Metal Effects on the Asymmetric Cycloaddition Reaction between 3,4-Dimethyl-1-phenylarsole and Diphenylvinylphosphine Oxide

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• 作者：Mengtao Ma ; Sumod A. Pullarkat ; Mingjun Yuan ; Na Zhang ; Yongxin Li ; Pak-Hing Leung
• 刊名：Organometallics
• 出版年：2009
• 出版时间：August 24, 2009
• 年：2009
• 卷：28
• 期：16
• 页码：4886-4889
• 全文大小：739K
• 年卷期：v.28,no.16(August 24, 2009)
• ISSN：1520-6041

文摘

The organopalladium complex containing ortho-metalated (S)-[1-(dimethylamino)ethyl]naphthalene as the chiral auxiliary has been used successfully to promote the asymmetric cycloaddition reaction between 3,4-dimethyl-1-phenylarsole and diphenylvinylphosphine oxide in high stereoselectivity (only one isomer). However, the neutral dichloro palladium complex obtained upon removal of the auxiliary is very unstable and instantly decomposed to produce the arsenic elimination reaction product (3,4-dimethyl-2,4-cyclohexadienyl)diphenylphosphine oxide. However when the same reaction was promoted by the analogous platinum complex, only one stereoisomer was again obtained, but the resulting dichloro platinum complex is very stable in the solid state as well as in solution and coordinates to the platinum center as a As−O bidentate ligand, as confirmed by ¹H NMR and single-crystal X-ray analysis. The enantiomerically pure AsP═O hetero-bidentate ligand could be readily liberated from the dichloro platinum complex as an air-sensitive solid by treatment of the complex with aqueous potassium cyanide.