DOI: 10.1002/chem.201406227
Communication
& Decarbonylation
Decarbonylative C C Bond-Forming Reactions of Saccharins by Nickel Catalysis: Homocoupling and Cycloaddition Pengbing Mi,[a] Peiqiu Liao,[a] Tao Tu,[c] and Xihe Bi*[a, b] Abstract: Decarbonylation of saccharins by nickel catalysis enables two kinds of C C bond-forming reactions; homocoupling of saccharins to form biaryls and cycloaddition with alkynes to form benzosultams. The former represents the first reported nickel-catalyzed decarbonylative C C homocoupling reaction, whereas the latter constitutes a powerful method to pharmaceutically relevant benzosultams. The reactions proceed with good functional-group tolerance and excellent regioselectivity.
Scheme 1. Transition metal-catalyzed decarbonylative C C bond-forming reactions.
Carbon–carbon bond formation is an intensely studied objective in organic chemistry. The development of transition metal (TM)-catalyzed processes has seen the concept undergo tremendous progress in the last few decades.[1] A number of acclaimed techniques for C C coupling reactions , including the Ullmann, Kumada, Negishi, Suzuki, and Stille reactions, have been reported.[2] Rapid progress in the field of C H bond activation has particularly revealed many powerful methods for such developments.[3] Nevertheless, the search for new methods for C C bond formation remains of great demand to organic chemists. Carbonyl compounds, such as aldehydes, ketones, carboxylic acids and their derivatives, are among the most abundant chemicals and the ubiquitous nature of carbonyl compounds makes TM-catalyzed decarbonylation strategies a versatile mode of reactivity, especially in C C bond forming reactions.[4] Four modes of C C bond formation following the in situ generation of CO-coordinated organometallic species (C M(CO) Z; Scheme 1 a) are known to date: Crosscoupling,[5] homocoupling,[6] addition to unsaturated hydrocarbons,[7] and the extrusion of CO from ketones.[8] Reports related to decarbonylative homocoupling of carbonyls have been few and restricted to aldehydes and acyl chlorides.[4, 6] Ni0 is capable of undergoing oxidative addition to a variety of C heteroatom
bonds, which has been utilized in decarbonylative C C bondforming reactions such as cross-coupling and cycloaddition reactions.[5, 7, 9] However, nickel-catalyzed decarbonylative C C homocoupling reactions remain unknown. Saccharins are easily available compounds with a range of synthetic applications,[10] including in amination,[11] ring-expansion,[12] isomerization,[13] and carbonylation reactions.[14] Herein, we report the first investigation of nickel-catalyzed decarbonylation of saccharins, which leads to the development of two C C bond-forming reactions; a mechanistically novel homocoupling to form biaryls and an efficient cycloaddition with alkynes to form benzosultams (Scheme 1 b). The initial discovery of the decarbonylative homocoupling of saccharins stemmed from the preparation of ortho-deuteriumlabeled sulfonamides during our studies in alkyne chemistry.[15] Recently, the research group of Kurahashi and Matsubara described a series of nickel-catalyzed decarbonylative cycloaddition reactions of carbonyls with unsaturated hydrocarbons.[7] Inspired by this work, we envisaged that treatment of the saccharins with stoichiometric amounts of nickel(0) catalyst and subsequent protonation with CF3SO3H could give sulfonamides. Surprisingly, the anticipated reaction failed to yield sulfonamide 2 a’; instead, the decarbonylative homocoupling product 2 a, a biphenyl-2,2’-disulfonamide, was isolated in 31 % yield accompanied with 58 % recovered saccharin (Table 1, entry 1). This reaction is quite unique, as it represents an unprecedented decarbonylative homocoupling mode for C C bond formation. Consequently, detailed studies to elucidate the effect of the additive on the reaction outcome were carried out. Firstly, the amount of CF3SO3H was found to significantly affect the distribution ratio of product 2 a and recovered substrate 1 a. For our three initial experiments, an exceptional result that afforded 94 % yield of 2 a was realized from the
[a] P. Mi, Dr. P. Liao, Prof. X. Bi Department of Chemistry, Northeast Normal University Changchun 130024 (P. R. China) E-mail: [email protected] Homepage: http://www.bigroup.com.cn/ [b] Prof. X. Bi State Key Laboratory of Elemento-Organic Chemistry Nankai University, Tianjin 300071 (P. R. China) [c] Prof. T. Tu Department of Chemistry, Fudan University 200433 Shanghai (P. R. China) Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/chem.201406227. Chem. Eur. J. 2015, 21, 1 – 6
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Entry Substrate Additive 1 2 3 4 5[b] 6 7 8
1a 1a 1a 1a 1a 1a 1a 1 ab
CF3SO3H CF3SO3H CF3SO3H CF3COOH HCl BF3·Et2O NaBH4 CF3SO3H
Amount [equiv]
Product yield [%][a]
Recovered starting material [%]
2.0 5.0 10.0 10.0 10.0 10.0 10.0 10.0
2 a, 31 2 a, 70 2 a, 94 2 a, 67 2 a, 42 2 a, trace 2 a, 0 2 ab, 0
58 18 0 19 51 90 95 100
[a] Yields of isolated compound; [b] HCl in Et2O (5 m).
