Visible-Light-Promoted Biomimetic Reductive Functionalization of Quaternary Benzophenanthridine Alkaloids

J Nat Prod. 2021 Aug 27;84(8):2390-2397. doi: 10.1021/acs.jnatprod.1c00512. Epub 2021 Jul 30.

Abstract

Reduction of an iminium C═N double bond is the most important phase I metabolism process associated with the cytotoxic property of quaternary benzophenanthridine alkaloids (QBAs). Inspired by the light-mediated reduction of QBAs with nicotinamide adenine dinucleotide, a visible-light-promoted reductive functionalization reaction of QBAs is reported in this study. C4-Alkyl-1,4-dihydropyridines (DHPs) enable the direct reductive alkylation of QBA independently, serving as both single-electron-transfer reductant reagents under irradiation with 455 nm blue light in the absence of photocatalysts and additional additives. Our protocol can be further applied to the semisynthesis of natural 6-substituted dihydrobenzophenanthridine derivatives such as O-acetyl maclekarpine E.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Alkylation
  • Benzophenanthridines / chemistry*
  • Benzophenanthridines / radiation effects
  • Biomimetic Materials / chemistry*
  • Biomimetic Materials / radiation effects
  • Electron Transport
  • Light
  • Molecular Structure

Substances

  • Benzophenanthridines