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

Chemistry : a European Journal
Mutsumi SadaSeijiro Matsubara

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.

References

Apr 1, 1978·Prostaglandins·C D Perchonock, B Loev
Sep 15, 1988·Physical Review A: General Physics·A D Becke
Jan 17, 2002·Journal of the American Chemical Society·André B CharetteJean-François Fournier
Feb 1, 1996·Chemical Reviews·Lutz F. Tietze
Feb 1, 1996·Chemical Reviews·Scott E. Denmark, Atli Thorarensen
Feb 1, 1996·Chemical Reviews·Jeffrey D. Winkler
Dec 19, 1996·Chemical Reviews·Ilane Marek, Jean-F. Normant
Aug 31, 2002·Organic Letters·J Brad ShotwellCraig M Crews
Mar 10, 2005·Chemical Reviews·Julia-Christina WasilkeGuillermo C Bazan
Oct 21, 2005·Organic Letters·Zenichi IkedaSeijiro Matsubara
Nov 16, 2007·Chemical Communications : Chem Comm·Akihiro OoguriSeijiro Matsubara
Jun 2, 2009·Chemical Reviews·Barry B Touré, Dennis G Hall
Dec 24, 2009·Journal of the American Chemical Society·Mutsumi Sada, Seijiro Matsubara
Jul 7, 2008·Advanced Synthesis & Catalysis·Venukrishnan KomanduriMichael J Krische

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