aryl triflones in about 40% yield. Aryl triflones could also be prepared from SO2CF3containing building blocks (Scheme 103). The [3 + 2] cycloaddition reaction of a substituted cyclopropenone acetal

Anionic thia-rearrangement of aryl triflates has been widely used in the preparation of various aryl triflones (Scheme 101). The first anionic thia-Fries rearrangement was only fairly recently reported by Lloyd-Jones in 2003.390 The rearrangement was observed only for some electron-poor naphthyl and a few chlorinated phenyl systems. Recently, Lloyd-Jones’ group and Butenschön’s group applied this rearrangement reaction to the synthesis of various o-hydroxyaryl triflones (eq a, Scheme 101).288,289,391−397 Mayabe and co-workers reported that treatment of 3-(trimethylsilyl)naphthalen-2-yl triflate with

Scheme 102. Synthesis of aryl triflones from trifluoromethylazosulfonylarenes

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Scheme 103. Transformation from SO2CF3-Containing Building Blocks

Scheme 105. Synthesis of Phenyl Triflone by Fluorination Reaction

4.2.2. Synthesis of Heteroaryl Triflones. The reported methods for direct electrophilic triflylation of heteroaromatic compounds are shown in Scheme 106. Our group developed a Scheme 106. Synthesis of Heteroaryl Triflones by Direct Triflylation

to phenyl(trifly1)acetylene gave triflyl-substituted cyclopentadienone acetals in moderate yields (eq a, Scheme 103).400 The further reaction of triflyl-substituted cyclopentadienone acetal and an equimolar amount of phenyl(trifly1)acetylene gave the corresponding benzene derivative as a single regioisomer (eq b, Scheme 103).401 The Diels−Alder reaction of tetraphenylcyclopentadienone and phenyl(trifly1)acetylene gave the adduct in 88% yield (eq c, Scheme 103).402 Recently, Taguchi and coworkers reported the treatment of dienes with activated MnO2 to produce the corresponding aryl triflones in high yields (eq d, Scheme 103).338 Another important method for the preparation of aryl triflones is the oxidation reaction of aryl trifluoromethyl sulfides (Scheme 104). Different oxidation systems, such as H 2 O 2 , 100,169, 403 MCPBA, 159 methyl(trifluoromethyl)dioxirane,404 H2Cr2O7,154 CrO3,405,406 CrO3/H5IO6,407 and NaIO4/RuCl3408 were applied to achieve aryl triflones. The last method for the preparation of aryl triflones is the fluorination reaction (Scheme 105).409 Kaneko and co-workers reported the reaction of fluoromethyl phenyl sulfoxide with molecular fluorine (5% F2/N2) affording phenyl triflone in low yield.

convenient synthesis of indole triflones by treating indoles with Tf2O/TTBP (eq a, Scheme 106).410 The desired products were obtained in good to excellent yields. Isoxazole triflone could be prepared by a halogen−lithium exchange reaction of 4iodoisoxazole followed by direct triflylation by using Tf2O; however, the yield was poor at 9% (eq b, Scheme 106).411 In 2010, Bertrand reported the synthesis of 4-triflyl imidazole-2ylidene by direct triflylation of 4,5-unsubstituted imidazol-2ylidene (eq c, Scheme 106).412 The rearrangement of heteroaryl triflates provides another synthetic method to produce various heteroaryl triflones (Scheme 107). In 2006, Bonesi and co-workers reported the photo-Fries rearrangement of 9H-carbazol-2-yl triflate giving ortho-rearranged products (eq a, Scheme 107).413 Our group reported the LDA (lithium diisopropylamine)-mediated anionic thia-Fries rearrangement for the synthesis of heteroaromatic triflones including oxindole, pyrazolone, pyridine, and quinoline triflones (eq b, Scheme 107).414 An unusual NaH-mediated remote anionic 1,5-thia-Fries rearrangement reaction was developed by our group (eq c, Scheme 107).415 This method provides an efficient approach for the regioselective synthesis of 2-(2-hydroxyphenyl)-3-indole triflones. An oxidation reaction was applied for the synthesis of various heteroaryl triflones (Schemes 108 and 109). 2[(Trifluoromethyl)thio]pyridine was converted into the corresponding triflone by oxidation with H2Cr2O7 in 60% yield (eq a, Scheme 108).154 The oxidation system of CrO3/H2SO4 was used for the synthesis of 2,3,5,6-tetrafluoro-4-triflylpyridine (eq b, Scheme 108)219 and 2,3,4,5-tetra(triflyl)pyrrole (eq c, Scheme 108),416 respectively. A series of 4,5-diaryl-2-triflyl1H-imidazoles were conveniently prepared by MCPBA oxidation (eq d, Scheme 108).217 Various triflyl-substituted furans and thiophenes were prepared under oxidative conditions (Schemes 109). Different

