1,4-Addition of bis(iodozincio)methane to α,β-unsaturated ketones: chemical and theoretical/computational studies.

Abstract

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 C--Zn bond of the silyl enol ether could be used in a cross-coupling reaction to form another C--C 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.

DOI: 10.1002/chem.201000738

Cite this paper

@article{Sada201014AdditionOB, title={1,4-Addition of bis(iodozincio)methane to α,β-unsaturated ketones: chemical and theoretical/computational studies.}, author={Mutsumi Sada and Taniyuki Furuyama and Shinsuke Komagawa and Masanobu Uchiyama and Seijiro Matsubara}, journal={Chemistry}, year={2010}, volume={16 34}, pages={10474-81} }