Asymmetric Allylic Alkylation with ‘Hard’ Amide Carbanions

Abstract

Until the work of Trost and Schroeder (J. Am. Chem. Soc. 1999, 121, 6759), transition-metal-catalyzed asymmetric allylic alkylation (AAA) reactions were confined to the use of ‘soft’, stabilized carbanions. However, general methods to apply carboxylic acid carb­anions in AAA reactions remain undeveloped. As a large step forward, the authors report the use of acyclic amides as nucleophiles in the Pd-catalyzed AAA reaction with 1,1′-P,N ferrocene ligand L1. Alkylation of a variety of α-substituted aliphatic and aromatic amides proceeded in high yield with good to high levels of asymmetric induction.