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Promoting the Hydrosilylation of Benzaldehyde by Using a Dicationic Antimony‐Based Lewis Acid: Evidence for the Double Electrophilic Activation of the Carbonyl Substrate
Author(s) -
Hirai Masato,
Cho Junsang,
Gabbaï François P.
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201600971
Subject(s) - chemistry , benzaldehyde , electrophile , lewis acids and bases , dication , adduct , hydrosilylation , substrate (aquarium) , antimony , medicinal chemistry , catalysis , aldehyde , silylation , denticity , photochemistry , organic chemistry , crystal structure , molecule , oceanography , geology
The concomitant activation of carbonyl substrates by two Lewis acids has been investigated by using [1,2‐(Ph 2 MeSb) 2 C 6 H 4 ] 2+ ([ 1 ] 2+ ), an antimony‐based bidentate Lewis acid obtained by methylation of the corresponding distibine. Unlike the simple stibonium cation [Ph 3 MeSb] + , dication [ 1 ] 2+ efficiently catalyzes the hydrosilylation of benzaldehyde under mild conditions. The catalytic activity of this dication is correlated to its ability to doubly activate the carbonyl functionality of the organic substrate. This view is supported by the isolation of [ 1 ‐μ 2 ‐DMF][OTf] 2 , an adduct, in which the DMF oxygen atom bridges the two antimony centers.