期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 57, 期 4, 页码 923-928出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201710206
关键词
alkynes; homogeneous catalysis; hydrosilylation; manganese; selectivity
资金
- NSFC [21472194, 21772202, 21521002]
- Alexander von Humboldt Foundation
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.
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