View Article Online

Organic & Biomolecular Chemistry

View Journal

Accepted Manuscript

This article can be cited before page numbers have been issued, to do this please use: A. K. Singh, R. Chawla, T. Keshari, V. K. Yadav and L.D.S. Yadav, Org. Biomol. Chem., 2014, DOI: 10.1039/C4OB00776J.

This is an Accepted Manuscript, which has been through the Royal Society of Chemistry peer review process and has been accepted for publication. Accepted Manuscripts are published online shortly after acceptance, before technical editing, formatting and proof reading. Using this free service, authors can make their results available to the community, in citable form, before we publish the edited article. We will replace this Accepted Manuscript with the edited and formatted Advance Article as soon as it is available. You can find more information about Accepted Manuscripts in the Information for Authors. Please note that technical editing may introduce minor changes to the text and/or graphics, which may alter content. The journal’s standard Terms & Conditions and the Ethical guidelines still apply. In no event shall the Royal Society of Chemistry be held responsible for any errors or omissions in this Accepted Manuscript or any consequences arising from the use of any information it contains.

www.rsc.org/obc

Journal Name

Organic & Biomolecular Chemistry

Dynamic Article Links ► View Article Online

DOI: 10.1039/C4OB00776J

Cite this: DOI: 10.1039/c0xx00000x

ARTICLE TYPE

www.rsc.org/xxxxxx

Published on 04 September 2014. Downloaded by Northern Illinois University on 11/09/2014 07:43:37.

Aerobic oxysulfonylation of alkenes using thiophenols: An efficient onepot route to β-ketosulfones† Atul K. Singh, Ruchi Chawla, Twinkle Keshari, Vinod K. Yadav, and Lal Dhar S. Yadav* 5

10

15

20

25

30

35

40

Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX DOI: 10.1039/b000000x We have developed a highly efficient synthetic route to βketosulfones via AgNO3 catalyzed oxysulfonylation of alkenes using thiophenols in the presence of air (O2) and K2S2O8 as eco-friendly oxidants. Thiophenols have been used as sulfonylation precursors for the first time in a dioxygen activation based radical process. Moreover, the protocol also offers a new and convenient method for the synthesis of β-hydroxysulfides at room temperature without use of any initiator.

45

50

Introduction A major challenge at the forefront of synthetic chemistry is to design multistep bond formation and bond cleavage in minimum number of synthetic steps. In this regard, one-pot cascade reaction is an attractive strategy for minimizing the energy cost and chemical waste. Dioxygen is an ideal source of oxygen because it is nontoxic, cheap, abundantly available, which is attractive from both economic and environmental standpoints. In this connection direct oxidative functionalization of organic molecules with dioxygen is one of the most ideal strategies for constructing oxygen-contaning compounds.1 On the other hand, alkenes are common, versatile and readily available starting materials, which have been extensively used in organic synthesis. Particularly, transition-metalcatalyzed oxidative difunctionalization of alkenes with dioxygen such as dioxygenation,2 aminooxygenation,3 oxyalkylation 4 and oxyphosphorylation,5 has become a powerful methodology for the construction of oxygenated compounds. Dioxygen-triggered oxidative radical sulfonylation of alkenes has been utilized as a robust synthetic method for construction of sulfones.6 Sulfone compounds are important materials because they include valuable biologically active compounds and useful building blocks in synthetic organic chemistry.7 To date, limited methods are available for the construction of β-ketosulfone compounds via oxidative difuntionalization of alkenes with dioxygen. The previously reported methods for the Green Synthesis Lab, Department of Chemistry, University of Allahabad, Allahabad 211 002, India; E-mail:[email protected]; Fax: (+91)532-246-0533; Tel.: (+91)532-250-0652 † Electronic supplementary information (ESI) available: experimental details,characterization data and copies of 1 H and 13C NMR spectra for the products. See DOI:……….

