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Exploring the Chemoselective Dehydrogenative Silylation and Hydrogenation of Divinyldisiloxane with Hydrosilane from DFT Computation
Author(s) -
Guo CaiHong,
Zhao Yan,
Yang Dandan,
Wang Qiong,
Jiao Haijun
Publication year - 2018
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201701725
Subject(s) - chemoselectivity , silylation , chemistry , catalysis , reductive elimination , cyclopentadienyl complex , medicinal chemistry , acetaldehyde , organic chemistry , combinatorial chemistry , ethanol
The chemoselective dehydrogenative silylation and hydrogenation of 1,3‐divinyldisiloxane by using HSiMe 3 catalyzed by CpFe(CO) 2 Me (Cp = η 5 ‐cyclopentadienyl) was explored by DFT computations. The active catalyst, CpFe(CO)SiMe 3 , was generated from a CO‐assisted pathway and HSiMe 3 ‐initiated acetaldehyde reductive elimination. Starting from the active catalyst, the dehydrogenative silylation step of the first vinyl group was found to be the rate‐determining step, and the subsequent chemoselective hydrogenation step of the second vinyl group was discovered to be kinetically more favored. Within the reaction, the oxygen atom of 1,3‐divinyldisiloxane was not found to play a role in competitive coordination. The computed results rationalize the experimentally observed chemoselectivity.