Scheme 2. Substrate scope for the decarbonylative homocoupling of saccharins. cod = 1,5-cyclooctadiene.
complete conversion of 1 a upon treatment with 10 equivalents of CF3SO3H (Table 1, entries 2 and 3). However, replacement of CF3SO3H with the slightly weaker CF3COOH led to an incomplete reaction with 67 % yield of 2 a (Table 1, entry 4). The proton-promoted coupling was verified, because HCl in Et2O could promote this reaction and result in a fair yield of 2 a, which excluded the necessity of acid anions (Table 1, entry 5). Furthermore, BF3·Et2O (a Lewis acid) and NaBH4 (a hydride donor) proved to be totally inactive for the decarbonylation as substrate 1 a was recovered almost completely (Table 1, entries 6 and 7). With the conditions listed in entry 3, the reactivity of phthalimide 1 ab, a compound similar to saccharin 1 a in structure, was examined. Surprisingly, substrate 1 ab was completely recovered, without coupled product 2 ab (Table 1, entry 8). The remarkable difference in reactivity between 1 a and 1 ab may be due to the strong electronegativity and steric effect of the SO2 group in saccharins.[16] From a synthetic point of view, we have found a new reaction toward the synthesis of biaryls.[17] Although biphenyl-2,2’disulfonamides, such as 2 a, are key structural motifs in radiation-sensitive pigments, known synthetic methods have been limited to the copper-catalyzed Ullmann coupling of ortho-iodosulfonamides, with low yields and efficiency.[18] This limitation inspired us to investigate the reaction scope for this new decarbonylative homocoupling reaction under nickel catalysis (Scheme 2). The N-aryl saccharins 1 b–h were readily applied to the nickel-promoted reactions, affording the corresponding coupling products 2 b–h in excellent yields. A diverse range of aromatic substituents, including electron-rich and -poor aryl, heteroaryl, and fused aryl groups, were well tolerated. The structure of 2 c was unambiguously confirmed by single-crystal X-ray diffraction analysis. The inability of the N-methyl reactant 1 i in this coupling reaction demonstrated the significant influence of N-substituents. &
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A cross-coupling reaction between saccharins 1 a and 1 h was performed by mixing the same equivalents of reactants in the reaction. A mixture consisting of homo-coupling products 2 a, 2 h, and a cross-coupling product 2 ah, was obtained in 86 % total yield [Eq. (1)]. This result is mechanistically important, as it implies that the decarbonylative C C homocoupling proceeded through an intermolecular process.
To capture the organonickel intermediates with other components and utilize this nickel-catalyzed decarbonylative methodology, we examined the cycloaddition of saccharins with alkynes, a potential pathway to pharmaceutically important benzosultams.[19] Although a number of synthetic protocols toward benzosultams have been reported, most of these methods involve intramolecular cyclizations using elaborately designed substrates and multistep routes.[20] However, step-economical,[21] metal-catalyzed cycloaddition approaches to benzosultams are comparatively less well-studied.[22] Screening of reaction conditions for the cycloaddition of saccharin 1 a with alkyne 3 a was conducted and the identified optimal conditions afforded the desired benzosultam 4 a in 85 % yield in the 2
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Communication cal alkynes, we were pleased to note that the regioisomers 4 s–u were generated regioselectively in good yields. The regiochemistry was established by NOE experiments. Next, attention was focused on the intramolecular decarbonylative cycloaddition. Under the standard conditions, the reaction of 5 a smoothly proceeded to afford a novel tricyclic product 6 a in 78 % yield, with a 1:1 ratio of Z and E stereoisomers (Scheme 4). The tricyclic structure was unequivocally resolved
presence of 50 mol % of nickel(0) catalyst [Eq. (2)]. This constituted a straightforward route to benzosultams.