This journal is © The Royal Society of Chemistry [year]

55

60

synthesis of sulfones include the intermolecular addition of sulfonyl radicals to alkenes using sulfonyl chlorides, 6a,c sulfonyl selenides,6d,e sulfonyl cyanides,6f sulfonyl azides,6g sulfonyl hyadrazides,6h-j sulfinic acids6k,l and 6m-o arenesulfinates as a source of sulfonyl radical (Scheme 1a). Considering the above points and in continuation of our efforts for the synthesis of sulfones,6m-o,8 we were prompted to develop a new and efficient protocol for the synthesis of β-ketosulfones from easily and commercially available reagent and catalyst. Herein, we report an AgNO3 catalyzed direct oxysulfonylation of alkenes with dioxygen and thiophenols leading to β-ketosulfones, which constitute a chemically and biologically relevant class of compounds. Chemical transformations that use thiophenols in oxygen capture reaction for functionalization of alkenes are limited to the synthesis of β-hydroxysulfides (Scheme 1b).9 To the best of our knowledge, this is the first report on the synthesis of β-ketosulfones via AgNO3 catalyzed oxysulfonylation of alkenes with thiophenols using K2S 2O8 as an additive in a one-pot operation (Scheme 1c). Previous work

O

O S

1

R

R2

3

1

R

R a)

initiator or

XO2S

O2 photolysis r ef . 6

2

R

R OH

R

R

1

R

S 2

R

R

3

OH

O2 or stoichiometric reagent/catalyst ref. 9

2

O R

base catalyst with UV / peroxide

3

HS

3

O

1

X = ha loge n, SePh, N 3 , CN, NHNH2 , H, Na

b)

O

or

R

S

1 2

R

R

3

Present work

c)

O

R1

O

AgNO 3 (20 mol%) HS

R3

O2

R2

R K 2S2 O8 (3 equiv)

S

1 2

R

R3

O

DMF, rt 65

Scheme 1 Aerobic oxysulfonylation of alkenes.

Results and discussion Initially, a model reaction was performed by stirring a mixture of styrene (1a, 0.25 mmol), thiophenol (2a, 0.25 mmol), FeCl3 (20 mol%) and K2S 2O8 (0.75 mmol) in DMF [journal], [year], [vol], 00–00 | 1

Organic & Biomolecular Chemistry Accepted Manuscript

Page 1 of 5

Organic & Biomolecular Chemistry

Page 2 of 5 View Article Online

Published on 04 September 2014. Downloaded by Northern Illinois University on 11/09/2014 07:43:37.