Scheme 104. Synthesis of Aryl Triflones by Oxidation Reactions

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Propargyl triflones are important building blocks for the synthesis of different heteroaryl triflones (Schemes 110).

Scheme 107. Synthesis of Heteroaryl Triflones by Rearrangement Reactions

Scheme 110. Synthesis of Heteroaryl Triflones from Propargyl Triflones

Scheme 108. Synthesis of Heteroaryl Triflones by Oxidation Reactions

Kawashima and co-workers reported a [2 + 2] reaction for the synthesis of pentacoordinate 1,2λ5-azaphosphetine (eq a, Scheme 110).417 The reaction of phenyl(trifly1)acetylene and N-substituted-N-formylglycines in Ac2O afforded 3-triflylpyrroles in moderate yields (eq b, Scheme 110).418 The 1,3-dipolar addition reaction of diazomethane and ethyldiazoacetate with phenyl(trifly1)acetylene was also reported (eq c, Scheme 110).419 The two isomers of SO2CF3-containing pyrazoles were prepared in moderate yields. Recently, our group reported the regioselective synthesis of pyrazole triflones by 1,3-dipolar cycloaddition of triflyl alkynes and hydrazonoyl chloride (eq d, Scheme 110).420 Pyrazolo[5,1-a]isoquinoline triflones were also regioselectively synthesized for the first time via tandem 1,3-dipolar cycloaddition/oxidative aromatization between triflyl alkynes and C,N-cyclic azomethine imines (eq e, Scheme 110).420 A general method for the preparation of 2-aryl-3triflylpyrroles has been developed by Barnes and Ward. The condensation of α-triflyl ketones with aminoacetaldehyde diethyl acetal afforded enamine intermediates, which were treated with CF3CO2H affording cyclized products (eq a, Scheme 111).375 Our group reported a convenient synthesis of isoxazole triflones from α-triflyl ketones and imidoyl chlorides in the presence of triethylamine (eq b, Scheme 111).411 The Knoevenagel condensation reaction of salicyaldehyde with ethyl(triflyl)acetate gave the vinyl triflone intermediate, which then underwent intramolecular cyclization to afford a coumarin derivative (eq a, Scheme 112).421 Recently, our group reported a one-pot synthesis of 3-triflyl-2-hydroxy-2H-chromenes (eq b, Scheme 112) and 3-triflyl-2H-chromen-2-one (eq c, Scheme 112).422 The reactions proceeded via a rearrange-

Scheme 109. Synthesis of Heteroaryl Triflones by Oxidation Reactions

oxidants, such as MCPBA (eq a, Scheme 109),211 KMnO4 (eq b, Scheme 109),269 and H2O2 (eq c and d, Scheme 109),212 were used to achieve these transformations. 753


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Scheme 111. Synthesis of Heteroaryl Triflones from α-Triflyl Ketones

Scheme 114. Synthesis of SO2CF3-Containing Heterocycles

Scheme 112. Synthesis of 3-Triflyl-2-hydroxy-2H-chromenes and 3-Triflyl-2H-chromen-2-one

ment/substitution/cyclization route giving the desired products in moderate yields. Triflyl substituted anilines are useful building blocks for the synthesis of various heteroaryl triflones (Scheme 113). Triflyl

