Catalytic reductive [4 + 1]-cycloadditions of vinylidenes and dienes

Cycloaddition reactions provide direct and convergent routes to cycloalkanes, making them valuable targets for the development of synthetic methods. Whereas six-membered rings are readily accessible from Diels-Alder reactions, cycloadditions that generate five-membered rings are comparatively limited in scope. Here, we report that dinickel complexes catalyze [4 + 1]-cycloaddition reactions of 1,3-dienes. The C1 partner is a vinylidene equivalent generated from the reductive activation of a 1,1-dichloroalkene in the presence of stoichiometric zinc. Intermolecular and intramolecular variants of the reaction are described, and high levels of asymmetric induction are achieved in the intramolecular cycloadditions using a C2-symmetric chiral ligand that stabilizes a metal-metal bond.

Source: ScienceNOW - February 21, 2019 Category: Science Authors: Zhou, Y.-Y., Uyeda, C. Tags: Chemistry reports Source Type: news