5

10

15

20

25

30

35

40

45

50

55

at rt overnight. The corresponding β-ketosulfone 3a was obtained in 70% yield (Table 1, entry 1). After the formation of β-ketosulfone, we focused our efforts to know the minimum time required for completion of the reaction and it was found to be 18 h. Encouraged by the result, we next focused our efforts on increasing the yield of βketosulfone by changing the additive. However, it was observed that the use of other additives like TBHP, DTBP, and (NH4)2S 2O8 in place of K2S 2O8 did not improve the yield (Table 1, entries 1-4). After the optimization of additive, we performed the screening of different metal salts. It was found that AgNO3 gave better result in comparison to FeCl3 and other tested metal salts (Table 1, entries 5-10). For comparison purpose, the reaction was also performed in various solvents but DMF remained the best in terms of yield and reaction time (Table 1, entries 8 and 1117). Subsequently, the quantitative optimization of catalyst, additive and thiophenol was done. Firstly, we optimized the quantitative ratio of thiophenol and it was found that the best yield of β-ketosulfone (92%) was obtained with 1 equiv of thiophenol (Table 1, entry 8). In the presence of 1.5 equiv of thiophenol, the yield of 3a did not change but the use of 0.8 equiv of thiophenol decreased the yield of βketosulfone to 70% even when the reaction time was extended up to 24 h (Table 1, entries 18,19). With the best solvent, metal salt and additive in hand, we further tried to optimize the molar ratio of AgNO3 and K2S 2O8 and the results are summarized in Table 1, entries 20-24. As can be seen from Table 1, equimolar amounts of styrene (1a) and thiophenol (2a) with 20 mol% of AgNO3 and 3 equiv of K2S 2O8 delivered the maximum yield (92%) of βketosulfone 3a (Table 1, entry 8). To evaluate the scope and limitations of this optimized reaction protocol, we investigated a variety of different alkenes 1 and thiophenols 2 (Table 2). As shown in Table 2, the alkenes 1 as well as thiophenols 2 having different electron-withdrawing and electron-donating substituents efficiently reacted to afford the corresponding βketosulfones 3 in good to excellent yields, demonstrating that this new AgNO3 catalyzed aerobic oxysulfonylation is a general and practically useful method for the preparation of such a valuable class of compounds. A variety of functionalities such as methyl, methoxy, fluoro, chloro, bromo, and cyano on alkenes were all well tolerated under the reaction conditions (3a-3j). Notably, the variation of position (o-, m- and p-) of substituents on the phenyl ring of styrene also gave excellent yield of the corresponding βketosulfones (3b-3f). The bicyclic substrate, 2naphthylethylene could also be employed in the reaction leading to β-ketosulfone 3k in 83% yield. Prop-1enylbenzene, an internal alkene, also served as a suitable reaction partner in this protocol and the desired product 3l was obtained in 84% yield. Subsequently, the scope of the reaction was explored for the synthesis of β-ketosulfones 3m-3t using different thiophenols 2. A series of functional groups on thiphenols including methyl, methoxy, bromo, chloro and fluoro were tolerable under the present mild reaction conditions. Even the bulky 2-naphthylthiophenol

2 | Journal Name, [year], [vol], 00–00

60

65

70

produced the ketosulfone 3t efficiently (yield 75%) under the reaction conditions. The scope of the reaction was also examined with other alkenes such as alkylethenes, 1,2dialkylethenes, 1,2-diarylethenes, trisubstituted alkenes, and electron-deficient alkenes, but either the reaction did not proceed or the desired products were formed in traces. The reaction was also successfully tried with a thiol, e.g. propanethiol, to afford the corresponding β-ketosulfone 3u in 84% yield (Table 2). Table 1 Optimization of reaction conditions for the synthesis of β-keto sulfonesa O O2

HS

O

Catalyst/ additive

S O

Solvent, rt, 18 h 1a

Entry 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24

2a

3a

Solvent Metal salt (mol%) Additive (equiv) Yield b (%) DMF DMF DMF DMF DMF DMF DMF DMF DMF DMF DMSO MeOH EtOH THF CH3CN DCM Dioxane DMF DMF DMF DMF DMF DMF DMF

FeCl3 (20) FeCl3 (20) FeCl3 (20) FeCl3 (20) Fe2O3 (20) [Fe(Pc)] (20) FeCl2 (20) AgNO3 (20) CuCl (20) Cu(OAc)2 (20) AgNO3 (20) AgNO3 (20) AgNO3 (20) AgNO3 (20) AgNO3 (20) AgNO3 (20) AgNO3 (20) AgNO3 (20) AgNO3 (20) AgNO3 (20) AgNO3 (20) AgNO3 (15) AgNO3 (25) -

K2S2O8 (3) TBHP (3) DTBP (3) (NH4)2S2O8 (3) K2S2O8 (3) K2S2O8 (3) K2S2O8 (3) K2S2O8 (3) K2S2O8 (3) K2S2O8 (3) K2S2O8 (3) K2S2O8 (3) K2S2O8 (3) K2S2O8 (3) K2S2O8 (3) K2S2O8 (3) K2S2O8 (3) K2S2O8 (3) K2S2O8 (3) K2S2O8 (2.5) K2S2O8 (3.5) K2S2O8 (3) K2S2O8 (3) K2S2O8 (3)

70 35 28 62 40 65 10 92 15 40 83 20 28 10 26 92c 70d 75 92 80 92 23

a

75

80

85

Reaction conditions: styrene (1a, 0.25 mmol), thiophenol (2a, 0.25 mmol), solvent (3 mL). b Isolated yield after column chromatography. c 2a (0.38 mmol). d 2a (0.20 mmol) and reaction time 24 h.

