Generation of Dithianyl and Dioxolanyl Radicals Using Photoredox Catalysis: Application in the Total Synthesis of the Danshenspiroketallactones via Radical Relay Chemistry

Org Lett. 2019 Mar 15;21(6):1708-1712. doi: 10.1021/acs.orglett.9b00271. Epub 2019 Feb 26.

Abstract

Visible-light-induced generation of dithianyl and dioxolanyl radicals via selective hydrogen atom transfer (HAT) has been achieved. This radical relay tactic enables remote C(sp3)-H functionalization to permit rapid access to polyol and spiroketal segments, and in turn has been exploited as a key synthetic construct in the total synthesis of the danshenspiroketallactones. The conformational stability of the danshenspiroketallactones has also been defined via experiments and DFT calculations.

Publication types

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

MeSH terms

  • Catalysis
  • Hydrogen / chemistry*
  • Light
  • Molecular Structure
  • Photochemical Processes
  • Polymers / chemistry*

Substances

  • Polymers
  • polyol
  • Hydrogen