Copper-catalyzed asymmetric allylic substitution of racemic/meso substrates

Abstract

The synthesis of enantiomerically pure compounds is a pivotal subject in the field of chemistry. Enantioselective catalysis currently stands as the primary approach for delivering a singular enantiomer. Among these...

Desymmetrization of Inert meso-Diethers through Copper-Catalyzed Asymmetric Allylic Alkylation with Grignard Reagents

“…The enantioselective desymmetrization of meso compounds is indeed a potent tool for the synthesis of enantiomerically enriched molecules, enabling the formation of multiple stereogenic centers in a single step. − The desymmetrization of meso -diol derivatives via transition-metal-catalyzed asymmetric allylic alkylation (AAA) has emerged as one of the most effective strategies for C–C bond-forming reactions. − While the use of stabilized nucleophiles (p K a < 25) in Pd-catalyzed desymmetrization processes has been particularly successful for the synthesis of natural products and derivatives, − the use of nonstabilized nucleophiles (p K a > 25) in Cu-catalyzed desymmetrization processes of meso starting materials has been less explored. Inspired by the pioneering work conducted by the Feringa group in 2000, the Gennari, Feringa, and Sawamura groups reported a series of Cu-catalyzed desymmetrization reactions involving meso -bisphosphates with alkylzinc reagents or allylic boronates.…”