In order to gain reasonable insight into the reaction mechanism, we conducted a number of experiments (Scheme 3). Initially, we studied the progress of reaction using styrene (1a, 0.25 mmol), thiophenol (2a, 0.25 mmol), AgNO3 (20 mol%) and K2S 2O8 (0.75 mmol) as model substrate in DMF at rt and the progress was monitored by TLC. After 4 hours, a new spot appeared on TLC and the corresponding intermediate product was isolated in 94% yield. It was confirmed to be β-hydroxysulfide 4a, as its spectral data were in full agreement with those reported in the literature.10 Next, we checked the role of catalyst/additive in the formation of β-hydroxysulfide. The control experiments indicated that the intermediate βThis journal is © The Royal Society of Chemistry [year]

Organic & Biomolecular Chemistry Accepted Manuscript

DOI: 10.1039/C4OB00776J

Page 3 of 5

Organic & Biomolecular Chemistry View Article Online

Published on 04 September 2014. Downloaded by Northern Illinois University on 11/09/2014 07:43:37.

5

10

15

hydroxysulfide was also formed in the absence of any additive in 94% yield (Scheme 3a). However, in the absence of the catalyst AgNO3, β-hydroxysulfide was not formed. Further, we performed the reaction without any additive using styrene (0.25 mmol), thiophenol (0.25 mmol), and AgNO3 (20 mol%) in DMF at rt for 18 h, but only βhydroxysulfide 4a was obtained instead of β-ketosulfone 3a. On the basis of above experiments, it was clear that for the formation of β-ketosulfone the additive K2S 2O8 was necessary, whereas it does not seem to play any role in the formation of the intermediate β-hydroxysulfides. Inspired by the previous reports that dioxygen activation based processes mostly involve radical species,6 a radical trapping experiment was performed using styrene (0.25 mmol), thiophenol (0.25 mmol), and AgNO3 (20 mol%) in DMF for the formation of β-hydroxysulfide. β-hydroxysulfide 4a was not at all formed in the presence of TEMPO under the

35

40

oxygen atom of β-hydroxysulfide originates from dioxygen (Scheme 3d). To further support that β-ketosulfones are formed by oxidation of β-hydroxysulfide 4a, it was subjected to the standard reaction conditions and product was isolated in 95% yield (Scheme 3e). This experiment also confirms that the reaction proceeds via βhydroxysulfide as an intermediate. It is in conformity with our earlier observation 6m that β-hydroxysulfones are not oxidized into β-ketosulfones under the given reaction conditions, so it clearly indicates that β-hydroxysulfides are first oxidized into β-ketosulfides which in turn are oxidized into β-ketosulfones.

45

a) synthesis of intermediate: SH

OH

AgNO3 (20 mol%)

S

DMF, rt, 4 h 4a, 94%

Table 2 Synthesis of β-ketosulfonesa R

1

HS R R

Entry

AgNO 3 (20 mol%) O2

2

DMF, rt

2

R1

R2

R3

S

R

R

Ph H Ph 3-MeC6H4 H Ph 2-MeC6H4 H Ph 4-MeC6H4 H Ph 4-MeOC6H4 H Ph 2-MeOC6H4 H Ph 4-BrC6H4 H Ph 4-ClC6H4 H Ph 4-FC6H4 H Ph 4-CNC6H4 H Ph 2-naphthyl H Ph Ph Me Ph Ph H 4-MeC6H4 4-MeC6H4 H 4-MeC6H4 4-BrC6H4 H 4-MeC6H4 Ph H 4-MeOC6H4 Ph H 4-BrC6H4 Ph H 4-ClC6H4 Ph H 4-FC6H4 Ph H 2-naphthyl Ph H C3H7

