葡萄糖及半乳糖衍生的手性双膦-铑(Ⅰ)配合物催化苯乙烯不对称氢甲酰化反应  

Asymmetric Hydroformylation of Styrene Catalyzed by Pyranoside Diphosphite-Rh(Ⅰ) Complexes

作　　者：贾小静[1] 王来来[2] 陈新滋[2] 李月明[2] 

机构地区：[1]中国科学院兰州化学物理研究所羰基合成与选择氧化国家重点实验室,甘肃兰州730000 [2]香港理工大学应用生物及化学科技学系手性药物合成与开发开放实验室

出　　处：《催化学报》2007年第6期492-494,共3页

基　　金：国家自然科学基金(20343005;20473107;20673130).

摘　　要：合成了四个从葡萄糖及半乳糖衍生的手性芳基双膦配体,制备了手性双膦-铑(Ⅰ)配合物催化剂,并将其用于苯乙烯不对称氢甲酰化反应中.结果表明,葡萄糖骨架手性中心与联萘基之间有协同作用,对映体过量值和转化率受配体C-4骨架立体中心的绝对构型影响,而产物的绝对构型则主要由联萘单元控制;配体4-双{[(S)-1,1′-联萘基-2,2′-双基]-磷}-苯基-3,6-脱水-β-D-葡萄糖的吡喃糖苷基和联萘基的匹配组合,给出41%的对映体选择性和74∶26(异构/正构)区域选择性.Several chiral aryl diphosphite ligands derived from pyranoside backbones of glucose and galactose were applied in Rh-catalyzed asymmetric hydroformylation of styrene. A synergic effect between the chiralities of glucose and the binaphthyl moieties was observed. The sense of enantioselectivity is mainly controlled by the binaphthyl moieties, and the chirality of the sugar moiety can also affect the enantioselectivity of the reactions. In the case of the matching combination of phenyl-3,6-anhydro-β-D-glucopyranoside and binaphthyl moiety, 4- his{ [ （ S ） - 1, 1＇-binaphthyl-2,2＇-diyl ] -phosphite} -phenyl-3,6-anhydro-β-D-gluco-pyranoside （ L4 ）, 41% ee and 74：26 of branch-to-normal ratio were obtained.

关 键 词：葡萄糖 半乳糖 手性芳基双膦配体 铑配合物 苯乙烯 不对称氢甲酰化 

分 类 号：O643.32[理学—物理化学]