Functional group transformations in derivatives of 6-oxoverdazyl

J Org Chem. 2013 Aug 2;78(15):7445-54. doi: 10.1021/jo400843y. Epub 2013 Jul 9.

Abstract

Transformations of functional groups, such as OCH2Ph, OCOPh, NO2 and I, in 1,3,5-triphenyl-6-oxoverdazyls 1a-1e were investigated in order to expand the range of synthetic tools for incorporation of the verdazyl system into more complex molecular architectures and to increase spin delocalization. Thus, Pd-catalyzed debenzylation of the OCH2Ph group or basic hydrolysis of the OCOPh group gave the phenol functionality, which was acylated, but could not be alkylated. Orthogonal deprotection of diphenol functionality was also demonstrated in radical 1c. Pt-catalyzed reduction of the NO2 group led to the aniline derivative, which was acylated. Attempted C-C coupling reactions to iodophenyl derivatives 1e and 5e were unsuccessful. Selected verdazyl radicals were characterized by EPR and electronic absorption spectroscopy, and results were analyzed with the aid of DFT computational methods.

Publication types

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

MeSH terms

  • Free Radicals / chemical synthesis
  • Free Radicals / chemistry
  • Heterocyclic Compounds / chemical synthesis
  • Heterocyclic Compounds / chemistry*
  • Molecular Structure
  • Quantum Theory

Substances

  • Free Radicals
  • Heterocyclic Compounds