P-Stereogenic monophosphines in Pd-catalysed enantioselective hydrovinylation of styrene

Two groups of P-stereogenic monodentate phosphines containing pendant groups bearing functionalities capable of having secondary interactions, PArPhR (Ar = 2-[(2′,6′-dimethoxy)-1,1′-biphenylyl] and R = OMe (6) or Me (8)) and PMeR(CH2R′) (13, R = t-Bu or 14 R = Fc and R′ = SiMe3 (a), SiMe2Ph (b) or CH 2(2-naphthyl) (c)) have been prepared in enantiomerically pure form by the Jugé and Evans methodologies and characterised, including the crystal structure for the borane adduct of 12b. Reaction of the phosphines with the Pd dimer [Pd(η3-2-Me-allyl)(μ-Cl)]2 produced neutral allylic complexes C [PdCl(η3-2-Me-C3H 4)P], which have been characterised in solution and shown to be a mixture of isomers with different absolute configuration at the Pd atom. After abstraction of the chloride ligand by AgBF4, the solutions of cationic complexes have been used as catalyst precursors in the hydrovinylation of styrene under mild conditions. Very good activities (up to 1015 h -1), moderate to good selectivities to 3-phenyl-1-butene and low to moderate enantioselectivities (<45% ee) have been found. Deep differences in the activity and enantioselectivity have been found depending on the structure of the ligand. In spite of that the results did not permit to confirm the improvement of the selectivities of the reaction by stabilization of the catalyst through secondary coordination with the potentially hemilabile ligands. © 2011 Elsevier B.V. All rights reserved.