title: Organocatalytic aryl-aryl bond formation: an atroposelective [3,3]-rearrangement approach to BINAM derivatives.
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(sp(2))-C(sp(2)) 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.
authors: Division of Chemistry, Department of Biochemistry, University of Texas Southwestern Medical Center, 5323 Harry Hines Boulevard, Dallas, Texas 75390, USA.
authors: Gong-Qiang
authors: GQ
authors: Li
authors: Hongyin
authors: H
authors: Gao
authors: Craig
authors: C
authors: Keene
authors: Michael
authors: M
authors: Devonas
authors: Daniel H
authors: DH
authors: Ess
authors: László
authors: L
authors: Kürti
mesh_terms: D002384:Catalysis; D006834:Hydrazines / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009281:Naphthalenes / Q000138:chemical synthesis* / Q000737:chemistry; D010756:Phosphoric Acids / Q000737:chemistry*
chemical_list: C431663:2,2'-diamino-1,1'-binaphthalene; D006834:Hydrazines; D009281:Naphthalenes; D010756:Phosphoric Acids