2

O

R

3

Product Time 3a 3b 3c 3d 3e 3f 3g 3h 3i 3j 3k 3l 3m 3n 3o 3p 3q 3r 3s 3t 3u

18 20 20 21 22 22 18 19 18 18 20 22 20 22 19 20 18 19 18 20 18

OH S

TEMPO (0.25 mmol) DMF, rt, 4 h

4a, 0%

Yieldb (%)

92 90 88 90 85 82 86 91 92 76 83 84 94 93 86 81 79 82 80 75 84

c) role of air as the oxidant:

DMF, rt, 4 h N2 atmosphere

This journal is © The Royal Society of Chemistry [year]

4a, traces

d) 18O-labelling experiment: 18

OH

SH

S

AgNO3 (20 mol%) DMF, rt, 4 h 18

O2/N2

4a', 88%

e) intermediate probe: OH S

K2S2O8 (3 equiv mol%)

O

O S O

DMF, rt, 16 h

3a, 95%

Scheme 3. Preliminary mechanistic investigations.

50

55

standard reaction conditions, elucidating a radical pathway (Scheme 3b). Studying the role of air in the reaction was also vital to unfold the intricacies of the mechanism. The reaction was considerably inhibited under nitrogen (Scheme 3c). We also performed oxygen labeling experiments. In the presence of 18O2/N2, 18O-labeled product β-hydroxysulfide 4a’ was obtained in 88% yield, confirming that the hydroxyl

S

AgNO3 (20 mol%)

Reaction conditions: styrene (1a, 0.25 mmol), thiophenol/thiol (2a, 0.25 mmol), AgNO3 (20 mol%), K2S2O8 (0.75 mmol), DMF (3 mL). b Isolated yield after column chromatography. 25

OH

SH

a

30

AgNO3 (20 mol%)

SH

3

(h)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21

b) evidence in support of radical pathway:

O

1

K 2S2 O8 (3 equiv)

1

20

3

O

60

On the basis of our experimental results and the literature precedents,6h,i,k,l,m,n a plausible mechanism for the formation of β-ketosulfones is depicted in Scheme 4. The AgNO3 catalyst triggers the thiyl radical formation from thiophenol. This thiyl radical attacks the double bond of alkene to furnish carbon centered radical 5, which is ultimately trapped by dioxygen to form β-hydroxysulfide 4. The βhydroxysulfide 4 is oxidized into β-ketosulfide 8 followed by further oxidation with K2S2O8 to afford the product βketosulfone 3. β-Hydroxysulfides are important building blocks for the synthesis of other functionalized organic molecules. 11 They exhibit great synthetic utility in the field of pharmaceuticals and natural products.12 Generally, they are synthesized by Journal Name, [year], [vol], 00–00 | 3

Organic & Biomolecular Chemistry Accepted Manuscript

DOI: 10.1039/C4OB00776J

Organic & Biomolecular Chemistry

Page 4 of 5 View Article Online

R2

R1

OH

OO

1

3

of β-hydroxysulfides at rt without use of any initiator. Table 3 Synthesis of β-hydroxysulfidesa

R

RS

S

1

R

5

O2 R

3

R

S

1

2

R

6

Ag0

R

R

3

1 H

Published on 04 September 2014. Downloaded by Northern Illinois University on 11/09/2014 07:43:37.

R

2

S

1

R

7

O

O S

R1 3 R2

O

R3

S

R1 8

R

R

K 2S2O8 R3

2

R

S

1

4

R

R3

2

Scheme 4. Plausible mechanism for the formation of β-ketosulfones.

