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

J Am Chem Soc. 2023 Jan 11;145(1):626-633. doi: 10.1021/jacs.2c11289. Epub 2022 Dec 19.

Abstract

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.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Alcohols*
  • Catalysis
  • Hydrogenation
  • Iridium*
  • Stereoisomerism

Substances

  • Iridium
  • allyl alcohol
  • Alcohols