Equilibrating C-S bond formation by C-H and S-S bond metathesis. Rhodium-catalyzed alkylthiolation reaction of 1-alkynes with disulfides
Equilibrating C-S bond formation by C-H and S-S bond metathesis. Rhodium-catalyzed alkylthiolation reaction of 1-alkynes with disulfides
复制标题
DOI：
10.1021/ja0527121
复制
发表时间：
2005-09-07
影响因子：
15
通讯作者：
Yamaguchi, M
中科院分区：
文献类型：
--
作者：
Arisawa, M;Fujimoto, K;Yamaguchi, M
在RhH(PPh3)4（2 mol %）和1,1′-二苯基膦二茂铁（dppf） （3 mol %）的催化作用下，硅基乙炔与二烷基二硫化物反应，产率高，得到1-烷基硫代-2-三烷基硅基乙炔。在此条件下，释放的烷硫醇不会对反应产生干扰，并且在硅乙炔上加成1-烷基硫代-1-烯烃的量可以最小化。烷基或芳基较大时，烷基乙炔和芳基乙炔也与二硫化物发生反应。二芳基二硫化物在稍作修饰的条件下得到芳硫基衍生物。C−S成键反应是可逆的：在铑催化剂存在下，巯基与1-烷基硫-1-炔反应生成1-炔；烷基硫基交换反应发生在1-烷基硫基-1-炔和二硫化物之间。这是有机分子与C - H和S - S键的平衡氧化反应，形成C - S和S - H键。
In the presence of a catalytic amount of RhH(PPh3)4(2 mol %) and 1,1‘-bis(diphenylphosphino)ferrocene (dppf) (3 mol %), silylacetylenes reacted with dialkyl disulfides giving 1-alkylthio-2-trialkylsilylethynes in high yields. Alkanethiols liberated in this reaction did not interfere with the reaction, and the addition to silylacetylene forming 1-alkylthio-1-alkenes could be minimized under the conditions. Alkylacetylenes and arylacetylenes also reacted with disulfides when the alkyl or aryl groups were bulky. Diaryl disulfides gave arylthio derivatives under slightly modified conditions. The C−S bond-forming reaction is reversible: A reaction of a thiol and a 1-alkylthio-1-alkyne in the presence of the rhodium catalyst gave a 1-alkyne; alkylthio exchange reaction proceeded between a 1-alkylthio-1-alkyne and a disulfide. This is an equilibrating oxidative reaction of organic molecules with C−H and S−S bond metathesis forming C−S and S−H bonds.