25

30

35

40

R1

ring opening of epoxides with thiols in the presence of promoters or catalysts but these method suffer from various disadvantages such as drastic reaction conditions, poor regioselectivity, lower yield and undesirable side-products by rearrangement of epoxides and oxidation of thiols. 13 However, another method commonly used for the straightforward synthesis of β-hydroxysulfides involves the use of thiols and olefins.9 These reactions usually require a base catalyst with a large excess of thiol and are initiated by UV irradiation or peroxides, or require stoichiometric amounts of reagents/catalysts. Advantageously, the present study also offers a catalytic synthesis of β-hydroxysulfides from styrene and thiols without use of any initiator in the presence of only 20 mol% of AgNO3 as a mild catalyst (Table 3). A variety of alkenes 1 and thiophenols 2 react to give the corresponding β-hydroxysulfides in good to excellent yield demonstrating the synthetic utility of present method. The scope of the reaction was also examined with other alkenes such as alkylethenes, 1,2-dialkylethenes, 1,2diarylethenes, trisubstituted alkenes, and electron-deficient alkenes, but either the reaction did not proceed or the desired products were formed in traces. However, when the reaction was tried with a thiol, e.g. propanethiol, βhydroxysulfide 4m was formed in 87% yield (Table 3, entry 13). Conclusions In conclusion, we have demonstrated a novel, efficient and AgNO3 catalyzed synthesis of β-ketosulfones directly from olefins by employing thiophenols in the presence of air (O2) and K2S 2O8 as eco-friendly oxidants at an ambient temperature. The facile formation of new C=O, C-S and S=O bond takes place through a radical pathway followed by oxidation. In this process breaking of 2 old bonds (1 σ and 1 π) and formation of 7 new bonds (4 σ and 3 π) take place in a one-pot operation. Apart from this, the protocol also offers a new and convenient method for the synthesis 4 | Journal Name, [year], [vol], 00–00

Ph 4-MeC6H4 4-MeOC6H4 4-BrC6H4 4-ClC6H4 Ph Ph Ph Ph 4-ClC6H4 4-ClC6H4 4-ClC6H4 Ph

1 2 3 4 5 6 7 8 9 10 11 12 13

3

2

OH

O K2S2O8

S

R1

R3

4

R3

OOH

3

R SH

20

AgNO3 (20 mol%)

O2

2

Entry

Ag

15

R3

45

I

10

HS

DMF, rt

2

O2

5

1

Ph Ph Ph Ph Ph 4-MeC6H4 4-BrC6H4 4-ClC6H4 4-FC6H4 4-MeC6H4 4-ClC6H4 4-FC6H4

C3H7

Product Time (h) 4a 4 4b 4 4c 5 4d 4 4e 4 4f 4 4g 4 4h 5 4i 5 4j 5 4k 5 4l 6 4m 2

Yieldb (%) 92 91 88 88 91 95 80 83 82 90 81 78 87

a

Reaction conditions: styrene (1a, 0.25 mmol), thiophenol/thiol (2a, 0.25 mmol), AgNO3 (20 mol%) and DMF (3 mL). b Isolated yield after column chromatography.

Experimental 50

General 1

55

60

65

70

75

80

H NMR spectra were recorded on a Bruker Avance II (400 MHz) FT spectrometer in CDCl3 using TMS as internal reference. 13C NMR spectra were recorded on the same instrument at 100 MHz in CDCl3 and TMS was used as internal reference. Mass (EI) spectra were recorded on JEOL D-300 mass spectrometer. Elemental analyses were carried out in a Coleman automatic carbon, hydrogen and nitrogen analyser. All chemicals used were reagent grade and were used as received without further purification. All reactions were performed using oven-dried glassware. Organic solutions were concentrated using a Buchi rotary evaporator. Column chromatography was carried out over silica gel (Merck 100–200 mesh) and TLC was performed using silica gel GF254 (Merck) plates. General procedure for the synthesis of β-ketosulfones 3. A mixture of alkene 1 (0.25 mmol), thiophenol/thiol 2 (0.25 mmol), AgNO3 (20 mol%), K2S 2O8 (0.75 mmol) and DMF (3 mL) was stirred at rt in an open flask for 18-22 h (Table 2). After completion of the reaction (monitored by TLC), the mixture was extracted with EtOAc (3 × 5 mL). The combined organic phases were dried over anhyd. Na2SO4, filtered, and concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography using a mixture of EtOAc-nhexane (1:4) as eluent to afford an analytically pure sample of β-keto sulfones 3 (Table 2). General

procedure

for

the

synthesis

of

β-

This journal is © The Royal Society of Chemistry [year]