The substrate scope for saccharins was next investigated (Scheme 3) Saccharins containing electron-rich or -poor N-aryl groups reacted efficiently with alkynes 3, affording the corresponding products (4 b–g) in good to excellent yields (70– 93 %). Representative functional groups such as ether, chloride, trifluoromethyl, and ester, were well tolerated. In addition to
Scheme 4. Intramolecular decarbonylative cyclization.
by X-ray crystallographic analysis. The length of the alkyl chain between the saccharin and alkyne moieties significantly affected the reaction outcome, as the reaction of 5 b resulted in an unidentified mixture. Although the precise mechanism of the reaction remains unclear, we proposed the following reaction pathways based on related precedents (Scheme 5).[7, 9, 23] First, oxidative addition of 1 a and Ni0 catalyst takes place to afford the nickelacycle A, which can be converted into intermediate B by the extrusion of CO. In the presence of large excess of TfOH, the decarbonylative homocoupling reaction takes place giving biaryl 2 a, in-
Scheme 3. Substrate scope for the decarbonylative cycloaddition of saccharins with alkynes.
the aryl groups, N-alkyl groups that also underwent reaction included benzyl (4 h), methyl (4 i), n-butyl (4 j, 4 l), and notably, 2,2-dimethoxyethyl (4 k), a masked aldehyde group capable of undergoing further synthetic derivatization. It is also notable that the 3-thienyl substituent was also amenable to the reaction conditions, affording N-thienyl benzosultam 4 m in 87 % yield. The scope of internal alkynes was also examined for their reaction with N-(p-tolyl)saccharin 1 b. Pleasingly, all selected symmetrical aryl and alkyl alkynes reacted smoothly with 1 b to afford the corresponding benzosultams 4 n–u in good yields. The structures of both 4 m and 4 o were unambiguously confirmed by X-ray diffraction analysis. Regarding unsymmetriChem. Eur. J. 2015, 21, 1 – 6
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Scheme 5. Proposed mechanism.
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Communication volving a ligand-exchange process to give intermediate C followed by sequential reductive elimination and protonation.[24] This proposal is supported by Colon’s work, as in nickel-catalyzed homocoupling reactions of aryl halides they observed that arylnickel(II) complexes gave high yields of homocoupled products in protic solvents without consuming aryl halide.[25] Regarding the reaction with alkynes, an initial coordination of intermediate B with alkyne 3 a generates active intermediate D. Following an insertion to C Ni bond, a seven-membered azanickelacycle E is produced, which undergoes reductive elimination to give benzosultam 4 a with regeneration of the Ni0 catalyst. In the intramolecular annulation, the extrusion of CO occurs to give complex F. Following the allenylation of the propargyl group,[26] intermediate G, containing an allene unit, is formed and subsequently forms intermediate H.[22a, 27] After reductive elimination the tricyclic product 6 a is released along with the Ni0 catalyst regeneration. In conclusion, our studies on the decarbonylative reactions of saccharins by nickel catalysis have led to the discovery of two novel decarbonylative C C bond-forming reactions; homocoupling to form biaryls and cycloaddition with alkynes to form benzosultams. The former represents the first nickel-catalyzed decarbonylative C C homocoupling reaction, whereas the later provides a powerful method to pharmaceutically relevant benzosultams, for which metal-catalyzed cycloaddition approaches have been relatively undeveloped. Although these features could be attributed to the strong electronegativity and steric effect of the SO2 group in the saccharins, further investigations toward elucidating the mechanism are still required.
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[7]
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[9] [10]
[11]
Acknowledgements This work was supported by the NNSFC (21172029, 21202016, 21372038), the Ministry of Education of the People’s Republic of China (NCET-13-0714), and the Jilin Provincial Research Foundation for Basic Research (20140519008JH).
