51.  "Platinum-Catalyzed Enantioselective Tandem Alkylation/Arylation of Primary Phosphines. Asymmetric Synthesis of P-Stereogenic 1-Phosphaacenaphthenes." Anderson, B. J.; Guino-o, M. A.; Glueck, D. S.; Golen, J. A.; DiPasquale, A. G.; Liable-Sands, L. M.; Rheingold, A. L. Org. Lett. 2008, 10, 4425–4428.

Abstract

Abstract: Enantioselective tandem alkylation/arylation of primary phosphines with 1-bromo-8-chloromethylnaphthalene catalyzed by Pt(DuPhos) complexes gave P-stereogenic 1-phosphaacenaphthenes (AcePhos) in up to 74% ee. Diastereoselective formation of four P C bonds in one pot with bis(primary) phosphines gave C₂-symmetric diphosphines, including the o-phenylene derivative DuAcePhos, for which the rac isomer was formed with high enantioselectivity. These reactions, which appear to proceed via an unusual metal-mediated nucleophilic aromatic substitution pathway, yield a new class of heterocycles with potential applications in asymmetric catalysis.