Iridium-Catalyzed Double Convergent 1,3-Rearrangement/Hydrogenation of Allylic Alcohols

Enantioconvergent catalysis has the potential to convert different isomers of a starting material to a single highly enantioenriched product. Here we report a novel enantioselective double convergent 1,3-rearrangement/hydrogenation of allylic alcohols using an Ir-N,P catalyst. A variety of allylic alcohols, each consisting of a 1:1:1:1 mixture of four isomers, were converted to the corresponding tertiary alcohols with two contiguous stereogenic centers, in up to 99% ee and 99:1 d.r. DFT calculations, and control experiments suggest that the 1,3-rearrangement is the crucial stereodetermining element of the reaction.

Automated summary

Enantioconvergent catalysis allows for the conversion of different isomers of a starting material to a single highly enantioenriched product. The study presents a novel enantioselective double convergent 1,3-rearrangement/hydrogenation of allylic alcohols using an Ir-N,P catalyst, achieving high enantioselectivity and diastereomeric ratio. DFT calculations and control experiments demonstrate the significance of the 1,3-rearrangement in determining the stereochemistry of the reaction.