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1,4‐Addition of Bis(iodozincio)methane to α,β‐Unsaturated Ketones: Chemical and Theoretical/Computational Studies
Author(s) -
Sada Mutsumi,
Furuyama Taniyuki,
Komagawa Shinsuke,
Uchiyama Masanobu,
Matsubara Seijiro
Publication year - 2010
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.201000738
Subject(s) - chemistry , silyl enol ether , silylation , exothermic reaction , enol , reagent , ketone , lewis acids and bases , cyclohexanone , medicinal chemistry , zinc , ether , addition reaction , organic chemistry , catalysis
1,4‐Addition of bis(iodozincio)methane to simple α,β‐unsaturated ketones does not proceed well; the reaction is slightly endothermic according to DFT calculations. In the presence of chlorotrimethylsilane, the reaction proceeded efficiently to afford a silyl enol ether of β‐zinciomethyl ketone. The CZn bond of the silyl enol ether could be used in a cross‐coupling reaction to form another CC bond in a one‐pot reaction. In contrast, 1,4‐addition of the dizinc reagent to enones carrying an acyloxy group proceeded very efficiently without any additive. In this case, the product was a 1,3‐diketone, which was generated in a novel tandem reaction. A theoretical/computational study indicates that the whole reaction pathway is exothermic, and that two zinc atoms of bis(iodozincio)methane accelerate each step cooperatively as effective Lewis acids.