94501-32-3Relevant academic research and scientific papers
Organocatalytic aryl-aryl bond formation: An atroposelective [3,3]-rearrangement approach to BINAM derivatives
Li, Gong-Qiang,Gao, Hongyin,Keene, Craig,Devonas, Michael,Ess, Daniel H.,Kürti, László
, p. 7414 - 7417 (2013)
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.