affording a dihydropyran derivative in excellent yield (eq c, Scheme 114).430 Starting from SO2CF3-containing α,βunsaturated ketones, Zhang’s group prepared triflyl substituted trans-2,3-dihydrofurans by the reaction of arsonium bromides (eq d, Scheme 114).431 Liu and Wang reported a dipolar cycloaddition reaction of allenyl triflones to nitrones (eq e, Scheme 114).432 Unusual zwitterionic cycloadducts were obtained in good yields due to the strong electron-withdrawing effect of the triflyl group. The reaction of 4-nitro-6triflylbenzofuroxan with cyclopentadiene proceeded stereoselectively to afford a single product in quantative yield (eq f, Scheme 114).433 4.2.3. Synthesis of Vinyl and Allenyl Triflones. In 2004, Ochiai and co-workers reported a novel synthesis of vinyl triflones (Scheme 115).434 The reaction of 1-alkynyl[p(trifluoromethyl)phenyl](tetrafluoroborato)-λ3-bromanes with sodium trifluoromethanesulfinate gave a 1-triflylcyclopentene derivative in 91% yield. The Michael addition of trifinate anion and subsequent elimination of p-(trifluoromethyl)bromobenzene gave reactive alkylidene carbene A. An intramolecular 1,5-carbon−hydrogen insertion in carbenes A gave

Scheme 113. Synthesis of Heteroaryl Triflone from Triflyl Substituted Anilines

substituted benzimidazole derivatives were readily prepared from 4-triflylbenzene-1,2-diamine (eq a and b, Scheme 113).423−425 The cyclocondensation reaction of 4-triflylaniline and malonate gave 4-hydroxy-3-phenyl-6-triflylquinolin-2(1H)one in 71% yield (eq c, Scheme 113).426,427 Different methods for the synthesis of SO2CF3-containing heterocycles are shown in Scheme 114. The reaction of γbutyrolactone with LiHMDS followed by PhNTf2 gave triflylsubstituted dihydrofuran in 43% yield (eq a, Scheme 114).428 Urabe and co-workers reported a novel Rh-catalyzed isomerization reaction from benzyl alkynyl ether to a dihydropyran derivative in good yield (eq b, Scheme 114).429 Zhu and coworkers reported the hetero Diels−Alder reaction of SO2CF3containing α,β-unsaturated ketone with electron-rich olefin

Scheme 115. Synthesis of Vinyl Triflones

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reaction affording the desired products in good yields. Taguchi and co-workers reported a thermal desulfonylation reaction giving triflyl-substituted diene in good yields (eq c, Scheme 118).338 Cyclic and acyclic allyl triflones were isomerized under basic conditions affording the corresponding vinyl triflones (Scheme 119).301,304 The vinyl triflones should be more stable than allyl triflones due to the conjugation.

triflyl substituted cyclopentene, while 1,2-migration of the triflyl group gave a rearrangement product, 1-alkynyl triflone. Braverman and co-workers reported a [2,3]-sigmatropic rearrangement of propargylic trifluoromethanesulfinates affording the corresponding allenyl triflones (Scheme 116).328,329,435 Scheme 116. Synthesis of Allenyl Triflones

Scheme 119. Synthesis of Vinyl Triflones from Allyl Triflones An anionic triflyl rearrangement was developed to synthesize different vinyl triflones (Scheme 117). The 1,3-migration of the Scheme 117. Synthesis of Vinyl Triflones by Rearrangement Reaction Another method for the preparation of vinyl triflones is the addition reaction of alkynyl triflones (Scheme 120).378,379,402,419,438−441 Typical examples include a copperScheme 120. Synthesis of Vinyl Triflones by the Addition Reaction

triflyl group in the iron-diene complex gave the rearrangement product in 43% yield (eq a, Scheme 117).436 Treatment of semicyclic 3-trifloxy propene iminium triflate with a polymersupported tertiary amine gave 3-triflyl-1,4,5,6-tetrahydropyridines in good yields (eq b, Scheme 117).437 Recently, our group reported the convenient synthesis of vinyl triflones by 1,5-triflyl migration of various ortho-gem-dibromovinylphenyl triflates (eq c, Scheme 117).422 Vinyl triflones could be prepared by the transformation from alkyl triflones (Scheme 118). Langlois and Billard developed the synthesis of vinyl triflones from β-sulfenyl or selenyl triflones by two different methods (eq a and b, Scheme 118).312,315 Both of the oxidants and base led to an elimination

mediated stereoselective reduction reaction,439 a stereo- and regiospecific addition reaction of lithium iodide,440 the Diels− Alder addition reaction,419 and others. The condensation reaction is widely used in the synthesis of various vinyl triflones (Scheme 121).306,314,339,340 Aromatic and aliphatic aldehydes, as well as α,β-unsaturated aldehydes, reacted with SO2CF3-containing building blocks affording the corresponding products. Other reactions of SO2CF3-containing building blocks are shown in Scheme 122. Zhu reported the synthesis of 1,1bis(alkylmercapto)-2-triflyl ethylenes by the condensation of methyl triflone with carbon disulfide, followed by subsequent

