Functionalized Organomagnesium Compounds: Synthesis and Reactivity

Abstract

Introduction Preparation of Functionalized Grignard Reagents Reactivity of Grignard Reagents

Asymmetric addition of Grignard reagents to ketones: culmination of the ligand-mediated methodology allows modular construction of chiral tertiary alcohols

“…Since Victor Grignard's early work at the beginning of the 20 th century, 1 organomagnesium reagents have been established as an essential tool in organic chemistry, gaining a central role in a broad range of transformations and synthetic applications, 2 and remain the privileged subject of ongoing research interest today. 3 Among the variety of applications offered by organomagnesium species, 4 the asymmetric 1,2-addition of Grignard reagents to prochiral ketones has emerged as a powerful strategy providing access to non-racemic tertiary alcohols, 5 widespread structural motifs and valuable synthetic intermediates for the preparation of complex chiral scaffolds, bioactive targets and APIs. 6 Owing to the synthetic flexibility of the 3-disconnection approach, the Grignard synthesis enables the straightforward and modular construction of molecular complexity from simple and cheap substrates ( Scheme 1 ).…”

Sodium-Mediated Reductive anti-Dimagnesiation of Diarylacetyl­enes with Magnesium Bromide

“…3 Naturally, methods to generate Grignard reagents have also been an important subject of investigation. 4 Typical approaches to the reagents include reduction of organic halides with magnesium metal 5 and halogen-magnesium exchange 6 (Scheme 1A). However, these approaches rely on organic halide precursors, thereby limiting accesses to certain organomagnesium compounds such as vicinal dimagnesio species due to inevitably rapid -elimination from 1-magnesio-2-halo intermediates (Scheme 1B).…”