Synthesis of 2,3-Dihydro-1-phenylbenzo[<i>b</i>]phosphole (1-Phenylphosphindane) and Its Use as a Mechanistic Test in the Asymmetric Appel Reaction: Decisive Evidence against Involvement of Pseudorotation in the Stereoselecting Step

Abstract

Racemic 2,3-dihydro-1-phenylbenzo[b]phosphole was obtained by reduction of 1-phenylbenzo[b]phosphole-1-oxide, itself derived by ring-closing metathesis of phenylstyrylvinylphosphine oxide. The title compound was then reoxidized under asymmetric Appel conditions. Comparison of the sense and degree of the stereoselectivity to those obtained with an open-chain analogue indicated that the ring system does not affect the selectivity of the process. This in turn strongly suggests that the stereoselection is not related to pseudorotamer preferences in putative phosphorane intermediates.