Synthesis of isochromene-type scaffolds via single-flask Diels-Alder-[4 + 2]-annulation sequence of a silyl-substituted diene with menadione

Org Lett. 2014 Jun 20;16(12):3320-3. doi: 10.1021/ol501329t. Epub 2014 Jun 11.

Abstract

A sequential Diels-Alder reaction/silicon-directed [4 + 2]-annulation was developed to assemble hydroisochromene-type ring systems from menadione 2. In the first step, a Diels-Alder of the 1-silyl-substituted butadiene 1 with 2 furnished an intermediate cyclic allylsilane. Subsequently, TMSOTf promoted a [4 + 2]-annulation through trapping of an oxonium, generated by condensation between an aldehyde and the TBS protected alcohol resulted in the formation of a cis-fused hydroisochromene 13.

Publication types

  • Research Support, N.I.H., Extramural

MeSH terms

  • Aldehydes / chemistry
  • Alkenes / chemistry*
  • Benzopyrans / chemical synthesis*
  • Benzopyrans / chemistry
  • Butadienes / chemistry
  • Cycloaddition Reaction
  • Molecular Structure
  • Polyenes / chemistry
  • Silanes / chemistry*
  • Stereoisomerism
  • Vitamin K 3 / chemical synthesis*
  • Vitamin K 3 / chemistry

Substances

  • Aldehydes
  • Alkenes
  • Benzopyrans
  • Butadienes
  • Polyenes
  • Silanes
  • allylsilane
  • Vitamin K 3
  • propylene