[12]
[13]
Keywords: cycloaddition · decarbonylation · homocoupling · nickel · saccharins
[14]
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Received: November 25, 2014 Revised: January 29, 2015 Published online on && &&, 0000
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COMMUNICATION & Decarbonylation
Decarbonylation of saccharins by nickel catalysis has led to the discovery of two novel C C bond-forming reactions; homocoupling to form biaryls, and cycloaddition with alkynes to give benzosultams. The former represents the first nickel-catalyzed decarbonylative C C homocoupling reaction, whereas the latter constitutes a powerful method to pharmaceutically relevant benzosultams with good functionalgroup tolerance and excellent regioselectivity.
P. Mi, P. Liao, T. Tu, X. Bi* && – && Decarbonylative C C Bond-Forming Reactions of Saccharins by Nickel Catalysis: Homocoupling and Cycloaddition
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& Decarbonylation
Decarbonylative C C Bond-Forming Reactions of Saccharins by Nickel Catalysis: Homocoupling and Cycloaddition Pengbing Mi,[a] Peiqiu Liao,[a] Tao Tu,[c] and Xihe Bi*[a, b] Abstract: Decarbonylation of saccharins by nickel catalysis enables two kinds of C C bond-forming reactions; homocoupling of saccharins to form biaryls and cycloaddition with alkynes to form benzosultams. The former represents the first reported nickel-catalyzed decarbonylative C C homocoupling reaction, whereas the latter constitutes a powerful method to pharmaceutically relevant benzosultams. The reactions proceed with good functional-group tolerance and excellent regioselectivity.
Scheme 1. Transition metal-catalyzed decarbonylative C C bond-forming reactions.
Carbon–carbon bond formation is an intensely studied objective in organic chemistry. The development of transition metal (TM)-catalyzed processes has seen the concept undergo tremendous progress in the last few decades.[1] A number of acclaimed techniques for C C coupling reactions , including the Ullmann, Kumada, Negishi, Suzuki, and Stille reactions, have been reported.[2] Rapid progress in the field of C H bond activation has particularly revealed many powerful methods for such developments.[3] Nevertheless, the search for new methods for C C bond formation remains of great demand to organic chemists. Carbonyl compounds, such as aldehydes, ketones, carboxylic acids and their derivatives, are among the most abundant chemicals and the ubiquitous nature of carbonyl compounds makes TM-catalyzed decarbonylation strategies a versatile mode of reactivity, especially in C C bond forming reactions.[4] Four modes of C C bond formation following the in situ generation of CO-coordinated organometallic species (C M(CO) Z; Scheme 1 a) are known to date: Crosscoupling,[5] homocoupling,[6] addition to unsaturated hydrocarbons,[7] and the extrusion of CO from ketones.[8] Reports related to decarbonylative homocoupling of carbonyls have been few and restricted to aldehydes and acyl chlorides.[4, 6] Ni0 is capable of undergoing oxidative addition to a variety of C heteroatom
bonds, which has been utilized in decarbonylative C C bondforming reactions such as cross-coupling and cycloaddition reactions.[5, 7, 9] However, nickel-catalyzed decarbonylative C C homocoupling reactions remain unknown. Saccharins are easily available compounds with a range of synthetic applications,[10] including in amination,[11] ring-expansion,[12] isomerization,[13] and carbonylation reactions.[14] Herein, we report the first investigation of nickel-catalyzed decarbonylation of saccharins, which leads to the development of two C C bond-forming reactions; a mechanistically novel homocoupling to form biaryls and an efficient cycloaddition with alkynes to form benzosultams (Scheme 1 b). The initial discovery of the decarbonylative homocoupling of saccharins stemmed from the preparation of ortho-deuteriumlabeled sulfonamides during our studies in alkyne chemistry.[15] Recently, the research group of Kurahashi and Matsubara described a series of nickel-catalyzed decarbonylative cycloaddition reactions of carbonyls with unsaturated hydrocarbons.