198019-34-0Relevant academic research and scientific papers
Preparation of chlorosilyl enolates
Denmark, Scott E.,Stavenger, Robert A.,Winter, Stephen B. D.,Wong, Ken-Tsung,Barsanti, Paul A.
, p. 9517 - 9523 (1998)
A variety of chlorosilyl enolates has been prepared starting from esters, thiol esters, acylsilanes, and ketones. Two general methods are involved, direct enolsilylation with trichlorosilyl triflate and diisopropylethylamine, and a number of methods based on electrophilic substitution of either C- or O-silyl or stannyl carbonyl compounds. The most useful method is a Hg(OAc)2-catalyzed transsilylation from trimethylsilyl to trichlorosilyl enol ethers, providing a wide range of ketone enolates in good to high yield.
The Chemistry of Chlorosilyl Enolates 3.: Variation of the Silyl Group and the Effect on Rate and Enantiomeric Excess of Acetate Aldol Additions
Denmark, Scott E.,Winter, Stephen B. D.
, p. 1087 - 1089 (2007/10/03)
The rales of reaction of the silyl ketene acetals CH2=C(OMe)OSiCl2R (1a-d) with benzaldehyde and pivalaldehyde have been determined and follow the order R = H ～ Cl > Ph > Me. These reactions are promoted by catalytic amounts of a chiral phosphoramide; enantioselectivities of the products obtained show a high sensitivity towards variation of the silyl group. The reactions of the dialkyl substituted chlorosilyl enolates CH2=C(OMe)OSiClR2 (1e,f) with benzaldehyde are not promoted by HMPA.
