Cross‐Coupling of Allenamides and C‐Based Nucleophiles by Pd‐Catalyzed Allylic Alkylation

Abstract

Pd-catalyzed allylic alkylation of C-based nucleophiles using both chiral and achiral allenamides is described. High yields were obtained to provide synthetically valuable (E)-enamide products in high E : Z-selectivity while generating a quaternary carbon atom. Some potential stereocontrolled applications of the resultant (E)-enamide functionality are described.

Boron-Catalyzed, Diastereo- and Enantioselective Allylation of Ketones with Allenes

“… 31 The only exception being copper-catalyzed examples which use allenes and hydrosilanes as the terminal reductant to give stereoselective ketone allylation ( Figure 1 b). 32 − 39 There are no examples of this reaction using a main-group catalyst or applications to allylboration.…”

“…The prior preparation of an allylic coupling partner was required for many catalytic allylation reactions. ,− Typically these prefunctionalized substrates are prepared by transition metal catalysis or using Grignard reagents . The only exception being copper-catalyzed examples which use allenes and hydrosilanes as the terminal reductant to give stereoselective ketone allylation (Figure b). − There are no examples of this reaction using a main-group catalyst or applications to allylboration.…”