Enantioselective Approach to (-)-Hamigeran B and (-)-4-Bromohamigeran B via Catalytic Asymmetric Hydrogenation of Racemic Ketone To Assemble the Chiral Core Framework

Org Lett. 2016 Mar 18;18(6):1434-7. doi: 10.1021/acs.orglett.6b00369. Epub 2016 Mar 4.

Abstract

A new strategy featuring an iridium-catalyzed asymmetric hydrogenation of a racemic ketone via dynamic kinetic resolution to generate a cyclopentanol with three contiguous stereocenters and a SmI2-promoted pinacol coupling to install the six-membered ring with correct stereochemistry has been described for the enantioselective total synthesis of (-)-hamigeran B (19 steps, 10.6% overall yield) and (-)-4-bromohamigeran B (19 steps, 12.3% overall yield).

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Biological Products / chemical synthesis*
  • Biological Products / chemistry
  • Catalysis
  • Cyclopentanes / chemical synthesis
  • Cyclopentanes / chemistry
  • Hydrogenation
  • Iridium / chemistry*
  • Ketones / chemistry*
  • Kinetics
  • Molecular Structure
  • Naphthoquinones / chemical synthesis*
  • Naphthoquinones / chemistry
  • Stereoisomerism

Substances

  • 4-bromohamigeran B
  • Biological Products
  • Cyclopentanes
  • Ketones
  • Naphthoquinones
  • hamigeran B
  • cyclopentanol
  • Iridium