Anne M. Hudrlik

Effect of trimethylsilyl groups on Beckmann rearrangements and fragmentations

Abstract Cyclic β-silyl ketones react with hydroxylamine- O -sulfonic acid in water to give as the major products olefinic nitriles resulting from silicon-directed Beckmann fragmentation reactions.

Synthesis of β-silyl ketones via reaction of trimethylsilyllthium with unsaturated hydrazones. Application to the synthesis of brevicomin

Abstract Trimethylsilyllithium undergoes conjugate addition to dimethylhydrazones of α,β-unsaturated ketones. The resulting metalloenamine intermediates can be alkylated, and the resulting hydrazone products cleaved to give α-substituted-β-silyl ketones. These reactions, together with a silicon-directed Baeyer-Villiger reaction, have been applied to the synthesis of brevicomin.

Protiodesilylation reactions of β- and γ-hydroxysilanes: Deuterium labeling and silicon-directed epoxide openings

Abstract Protiodesilylation reactions of β-hydroxysilanes are catalyzed by crown ether, can be used to introduce deuterium, and can be used to prepare silicon-free products of silicon-directed epoxide openings; similar reactions of γ-hydroxysilanes are possible.

Base-induced reactions of α,β-dihydroxysilanes: stereochemistry and mechanisms

Abstract Cyclic α,β-dihydroxysilanes undergo base-induced elimination reactions if the silicon and the β-OH can be anti; otherwise protiodesilylation predominates.

Stereospecific synthesis of enamines from α,β-epoxysilanes

Abstract Isomerically pure cis and trans enamines were prepared from α,β-epoxysilanes by alumina-assisted ring opening with pyrrolidine and morpholine followed by β-elimination.

Preparation of O-(Silyl)benzyl Alcohols

Abstract Abstract: γ-Hydroxysilanes 4 can be easily prepared from bromosilyl ethers 3 by a reaction involving 1,4-migration of the silicon group from oxygen to carbon.

Migration of trimethylsilyl groups in enolates of silyl esters

Abstract The lithium enolate of trimethylsilyl acetate ( 1 ) undergoes a 1,3-O → C migration of the trimethylsilyl group.