Organocatalytic aryl-aryl bond formation: An atroposelective [3,3]-rearrangement approach to BINAM derivatives

Gong Qiang Li, Hongyin Gao, Craig Keene, Michael Devonas, Daniel H. Ess, László Kürti

Research output: Contribution to journalArticle

153 Scopus citations

Abstract

Herein we disclose an organocatalytic aryl-aryl bond-forming process for the regio- and atroposelective synthesis of 2,2′-diamino-1,1′- binaphthalenes (BINAMs). In the presence of catalytic amounts of axially chiral phosphoric acids, achiral N,N′-binaphthyl hydrazines undergo a facile [3,3]-sigmatropic rearrangement to afford enantiomerically enriched BINAM derivatives in good to excellent yield. This transformation represents the first example of a metal-free, catalytic C(sp2)-C(sp2) bond formation between two aromatic rings with concomitant de novo atroposelective installation of an axis of chirality. Density functional calculations reveal that, in the transition state for C-C bond formation, the phosphoric acid proton of the catalyst is fully transferred to one of the N-atoms of the substrate, and the resulting phosphate acts as a chiral counterion.

Original languageEnglish (US)
Pages (from-to)7414-7417
Number of pages4
JournalJournal of the American Chemical Society
Volume135
Issue number20
DOIs
StatePublished - May 22 2013

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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