新型手性胺膦-铱体系催化芳香酮的不对称转移氢化  

Asymmetric Transfer Hydrogenation of Aromatic Ketones Catalyzed by New Chiral Diaminodiphosphine-Iridium(I) Systems

作　　者：程智博[1] 李岩云[1] 董振荣[1] 张学勤[1] 余神銮[1] 孙果宋 黄科林 高景星[1] 

机构地区：[1]厦门大学固体表面物理化学国家重点实验室醇醚酯化工清洁生产国家工程实验室化学化工学院化学系,福建厦门361005 [2]广西化工研究院,广西南宁530001

出　　处：《分子催化》2009年第6期483-487,共5页Journal of Molecular Catalysis(China)

基　　金：国家自然科学基金(No.2042300220703034);福建省自然科学基金(No.2008J0235);广西自然科学基金资助(No.0832192)

摘　　要：合成了含-CH3取代基的PNNP型手性双胺双膦配体,并采用核磁共振、质谱、红外光谱及圆二色光谱等方法对其进行了表征.在异丙醇溶液中,考察了该配体与[IrHC l2(COD)]2组成的手性胺膦-铱体系对多种芳香酮的不对称转移氢化性能.结果表明,该手性胺膦-铱体系是催化多种芳香酮不对称氢转移氢化的优秀催化剂.在室温下,用该体系催化1,1-二苯基丙酮时,可得到99%的转化率和99%ee的对映选择性.The chiral PNNP ligands containing -CH3substituents have been synthesized and characterized by NMR, MS, IR and CD spectra. The chiral diaminodiphosphine-iridium （Ⅰ） systems, prepared in situ from [ IrHCl2 （COD） ] 2 and the ligands 1 and 2, have been explored. The catalytic performance was investigaed in the asymmetric transfer hydrogenation of various aromatic ketones in ^1PrOH. The resuhs indicated that the catalytic system acted as an excellent catalyst precursor in asymmetric transfer hydrogenation of various aromatic ketone. When the （R, R）-2/[ IrHCl2 （COD） ] 2 as catalyst was employed for the reduction of the 1,1-diphenylacetone at room tempreture, high activity （99% conversion） and excellent enantioselcctivity （99% ee ） were obtained.

关 键 词：手性双胺双膦配体 铱络合物 芳香酮 不对称转移氢化 

分 类 号：O643.32[理学—物理化学]