Precatalyst-Enabled Selectivity: Enantioselective NiH-Catalyzed anti-Hydrometalative Cyclization of Alkynones to Endo- and Hetero-cyclic Allylic Alcohols

A highly enantioselective NiH-catalyzed hydrocyclization of alkynones with unparalleled anti- and endocyclic selectivities is described. The choice of the precatalysts has significant influence in tuning the regio- and enantioselectivity. Using Ni(OTs)(2)/Phox as a precatalyst and (EtO)(2)MeSiH as a hydride source, an array of enantioenriched O-, N-, and S-containing heterocyclic tertiary allylic alcohols are obtained in 24-81 % yields with 80:20-99:1 er. Mechanistic investigations and synthetic application are also carried out. This study represents an efficient access to a set of allylic alcohols that are unable to access by the state-of-the-art coupling reactions.

Automated summary

This study presents a highly enantioselective NiH-catalyzed hydrocyclization of alkynones, yielding an array of enantioenriched heterocyclic tertiary allylic alcohols. The choice of precatalysts significantly influences the selectivity of the products, with yields reaching up to 81%.