Palladium-catalyzed addition and carbonylative addition of diaryl disulfides and diselenides to terminal acetylenes

Kuniyasu, Hitoshi; Ogawa, Akira; Miyazaki, Shin Ichiro; Ryu, Ilhyong; Kambe, Nobuaki; Sonoda, Noboru

doi:10.1021/ja00026a013

Cited by 251 publications

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“…[6,12,15,16] A similar behaviour was found for the nickel complexes as well (Table 6). Addition of P(OPh) 3 , P(OBu) 3 , P(O-i-Pr) 3 or DPPE to the catalytic system facilitated the formation of compound 3 (Table 6, entries 2 -5).…”

Section: Full Paperssupporting

confidence: 80%

“…In contrast to NiCl 2 , phosphine complexes of palladium are efficient catalysts of the PhS-SPh addition to alkynes. [15,16] It is interesting to understand the role of the amine in the studied reaction. The mechanism of the reaction may include generation of the nucleophilic anion PhS À from PhSH, followed by substitution of chloride ligands in NiCl 2 by PhS À .…”

Section: Full Papersmentioning

confidence: 99%

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Nickel(II) Chloride‐Catalyzed Regioselective Hydrothiolation of Alkynes

et al. 2005

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Regioselective Markovnikov-type addition of PhSH to alkynes (HC C-R) has been performed using easily available nickel complexes. The non-catalytic side reaction leading to anti-Markovnikov products was suppressed by addition of g-terpinene to the catalytic system. The other side reaction leading to the bis(phenylthio)alkene was avoided by excluding phosphine and phosphite ligands from the catalytic system. It was found that catalytic amounts of Et 3 N significantly increased the yield and selectivity of the catalytic reaction. Under optimized conditions high product yields of 60 -85% were obtained for various alkynes [R ¼ n-C 5 H 11 , CH 2 NMe 2 , CH 2 OMe, CH 2 SPh, C 6 H 11 (OH), (CH 2 ) 3 CN]. The X-ray structure of one of the synthesized products is reported.

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confidence: 80%

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confidence: 99%

Nickel(II) Chloride‐Catalyzed Regioselective Hydrothiolation of Alkynes

et al. 2005

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“…Only diaryl dichalcogenides showed good reactivity in the studied reaction, while nBu 2 Se 2 (24 % yield; R = nC 6 H 13 ) and (PhCH 2 Se) 2 (no product) were dramatically less active. [24,25] Scheme 2.…”

Section: Introductionmentioning

confidence: 99%

“…[24] A plausible catalytic reaction mechanism involves the following steps (Scheme 3): 1) oxidative addition of the E-E bond to Pd 0 , 2) alkyne coordination to the metal center, 3) alkyne insertion into the M-E bond, and 4) C-E reductive elimination to afford the product 2 and to regenerate Pd 0 . This represents a general framework of transition metal-catalyzed E-E bond addition to unsaturated molecules.…”

Section: Introductionmentioning

confidence: 99%

Unusual Influence of the Structures of Transition Metal Complexes on Catalytic C–S and C–Se Bond Formation Under Homogeneous and Heterogeneous Conditions

2007

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In the presence of transition metal catalysts, hydrothiolation and hydroselenation reactions, as well as bisthiolation and bisselenation reactions, have been successfully carried out with high selectivities and yields. New transition metal-catalyzed synthetic methods have been developed for the preparation of vinyl sulfides and vinyl selenides of various types. Mechanistic study has revealed that a homogeneous catalytic system based on phosphine complexes of palladium is the

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“…Unlike the reaction of alkynes, the reaction of allene is accompanied by hydride transfer.Keywords: (E)-2-(alkylthio)alka-1,3-diene; allene; diselenide; disulfide; hydride transfer; rhodium Reaction of organic disulfides or diselenides with unsaturated compounds catalyzed by a transition metal complex is becoming one of the important methodologies for the synthesis of organosulfur and organoselenium compounds.[1] The cis-addition of disulfides and diselenides to alkynes and alkenes with S-S and SeSe bond cleavage has been studied by others [2] and by us. [3] We have shown that a catalyst system of a rhodiumphosphine complex and trifluoromethanesulfonic acid is effective not only for the addition of aromatic disulfides to alkynes but also of aliphatic disulfides.…”

