Organocatalytic Aryl−Aryl Bond Formation: An Atroposelective [3,3]‑Rearrangement Approach to BINAM Derivatives

Authors

Gong-Qiang Li, Brigham Young University
Hongyin Gao, Brigham Young University
Craig Keene, Brigham Young University
Michael Devonas, Brigham Young University
Daniel H. Ess, Brigham Young University
LaśzlóKürti *, Brigham Young University

Keywords

organocatalytic aryl, aryl bond, atroposelective rearrangement, BINAM derivatives

College

Physical and Mathematical Sciences

Department

Chemistry and Biochemistry

Abstract

Herein we disclose an organocatalytic aryl− aryl bond-forming process for the regio- and atropo- selective 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.

Recommended Citation

Li, Gong-Qiang; Gao, Hongyin; Keene, Craig; Devonas, Michael; Ess, Daniel H.; and *, LaśzlóKürti (2015) "Organocatalytic Aryl−Aryl Bond Formation: An Atroposelective [3,3]‑Rearrangement Approach to BINAM Derivatives," Journal of Undergraduate Research: Vol. 2015: Iss. 1, Article 186.
Available at: https://scholarsarchive.byu.edu/jur/vol2015/iss1/186