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The organopalladium complex containing ortho-metallated (S)-[1-(dimethylamino)ethyl]naphthalene as a chiral auxiliary has been successfully employed to promote the asymmetric cycloaddition reaction between 3,4-dimethyl-1-phenylarsole and diphenylvinylarsine. In the intramolecular cycloaddition reaction, a pair of separable diastereomeric palladium complexes was obtained in the ratio of 6:1. The chiral naphthylamine auxiliary could be removed chemoselectively from the template by treatment with HCl and subsequently NaI to generate the neutral diiodo complex [(As-As)PdI2]. Treatment of the diiodo complex with KCN gave the enantiomerically pure As-As bidentate ligand in quantitative yield. In contrast to the reported similar P-P and As-P analogues, both arsenic donors in the diiodo complex could be readily eliminated to produce a structurally novel dimetallic complex. [ABSTRACT FROM AUTHOR]

Ester- and keto-functionalized allylic monophosphine palladium complexes containing ortho-metalated (R)-(1-(dimethylamino)ethyl)naphthalene as the chiral auxiliary were synthesized via a versatile one-pot process. Subsequent asymmetric hydrophosphination of the coordinated allylic substrates promoted by the chiral auxiliary gave the corresponding functionalized chiral 1,2-bis(diphenylphosphino)ethane ligands in high yields under mild conditions. The coordination properties and absolute configurations of the resultant diphosphine ligands were established by single-crystal X-ray crystallography. The coordinated 1,2-diphosphine ligands could be subsequently liberated stereospecifically to yield enantiomerically pure functionalized diphosphines in high yields. [ABSTRACT FROM AUTHOR]