Markovnikov Hydrosilylation of Alkynes with Tertiary Silanes Catalyzed by Dinuclear Cobalt Carbonyl Complexes with NHC Ligation
作者:Dongyang Wang、Yuhang Lai、Peng Wang、Xuebing Leng、Jie Xiao、Liang Deng
DOI:10.1021/jacs.1c06583
日期:2021.8.18
with PhC≡CH and HSiEt3 can furnish the dinuclear cobalt alkyne and mononuclear cobalt silyl complexes [(IPr)(CO)2Co(μ–η2:η2-HCCPh)Co(CO)3], [(IPr)(CO)2Co(μ-η2:η2-HCCPh)Co(CO)2(IPr)], and [(IPr)Co(CO)3(SiEt3)], respectively. Both dicobalt bridging alkyne complexes can react with HSiEt3 to yield α-triethylsilyl styrene and effect the catalytic Markovnikov hydrosilylation reaction. However, the mono(NHC)
炔烃的金属催化氢化硅烷化是制备乙烯基硅烷的理想原子经济方法,乙烯基硅烷是有机合成和有机硅工业中的有用试剂。尽管通过炔烃的金属催化氢化硅烷化反应制备 β-乙烯基硅烷已取得巨大成功,但报道的用于合成 α-乙烯基硅烷的金属催化反应存在底物范围窄和/或选择性差的问题。在此,我们使用羰基N-杂环卡宾 (NHC) 配合物 [(IPr) 2 Co 2 (CO) 6] (IPr = 1,3-二(2,6-二异丙基苯基)咪唑-2-亚基)作为催化剂。这种钴催化剂影响烷基和芳基取代的末端炔烃与各种具有良好官能团相容性的叔硅烷的氢化硅烷化,从而提供具有高产率和高α / β选择性的α-乙烯基硅烷。机理研究表明[(IPr) 2 Co 2 (CO) 6 ]与PhC≡CH和HSiEt 3的化学计量反应可以提供双核钴炔和单核钴甲硅烷基配合物[(IPr)(CO) 2 Co(μ– η 2 :η 2 -HCCPh)Co(CO) 3