title: Platinum-catalyzed enantioselective tandem alkylation/arylation of primary phosphines. Asymmetric synthesis of P-stereogenic 1-phosphaacenaphthenes.
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.
authors.affiliation: Department of Chemistry, Dartmouth College, Hanover, New Hampshire 03755, USA.
authors.forename: Brian J
authors.initials: BJ
authors.lastname: Anderson
authors.forename: Marites A
authors.initials: MA
authors.lastname: Guino-o
authors.forename: David S
authors.initials: DS
authors.lastname: Glueck
authors.forename: James A
authors.initials: JA
authors.lastname: Golen
authors.forename: Antonio G
authors.initials: AG
authors.lastname: DiPasquale
authors.forename: Louise M
authors.initials: LM
authors.lastname: Liable-Sands
authors.forename: Arnold L
authors.initials: AL
authors.lastname: Rheingold