Scheme 118. Synthesis of Vinyl Triflones from Alkyl Triflones

Scheme 121. Synthesis of Vinyl Triflones by the Condensation Reaction

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Scheme 122. Synthesis of Vinyl Triflones from SO2CF3Containing Building Blocks

Scheme 125. Synthesis of Trifluoromethylated Sulfilimines

Scheme 126. Synthesis of Bis(trifluoromethy1)sulfimide and Bis(trifluoromethy1)-N-alkylsulfimides alkylation (eq a, Scheme 122).442 Hanack and co-workers reported the reaction of bis(triflyl)methane and diisopropylcarbodiimide giving 2,2-bis(isopropylamino)-1,1-bis(triflyl)ethene in 64% yield (eq b, Scheme 122).443 Yamamoto and co-workers reported the pyrolysis of benzenediazonium bis(triflyl)methide in acetonitrile to give a novel acetonitrileinserted compound, PhNH(Me)CC(SO2CF3)2, quantitatively (eq c, Scheme 122).342 In this reaction, bis(triflyl)methide anion reacted with an ammonium ion intermediate, which was generated by the nucleophilic attack of the nitrogen atom in acetonitrile until the phenyl cation formed. The last method for the synthesis of vinyl triflone is the oxidation reaction (Scheme 123).128 Hanack and Massa reported the reaction of propargyl trifluoromethyl sulfide with 4-nitrobenzoperoxoic acid affording the corresponding allenyl triflone.

bis(trifluoromethy1)sulfur difluoride with ammonia in the presence of benzylamine (eq a, Scheme 126), while bis(trifluoromethy1)-N-alkylsulfimides were directly synthesized from bis(trifluoromethy1)sulfur difluoride with primary amines (eq b, Scheme 126). The oxidation of trifluoromethylated sulfilimines with different oxidation systems, such as NaIO4/RuCl3 and KMnO4, was used to prepare trifluoromethylated sulfoximines (Scheme 127).159,445,450−452 Scheme 127. Synthesis of Trifluoromethylated Sulfoximines from Sulfilimines

Scheme 123. Synthesis of Allenyl Triflone

4.3. Synthesis of C−SO2CF3 (sp) Compounds

Alkynyl triflones are normally prepared by the electrophilic triflylation of alkynes (Scheme 124).378,402,419,440,444 Treatment

Trifluoromethylated sulfoximines could also be prepared from the corresponding sulfoxides (Scheme 128).104,453−456 Treatment of trifluoromethylated sulfoxides with NaN3/H2SO4 gave the desired products in good yields.

Scheme 124. Synthesis of Alkynyl Triflones

Scheme 128. Synthesis of Trifluoromethylated Sulfoximines from Sulfoxides

of the substrates with bases, such as n-BuLi and Na, gave the metal salts, which then reacted with (CF3SO2)2O giving the corresponding alkynyl triflones in good yields. In 2011, Bolm and co-workers reported another synthetic method to synthesize trifluoromethylated sulfoximines (Scheme 129).457,458 Treatment of sulfonimidoyl fluorides with a combination of TMSCF3 and TBAF gave the desired products in moderate yields.

5. SYNTHESIS OF C−S(O)X(NR)CF3 COMPOUNDS The synthesis of trifluoromethylated sulfilimines is shown in Scheme 125.159,299,445,446 Treatment of aryl trifluoromethyl sulfoxides with Tf2O and nitriles or triflic amide gave a wide range of sulfilimines in good yields. Shreeve and co-workers developed another method for the synthesis of bis(trifluoromethy1)sulfimide and bis(trifluoromethy1)-N-alkylsulfimides (Scheme 126).447−449 Bis(trifluoromethyl)sulfimide was prepared by the reaction of

6. CONCLUSION As emphasized in this review, the introduction of SOnCF3 groups into organic compounds drastically changes their biological and physicochemical properties. Although most of 756


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Scheme 129. Synthesis of Trifluoromethylated Sulfoximines from Sulfonimidoyl Fluorides

supervision of Professor Feng-Ling Qing at the Shanghai Institute of Organic Chemistry (SIOC), Chinese Academy of Sciences in 2008. After spending 16 months as a postdoctoral associate with Dr. Dominique Cahard at the University of Rouen, he joined Professor Norio Shibata’s group as a JSPS postdoctoral associate at the Nagoya Institute of Technology in 2010. He returned to SIOC at the end of 2013 working in Professor F.-L. Qing’s group. His research interests are trifluoromethylation and trifluoromethylthiolation.

