Palladium optically phosphine complex

Asymmetric hydrosilylation of prochiral olefins, e.g. 1,1-disubstituted olefins, catalyzed by chiral phosphine complexes of platinum(II) [21], nickel(II) [22], and palladium(II) [23] has been reported. When a platinum complex of the type [L PtCl2]2, where L stands for (/ )-benzylmethylphenylphosphine (BMPP), was used as catalyst, methyldichlorosilane, but not trichlorosilane, reacted satisfactorily- with a-methylstyrene, 2,3-dimethyl-l-butene, and 2-methyl-l-butene to give the corresponding optically active addition products, RMeC HCH2SiMeCl2, R = Ph, /-Pr,... 

Asymmetric decarboxylative rearrangement (Carroll rearrangement) of allyl a-acetamido-/3-ketocarboxylates, catalysed by a palladium complex modified with a chiral phosphine ligand, has been reported to give optically active /,5-unsaturated a-amino ketones with up to 90% ee (Scheme 92).135 The mechanism for the Carroll rearrangement is shown in Scheme 93. 

The coordination chemistry of optically pure, chiral phosphetanes has been studied with special attention to the preparation and characterization of complexes since they are suitable for asymmetric catalytic reactions. The optically active P-menthylphosphetanes showed similar reactivities with usual trivalent phosphines to afford stable palladium(n) and ruthenium complexes, under usual reaction conditions. Similarly, the Pd-allyl complex 28 <1997JOM(529)465> has been prepared from [(allyl)PdCl]2 and was characterized by X-ray crystallography. Reaction of the P(R),C(3 )-2-benzyl-3,3,4,4-tetramethyl-l-menthylphosphetane 64 with Ru3(C0)12/HC02H proceeds normally to give the formato bridged dimer 65 (Figure 11) <1998S1539>. 

Recently, a palladium complex coordinated with an axially chiral, monoden-tate phosphine ligand, MeO-MOP (7a) or its analogs [21], has been reported to be highly effective for the enantioselective hydrosilylation of alkyl-substituted terminal olefins (Scheme 4) [22,23]. Simple terminal olefins 8 were transformed efficiently into the corresponding optically active 2-alkanols 11 with enantiose-lectivities ranging between 94% and 97% ee by the catalytic hydrosilylation-ox-... 

Musco [92] and Consiglio [93] have used palladium-oxazoline complexes (28,29) to produce styrenic copolymers that exhibit high optical rotations. Takaya has briefly noted the use of his novel phosphine-phosphite bi-dentate ligands for the enantioselective production of aromatic polyketones [82]. 

The asymmetric hydrosilylation of 1-alkenes giving highly optically active 2-tri-chlorosilylalkanes is catalyzed by palladium complexes with chiral monodentate binaphthyl phosphine (MOP) ligands. ... 

Asymmetric hydrosilylation of cyclopentadiene and cyclohexa-1,3-diene using chiral phosphine-palladium complexes gives optically active 3-trimethylsilylcyclohex-1-ene after methylation ... 

Asymmetric hydrosilylation of cyclopentadiene and 1,3-cyclohexadiene was performed using chiral phosphine-palladium complexes to give optically active 3-trimethylsilyl-1-cyclopentene95 and 3-trimethylsilyl-l-cyclohexene68, respectively, after methylation (equations 42 and 43). 

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