Dichotomy of Manganese Catalysis via Organometallic or Radical Mechanism: Stereodivergent Hydrosilylation of Alkynes

被引:109
作者
Yang, Xiaoxu [1 ,2 ]
Wang, Congyang [1 ,2 ]
机构
[1] Chinese Acad Sci, Beijing Natl Lab Mol Sci, CAS Key Lab Mol Recognit & Funct, CAS Res Educ Ctr Excellence Mol Sci,Inst Chem, Beijing 100190, Peoples R China
[2] Univ Chinese Acad Sci, Beijing 100049, Peoples R China
关键词
alkynes; homogeneous catalysis; hydrosilylation; manganese; selectivity; C-H ACTIVATION; STEREOSELECTIVE HYDROSILYLATION; MARKOVNIKOV HYDROSILYLATION; ALKENE HYDROSILYLATION; CARBONYL; REGIO; HYDROSILATION; COMPLEXES; ALDEHYDES; EFFICIENT;
D O I
10.1002/anie.201710206
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Herein, we disclose the first manganese-catalyzed hydrosilylation of alkynes featuring diverse selectivities. The highly selective formation of E-products was achieved by using mononuclear MnBr(CO)(5) with the arsenic ligand, AsPh3. Whereas using the dinuclear catalyst Mn-2(CO)(10) and LPO (dilauroyl peroxide) enabled the reversed generation of Z-products in good to excellent stereo-and regioselectivity. Such a way of controlling the reaction stereoselectivity is unprecedented. Mechanistic experiments revealed the dichotomy of manganese catalysis via organometallic and radical pathways operating in the E- and Z-selective routes, respectively.
引用
收藏
页码:923 / 928
页数:6
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