Organic & Biomolecular Chemistry Accepted Manuscript

DOI: 10.1039/C4OB00776J

Page 5 of 5

Organic & Biomolecular Chemistry View Article Online

Published on 04 September 2014. Downloaded by Northern Illinois University on 11/09/2014 07:43:37.

5

10

hydroxysulfides 4. A mixture of alkene 1 (0.25 mmol), thiophenol/thiol 2 (0.25 mmol), AgNO3 (20 mol%), and DMF (3 mL) was stirred at rt in an open flask for 2-6 h (Table 3). After completion of the reaction (monitored by TLC), the mixture was extracted with EtOAc (3 × 5 mL). The combined organic phases were dried over anhyd. Na2SO4, filtered, and concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography using a mixture of EtOAc-nhexane (1:4) as eluent to afford an analytically pure sample of β-hydroxysulfides 4 (Table 3).

70

11 12 75

13 80

Acknowledgement

15

We sincerely thank SAIF, Punjab University, Chandigarh, for providing microanalyses and spectra. A. K. S. is thankful to CSIR for the award of a Junior Research Fellowship (File No. 09/001(0379)/2013-EMR-I).

10

85

Rajendar, J. Mol. Catal. A: Chem., 2007, 272, 26; (e) C. Muangkaew, P. Katrun, P. Kanchanarugee, M. Pohmakotr, V. Reutrakul, D. Soorukram, T. Jaipetch and C. Kuhakarn, Tetrahedron, 2013, 69, 8847. J. X. Chen, H. Y. Wu, C. Jin, , X. X. Zhang Y. Y. Xie and W. K. Su, Green Chem., 2006, 8, 330. V. Kesavan, D. Bonnet-Delpon and J. P. Bégué, Tetrahedron Lett., 2000, 41, 2895. (a) C. G. Aifheli and P. T. Kaye, Synth. Commun., 1996, 26, 4459; (b) H. Sugihara, H. Mabuchi, M. Hirata, T. Iamamoto and Y. Kawamatsu, Chem. Pharm. Bull., 1987, 35, 1930; (c) J. R. Lucy, N. Yi, J. Soderquist, H. Stein, J. Cohen, T. J. Perun and J. J. Plattner, J. Med. Chem., 1987, 30, 1609. (a) B. Movassagh and M. Soleiman-Beigi, Synth. Commun., 2007, 37, 3239; (b) B. Movassagh, S. Sobhani, F. Kheirdoush and Z. Fadaei, Synth. Commun., 2003, 33, 3103; (c) F. Fringuelli, F. Pizzo, S. Tortoioli and L. Vaccaro, Tetrahedron Lett., 2003, 44, 6785; (d) F. Fringuelli, F. Pizzo, S. Tortoioli, L. Vaccaro, J. Org. Chem., 2003, 68, 8248; (e) V. Pironti and S. Colonna, Green Chem. 2005, 7, 43.

