Rudolf Pock

Electrophilic attack at allylsilanes: a quantitative determination of the β-silyl effect

The relative reactivities of allylsilanes and alkenes towards diarylmethyl cations have been determined by competition experiments. Introduction of a β-trimethylsilyl group increases the reactivity of propene towards the diphenylmethyl cation by a factor of 30700.

Synthesis of γ-lactones from alkenes employing p-methoxybenzyl chloride as +CH2CO−2 equivalent☆

The ZnCl2 catalyzed reaction of p-methoxybenzyl chloride with alkenes yields the 1:1 addition products 3, which are converted into the γ-lactones 4 via Ru(VIII) catalyzed oxidative degradation of the aromatic ring.

Relative reactivities of alkenes toward the diphenylmethyl cation

The relative reactivities of alkyl and phenyl substituted alkenes toward diphenylmethyl chloride/ZnCl2/Et2O in dichloromethane at −78°C have been determined by competition experiments. The transition state structure is discussed.