C2-Symmetric Dinickel Catalysts for Enantioselective [4 + 1]-Cycloadditions

J Am Chem Soc. 2020 Oct 14;142(41):17294-17300. doi: 10.1021/jacs.0c08262. Epub 2020 Sep 30.

Abstract

Dinickel naphthyridine-bis(oxazoline) catalysts promote enantioselective intermolecular [4 + 1]-cycloadditions of vinylidene equivalents and 1,3-dienes. The products of this reaction are methylenecyclopentenes, and the exocyclic alkene is generally obtained with high Z selectivity. E- and Z-dienes react in a stereoconvergent fashion, providing cycloadducts with the same sense of absolute stereochemistry and nearly identical ee values. This feature allows dienes that are commercially available as E/Z mixtures to be used as substrates for the cycloaddition. A DFT model for the origin of asymmetric induction is provided.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Alkenes / chemistry*
  • Catalysis
  • Coordination Complexes / chemistry*
  • Cycloaddition Reaction
  • Density Functional Theory
  • Models, Molecular
  • Molecular Structure
  • Naphthyridines / chemistry*
  • Nickel / chemistry*
  • Oxazoles / chemistry
  • Stereoisomerism
  • Zinc / chemistry*

Substances

  • Alkenes
  • Coordination Complexes
  • Naphthyridines
  • Oxazoles
  • Nickel
  • Zinc