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Catalytic Selective Dihydrosilylation of Internal Alkynes Enabled by Rare‐Earth Ate Complex
Author(s) -
Chen Wufeng,
Song Haibin,
Li Jianfeng,
Cui Chunming
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201913773
Subject(s) - hydrosilylation , chemistry , medicinal chemistry , samarium , aryl , silanes , catalysis , steric effects , alkyl , rare earth , selectivity , yttrium , ligand (biochemistry) , silylation , organic chemistry , mineralogy , oxide , biochemistry , receptor , silane
Hydrosilylation of alkynes generally yield vinylsilanes, which are inert to the further hydrosilylation because of the steric effects. Reported here is the first successful dihydrosilylation of aryl‐ and silyl‐substituted internal alkynes enabled by a rare‐earth ate complex to yield geminal bis‐ and tris(silanes), respectively. The lanthanum bis(amido) ate complex supported by an ene‐diamido ligand proved to be the ideal catalyst for this unprecedented transformation, while the same series of yttrium and samarium alkyl and samarium bis(amido) ate complexes exhibited poor activity and selectivity, indicating significant effects of the ionic size and ate structure of the rare‐earth catalysts.