Journal of Undergraduate Research


organocatalytic aryl, aryl bond, atroposelective rearrangement, BINAM derivatives


Physical and Mathematical Sciences


Chemistry and Biochemistry


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.

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