[7] Inspired by this work, we envisaged that treatment of the saccharins with stoichiometric amounts of nickel(0) catalyst and subsequent protonation with CF3SO3H could give sulfonamides. Surprisingly, the anticipated reaction failed to yield sulfonamide 2 a’; instead, the decarbonylative homocoupling product 2 a, a biphenyl-2,2’-disulfonamide, was isolated in 31 % yield accompanied with 58 % recovered saccharin (Table 1, entry 1). This reaction is quite unique, as it represents an unprecedented decarbonylative homocoupling mode for C C bond formation. Consequently, detailed studies to elucidate the effect of the additive on the reaction outcome were carried out. Firstly, the amount of CF3SO3H was found to significantly affect the distribution ratio of product 2 a and recovered substrate 1 a. For our three initial experiments, an exceptional result that afforded 94 % yield of 2 a was realized from the
[a] P. Mi, Dr. P. Liao, Prof. X. Bi Department of Chemistry, Northeast Normal University Changchun 130024 (P. R. China) E-mail: [email protected] Homepage: http://www.bigroup.com.cn/ [b] Prof. X. Bi State Key Laboratory of Elemento-Organic Chemistry Nankai University, Tianjin 300071 (P. R. China) [c] Prof. T. Tu Department of Chemistry, Fudan University 200433 Shanghai (P. R. China) Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/chem.201406227. Chem. Eur. J. 2015, 21, 1 – 6
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Entry Substrate Additive 1 2 3 4 5[b] 6 7 8
1a 1a 1a 1a 1a 1a 1a 1 ab
CF3SO3H CF3SO3H CF3SO3H CF3COOH HCl BF3·Et2O NaBH4 CF3SO3H
Amount [equiv]
Product yield [%][a]
Recovered starting material [%]
2.0 5.0 10.0 10.0 10.0 10.0 10.0 10.0
2 a, 31 2 a, 70 2 a, 94 2 a, 67 2 a, 42 2 a, trace 2 a, 0 2 ab, 0
58 18 0 19 51 90 95 100
[a] Yields of isolated compound; [b] HCl in Et2O (5 m).
Scheme 2. Substrate scope for the decarbonylative homocoupling of saccharins. cod = 1,5-cyclooctadiene.
complete conversion of 1 a upon treatment with 10 equivalents of CF3SO3H (Table 1, entries 2 and 3). However, replacement of CF3SO3H with the slightly weaker CF3COOH led to an incomplete reaction with 67 % yield of 2 a (Table 1, entry 4). The proton-promoted coupling was verified, because HCl in Et2O could promote this reaction and result in a fair yield of 2 a, which excluded the necessity of acid anions (Table 1, entry 5). Furthermore, BF3·Et2O (a Lewis acid) and NaBH4 (a hydride donor) proved to be totally inactive for the decarbonylation as substrate 1 a was recovered almost completely (Table 1, entries 6 and 7). With the conditions listed in entry 3, the reactivity of phthalimide 1 ab, a compound similar to saccharin 1 a in structure, was examined. Surprisingly, substrate 1 ab was completely recovered, without coupled product 2 ab (Table 1, entry 8). The remarkable difference in reactivity between 1 a and 1 ab may be due to the strong electronegativity and steric effect of the SO2 group in saccharins.[16] From a synthetic point of view, we have found a new reaction toward the synthesis of biaryls.[17] Although biphenyl-2,2’disulfonamides, such as 2 a, are key structural motifs in radiation-sensitive pigments, known synthetic methods have been limited to the copper-catalyzed Ullmann coupling of ortho-iodosulfonamides, with low yields and efficiency.[18] This limitation inspired us to investigate the reaction scope for this new decarbonylative homocoupling reaction under nickel catalysis (Scheme 2). The N-aryl saccharins 1 b–h were readily applied to the nickel-promoted reactions, affording the corresponding coupling products 2 b–h in excellent yields. A diverse range of aromatic substituents, including electron-rich and -poor aryl, heteroaryl, and fused aryl groups, were well tolerated. The structure of 2 c was unambiguously confirmed by single-crystal X-ray diffraction analysis. The inability of the N-methyl reactant 1 i in this coupling reaction demonstrated the significant influence of N-substituents. &
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A cross-coupling reaction between saccharins 1 a and 1 h was performed by mixing the same equivalents of reactants in the reaction. A mixture consisting of homo-coupling products 2 a, 2 h, and a cross-coupling product 2 ah, was obtained in 86 % total yield [Eq. (1)]. This result is mechanistically important, as it implies that the decarbonylative C C homocoupling proceeded through an intermolecular process.