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Transition Metal‐Catalyzed Synthesis of (E)‐2‐(Alkylthio)alka‐1,3‐dienes from Allenes and Dialkyl Disulfides with Concomitant Hydride Transfer

et al. 2003

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Reaction of dialkyl disulfides or diselenides with allenes is catalyzed by a rhodiumphosphine complex and trifluoromethanesulfonic acid giving (E)-2-alkylthio(seleno)-1,3-dienes and (E)-2-alkylthio(seleno)-2-alkenes. Unlike the reaction of alkynes, the reaction of allene is accompanied by hydride transfer.Keywords: (E)-2-(alkylthio)alka-1,3-diene; allene; diselenide; disulfide; hydride transfer; rhodium Reaction of organic disulfides or diselenides with unsaturated compounds catalyzed by a transition metal complex is becoming one of the important methodologies for the synthesis of organosulfur and organoselenium compounds.[1] The cis-addition of disulfides and diselenides to alkynes and alkenes with S-S and SeSe bond cleavage has been studied by others [2] and by us. [3] We have shown that a catalyst system of a rhodiumphosphine complex and trifluoromethanesulfonic acid is effective not only for the addition of aromatic disulfides to alkynes but also of aliphatic disulfides. [3] Notably, when allene is employed as the substrate, concomitant hydride transfer takes place giving (E)-2-alkylthio(seleno)-1,3-dienes and (E)-2-alkylthio(seleno)-2-alkenes. The results are contrasted to the fact that organic disulfides and diselenides undergo 1,2-addition to allenes under radical conditions.[4] Previous syntheses of (E)-2-(alkylthio)alka-1,3-dienes employed stepwise methods, [5,6] and the present reaction provides a convenient access to such organosulfur and organoselenium compounds.When undeaca-1,2-diene 1a was treated with dibutyl disulfide 2a (0.5 equiv.) in the presence of RhH(PPh 3 ) 4 (3 mol %), tris(p-tolyl)phosphine (12 mol %), and trifluoromethanesulfonic acid (3 mol %) in refluxing acetone for 2 h, (E)-2-(butylthio)undeca-1,3-diene (E)-3a and (E)-2-butylthio-2-undecene (E)-4a were obtained in 47% and 47% yields, respectively (Table 1, entry 1).The stereochemistry of (E)-3a was determined by the 1 H-NMR coupling constant (J 15.6 Hz) and that of (E)-4a by the NOE between 1-and 4-protons. Both the rhodium complex and trifluoromethanesulfonic acid are essential, and no reaction occurs in the absence of either of the reagents. Addition of tris(p-tolyl)phosphine increases the yields (vide infra). Since allene 1a is used for the acceptor of thiol giving (E)-4a, the yield of (E)-3a does not exceed 50%. The mass balance, however, is almost quantitative. The reaction can be applied to various combinations of monosubstituted allenes and aliphatic disulfides (Table 1). A 1,3-diene derived from diphenyl disulfide is relatively unstable, and decomposes during silica gel chromatography (entry 8). A cystine derivative (R,R)-2b gives the adducts (R,E)-3b and (R,E)-4b without racemization (Scheme 1): Reaction of (R,R)-2b containing 3% of meso-2b gives (R,E)-3b and (R,E)-4b in more the 97% ee.Alkyl diselenides react similarly. When 1a was treated with dioctyl diselenide 5a (0.5 equiv.) in the presence of RhH(PPh 3 ) 4 (5 mol %), tris(p-chlorophenyl)phosphine (15 mol %), and trifluoromethanesulfonic acid (5 mol %) in refl...

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Palladium-catalyzed addition and carbonylative addition of diaryl disulfides and diselenides to terminal acetylenes

Cited by 251 publications

References 0 publications

Nickel(II) Chloride‐Catalyzed Regioselective Hydrothiolation of Alkynes

Nickel(II) Chloride‐Catalyzed Regioselective Hydrothiolation of Alkynes

Unusual Influence of the Structures of Transition Metal Complexes on Catalytic C–S and C–Se Bond Formation Under Homogeneous and Heterogeneous Conditions

Transition Metal‐Catalyzed Synthesis of (E)‐2‐(Alkylthio)alka‐1,3‐dienes from Allenes and Dialkyl Disulfides with Concomitant Hydride Transfer

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