References 1 20

25

2 3 4

30

5 6 35

40

45

50

55

7 8 60

9

65

(a) T. Punniyamurthy, S. Velusamy and J. Iqbal, Chem. Rev., 2005, 105, 2329; (b) A. E. Wendlandt, A. M. Suess and S. S. Stahl, Angew. Chem. Int. Ed., 2011, 50, 11062; (c) Z. Shi, C. Zhang, C. Tang and N. Jiao, Chem. Soc. Rev., 2012, 41, 3381; (d) W. Wu, H. Jiang and S. Adimurthy, Acc. Chem. Res., 2012, 45, 1736. B. C. Giglio, V. A. Schmidt and E. J. Alexanian, J. Am. Chem. Soc., 2011, 133, 13320. H. Wang, Y. Wang, D. Liang, L. Liu, J. Zhang and Q. Zhu, Angew. Chem. Int. Ed., 2011, 50, 5678. Z.-Q. Wang, W.-W. Zhang, L.-B. Gong, R.-Y. Tang, X.-H. Yang, Y. Liu and J.-H. Li, Angew. Chem., Int. Ed., 2011, 50, 8968. W. Wei and J. X. Ji, Angew. Chem. Int. Ed., 2011, 50, 9097. (a) R. P. Nair, T. H. Kim and B. J. Frost, Organometallics, 2009, 28, 4681; (b) S.-K. Kang, H.-W. Seo and Y.- H. Ha, Synthesis, 2001, 1321; (c) D. C. Craig, G. L.; Edwards and C. A. Muldoon, Tetrahedron, 1997, 53, 6171; (d) D. H. R. Barton, M. S. Csiba and J. C. Jaszberenyi, Tetrahedron Lett., 1994, 35, 2869; (e) M. Yoshimatsu, M. Hayashi, G. Tanabe and O. Muraoka, Tetrahedron Lett., 1996, 37, 4161. (f) J.-M. Fang and M.-Y. Chen, Tetrahedron Lett. 1987, 28, 2853; (g) N. Mantrand and P. Renaud, Tetrahedron, 2008, 64, 11860; (h) T. Taniguchi, H. Zaimoku and H. Ishibashi, Chem. Eur. J., 2011, 17, 4307; (i) T. Taniguchi, A. Idota and H. Ishibashi, Org. Biomol. Chem. 2011, 9, 3151; (j) W. Wei, C. Liu, D. Yang, J. Wen, J. You, Y. Suo and H. Wang, Chem. Commun., 2013, 49, 10239; (k) Q. Lu, J. Zhang, G. Zhao, Y. Qi, H. Wang and A. W. Lei, J. Am. Chem. Soc., 2013, 135, 11481; (l) Q. Lu, J. Zhang, F. Wei, Y. Qi, H. Wang, Z. Liu and A. W. Lei, Angew. Chem. Int. Ed., 2013, 52, 7156; (m) R. Chawla, A. K. Singh and L. D. S. Yadav, Eur. J. Org. Chem., 2014, 2032; (n) A. K. Singh, R. Chawla and L. D. S. Yadav, Tetrahedron Lett.,2014, 55, 2845; (o) A. K. Singh, R. Chawla and L. D. S. Yadav, Tetrahedron Lett., 2014, 55, 4742. Y. M. Markitanov, V. M. Timoshenko and Shermolovich, Y. G. J. Sulfur Chem., 2014, 35, 188. (a) R. Chawla, R. Kapoor, A. K. Singh and L. D. S. Yadav, Green Chem., 2012, 14, 1308; (b) R. Chawla, A. K. Singh and Yadav, L. D. S. Tetrahedron, 2013, 69, 1720. A. L. J. Beckwith and R. D. Wagner, J. Org. Chem., 1981, 46, 3638; (b) H. H. Szmant, A. J. Mata, A. J. Namis and A. M. Panthananickal, Tetrahedron, 1976, 32, 2665; (c) K. Surendra, N. S. Krishnaveni, R. Sridhar and K. R. Rao, J. Org. Chem., 2006, 71, 5819; (d) Kamal, A. D. R. Reddy and

This journal is © The Royal Society of Chemistry [year]

Journal Name, [year], [vol], 00–00 | 5

Organic & Biomolecular Chemistry Accepted Manuscript

DOI: 10.1039/C4OB00776J

Aerobic oxysulfonylation of alkenes using thiophenols: an efficient one-pot route to β-ketosulfones.

We have developed a highly efficient synthetic route to β-ketosulfones via AgNO3 catalyzed oxysulfonylation of alkenes using thiophenols in the presen...
642KB Sizes 4 Downloads 9 Views