To capture the organonickel intermediates with other components and utilize this nickel-catalyzed decarbonylative methodology, we examined the cycloaddition of saccharins with alkynes, a potential pathway to pharmaceutically important benzosultams.[19] Although a number of synthetic protocols toward benzosultams have been reported, most of these methods involve intramolecular cyclizations using elaborately designed substrates and multistep routes.[20] However, step-economical,[21] metal-catalyzed cycloaddition approaches to benzosultams are comparatively less well-studied.[22] Screening of reaction conditions for the cycloaddition of saccharin 1 a with alkyne 3 a was conducted and the identified optimal conditions afforded the desired benzosultam 4 a in 85 % yield in the 2
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Communication cal alkynes, we were pleased to note that the regioisomers 4 s–u were generated regioselectively in good yields. The regiochemistry was established by NOE experiments. Next, attention was focused on the intramolecular decarbonylative cycloaddition. Under the standard conditions, the reaction of 5 a smoothly proceeded to afford a novel tricyclic product 6 a in 78 % yield, with a 1:1 ratio of Z and E stereoisomers (Scheme 4). The tricyclic structure was unequivocally resolved
presence of 50 mol % of nickel(0) catalyst [Eq. (2)]. This constituted a straightforward route to benzosultams.
The substrate scope for saccharins was next investigated (Scheme 3) Saccharins containing electron-rich or -poor N-aryl groups reacted efficiently with alkynes 3, affording the corresponding products (4 b–g) in good to excellent yields (70– 93 %). Representative functional groups such as ether, chloride, trifluoromethyl, and ester, were well tolerated. In addition to
Scheme 4. Intramolecular decarbonylative cyclization.
by X-ray crystallographic analysis. The length of the alkyl chain between the saccharin and alkyne moieties significantly affected the reaction outcome, as the reaction of 5 b resulted in an unidentified mixture. Although the precise mechanism of the reaction remains unclear, we proposed the following reaction pathways based on related precedents (Scheme 5).[7, 9, 23] First, oxidative addition of 1 a and Ni0 catalyst takes place to afford the nickelacycle A, which can be converted into intermediate B by the extrusion of CO. In the presence of large excess of TfOH, the decarbonylative homocoupling reaction takes place giving biaryl 2 a, in-
Scheme 3. Substrate scope for the decarbonylative cycloaddition of saccharins with alkynes.
the aryl groups, N-alkyl groups that also underwent reaction included benzyl (4 h), methyl (4 i), n-butyl (4 j, 4 l), and notably, 2,2-dimethoxyethyl (4 k), a masked aldehyde group capable of undergoing further synthetic derivatization. It is also notable that the 3-thienyl substituent was also amenable to the reaction conditions, affording N-thienyl benzosultam 4 m in 87 % yield. The scope of internal alkynes was also examined for their reaction with N-(p-tolyl)saccharin 1 b. Pleasingly, all selected symmetrical aryl and alkyl alkynes reacted smoothly with 1 b to afford the corresponding benzosultams 4 n–u in good yields. The structures of both 4 m and 4 o were unambiguously confirmed by X-ray diffraction analysis. Regarding unsymmetriChem. Eur. J. 2015, 21, 1 – 6
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Scheme 5. Proposed mechanism.
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[7]
[8]
[9] [10]
[11]
Acknowledgements This work was supported by the NNSFC (21172029, 21202016, 21372038), the Ministry of Education of the People’s Republic of China (NCET-13-0714), and the Jilin Provincial Research Foundation for Basic Research (20140519008JH).
[12]
[13]
Keywords: cycloaddition · decarbonylation · homocoupling · nickel · saccharins
[14]
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Received: November 25, 2014 Revised: January 29, 2015 Published online on && &&, 0000
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COMMUNICATION & Decarbonylation
Decarbonylation of saccharins by nickel catalysis has led to the discovery of two novel C C bond-forming reactions; homocoupling to form biaryls, and cycloaddition with alkynes to give benzosultams. The former represents the first nickel-catalyzed decarbonylative C C homocoupling reaction, whereas the latter constitutes a powerful method to pharmaceutically relevant benzosultams with good functionalgroup tolerance and excellent regioselectivity.
P. Mi, P. Liao, T. Tu, X. Bi* && – && Decarbonylative C C Bond-Forming Reactions of Saccharins by Nickel Catalysis: Homocoupling and Cycloaddition
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