Polarity-Reversed Functionalization of Aliphatic Aldehydes via Divergent Nickel Hydride Catalysis

Abstract

Divergent catalysis represents an exciting frontier for unlocking molecular structural diversity and exploring new activation modes. Here, we report the unexpected discovery of polarity-reversed divergent activation and functionalization of aliphatic aldehydes, where enolizable aliphatic aldehydes are selectively activated by nickel hydride to form two distinct alkylnickel intermediates divergently. This mild and operationally simple process enables the transformation of a wide variety of readily available aliphatic aldehydes, along with alkyl or aryl electrophiles, into the corresponding secondary alcohols or more challenging deoxygenated alkanes with excellent chemoselectivity.