Nickel-catalyzed hydroalkylation of 1,3-dienes with malonates using a homoallyl carbonate as the 1,3-diene and hydride source

The use of a malonate nucleophile in the transition metal-catalyzed hydroalkylation of 1,3-dienes remains immature. Herein, we report the nickel-catalyzed hydroalkylation of 1,3-dienes with malonates using a homoallyl carbonate as the 1,3-diene and hydride source. A broad range of homoally carbonates and malonate derivatives were well tolerated under a Ni/DPEphos catalyst system, providing the corresponding 1,2-hydroalkylation products in 40-94% yields with excellent regioselectivity (32 examples). We also suggested the possible reaction mechanism for the nickel-catalyzed hydroalkylation of in situ generated 1,3-dienes with malonates. (C) 2021 Elsevier Ltd. All rights reserved.

Automated summary

This study reported the nickel-catalyzed hydroalkylation of 1,3-dienes with malonates using a homoallyl carbonate as the 1,3-diene and hydride source. Various homoallyl carbonates and malonate derivatives were well tolerated under a Ni/DPEphos catalyst system, providing high yields and regioselectivity for the 1,2-hydroalkylation products. The possible reaction mechanism for this nickel-catalyzed hydroalkylation was also proposed.