Two-Step Substitution Reaction of Phosphonates Carrying a Binaphthyl Group with Grignard Reagents Leading to the Formation of P-Chirogenic Phosphine Oxides

This paper is dedicated to Professor Masahiro Murakami for his contribution to science.

Abstract

The reaction of phosphonates carrying a binaphthyl group with a range of Grignard reagents was complete within two hours at 0 °C to give phosphinates carrying a hydroxybinaphthyl group with high ­efficiency and diastereoselectivity. The resulting phosphinates were further subjected to a substitution reaction with MeMgBr. The reaction at reflux temperature in THF or toluene permitted the formation of P-chirogenic tertiary phosphine oxides with a high enantiomeric ratio. Rare examples of P-chirogenic alkynyl phosphine oxides were also obtained. The sequential one-pot substitution reaction of phosphonates bearing a binaphthyl group with two different Grignard reagents successfully gave the corresponding P-chirogenic phosphine oxides with enantiomeric ratios nearly equal to those of oxides derived from two-step reactions.

Key words

chirogenic compounds - phosphine oxides - binaphthyl phosphonates - chirality transfer reaction - one-pot reaction

Publication History

Received: 25 October 2022

Accepted: 15 November 2022

Accepted Manuscript online:
15 November 2022

Article published online:
01 December 2022

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