TY - JOUR
T1 - Organocatalytic aryl-aryl bond formation
T2 - An atroposelective [3,3]-rearrangement approach to BINAM derivatives
AU - Li, Gong Qiang
AU - Gao, Hongyin
AU - Keene, Craig
AU - Devonas, Michael
AU - Ess, Daniel H.
AU - Kürti, László
PY - 2013/5/22
Y1 - 2013/5/22
N2 - 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.
AB - 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.
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U2 - 10.1021/ja401709k
DO - 10.1021/ja401709k
M3 - Article
C2 - 23659490
AN - SCOPUS:84878219684
SN - 0002-7863
VL - 135
SP - 7414
EP - 7417
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 20
ER -