the methods for the synthesis of C−SOnCF3 compounds introduced here are not asymmetric reactions, another effect of fluorinated compounds on chiroptical properties, the enhanced magnitude of the self-disproportionation of enantiomers, should be concerned in the case of chiral fluorinated compounds.459−461 It has been confidingly demonstrated that besides achiral chromatography462,463 sublimation is the major concern in the accurate determination of the enantiomeric purity of fluorinated compounds;464−468 quite unfortunately, the researchers in the area of asymmetric catalysis, in general, and in particular in asymmetric catalytic synthesis of fluorinated compounds are still unaware of this problem and may have reported erroneous data on the outcome of the asymmetric reactions. Some of the compounds containing SOnCF3 groups would be volatile. Hence it might be highly possible to indicate the phenomenon of self-disproportionation of enantiomers during the purification stage of them by achiral chromatography and/or distillation in the case of chiral compounds. As a class of important fluorinated compounds, C−SOnCF3 compounds find increasing utility in agrochemical and pharmaceutical applications. A summary of the known methods for these compounds are presented in this review. The variety of methods reflects the level of interest chemists have shown to generate these compounds. Despite the remarkable advances that have been made, further developments are still necessary. The direct introduction of fluorine-containing groups into organic molecules, through C−H activation or in an asymmetric process, has rarely been reported. It is our hope that this review will encourage organic chemists to develop new and exciting methods for the synthesis of even more C− SOnCF3 compounds.

Kohei Matsuzaki received his B.Sc. (2012) and M.Sc. (2014) in chemistry from the Nagoya Institute of Technology under the supervision of Professor Norio Shibata, and he is currently in the same group for his Ph.D. He received an award for graduate students in the Tokai Branch of the Chemical Society of Japan (2014). His research interests have centered on hypervalent iodine chemistry.

AUTHOR INFORMATION Corresponding Author

*E-mail: [email protected]. Notes

The authors declare no competing financial interest.

Norio Shibata (born July 3, 1965 in Osaka, Japan) is a Professor at the Nagoya Institute of Technology, since 2008. He received a Ph.D. (1993) in pharmaceuitcal sciences from Osaka University under the direction of Professor Yasuyuki Kita. He worked at Dyson Perrins Laboratory (Professor Sir Jack. E. Baldwin), Oxford University (JSPS fellow, 1994−1996), Sagami Chemical Research Institute (Dr. Shiro Terashima, 1996), after which he was a lecturer at Toyama Medical & Pharmaceutical University (1997−2003), and an associate professor at the Nagoya Institute of Technology (2003−2008). He also acted as a visiting professor (2008, 2012) at the University of Rouen. He received the “Takeda Pharmaceutical Company Award in Synthetic Organic Chemistry, Japan 2000”, the “Fujifilm Award in Synthetic Organic Chemistry, Japan 2003”, the “Incentive Award in Synthetic Organic Chemistry, Japan (2004)”, the “RSC Fluorine Prize (inaugural Prize in 2005)”, the “20th Lecture Award for Young Chemists in Chemical Society of Japan (2005)”, the “Fluorine Chemistry Research Incentive Award in Research Foundation ITSUU Laboratory (inaugural Prize in 2009)”, “The Pharmaceutical Society of Japan Award for Divisional Scientific Promotions (2010)”, and “Prizes for

Biographies

Xiu-Hua Xu was born in 1981 in Jiangsu province, China. He received his B.Sc. degree from Nankai University in 2003 and Ph.D. under the 757


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Science and Technology, The Commendation for Science and Technology by the Minister of Education, Culture, Sports, Science and Technology (2014)”. His research interests are synthetic and medicinal fluorine chemistry.

ACKNOWLEDGMENTS The authors’ research on the review topic was financially supported in part by the Platform for Drug Discovery, Informatics, and Structural Life Science, Grant-in-Aids for Scientific Research on Innovative Areas (“Advanced Molecular Transformations by Organocatalysts”, 24105513) and Scientific Research (B) (25288045) from MEXT Japan, ACT-C from JST, Exploratory Research (25670055).

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