Catalytic Asymmetric [4+2]-Cycloaddition of Dienes with Aldehydes

J Am Chem Soc. 2017 Oct 4;139(39):13656-13659. doi: 10.1021/jacs.7b08357. Epub 2017 Sep 25.

Abstract

Despite its significant potential, a general catalytic asymmetric [4+2]-cycloaddition of simple and electronically unbiased dienes with any type of aldehyde has long been unknown. Previously developed methodologies invariably require activated, electronically engineered substrates. We now provide a general solution to this problem. We show that highly acidic and confined imidodiphosphorimidates (IDPis) are extremely effective Brønsted acid catalysts of the hetero-Diels-Alder reaction of a wide variety of aldehydes and dienes to give enantiomerically enriched dihydropyrans. Excellent stereoselectivity is generally observed and a variety of scents and natural products can be easily accessed.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Acids / chemistry*
  • Aldehydes / chemistry*
  • Alkadienes / chemistry*
  • Catalysis
  • Cycloaddition Reaction
  • Molecular Structure

Substances

  • Acids
  • Aldehydes
  • Alkadienes