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Dichotomy of Manganese Catalysis via Organometallic or Radical Mechanism: Stereodivergent Hydrosilylation of Alkynes
Author(s) -
Yang Xiaoxu,
Wang Congyang
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201710206
Subject(s) - hydrosilylation , manganese , regioselectivity , stereoselectivity , catalysis , chemistry , ligand (biochemistry) , peroxide , organometallic chemistry , combinatorial chemistry , reaction mechanism , medicinal chemistry , organic chemistry , biochemistry , receptor
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, AsPh 3 . 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.