具有C2对称的氮磷-氧磷配体双噁唑啉磷乙烷的合成及在不对称催化加氢中的应用  

Synthesis of Aminophosphine Phosphinite Ligand Bis(oxaza- phospholano)-ethane with C_2-Symmetric Axis and Its Application in Asymmetric Hydrogenation

作　　者：龚大春[1,2] 周华[3] 韦萍[3] 王泰山[4] 欧阳平凯[3] 

机构地区：[1]三峡大学化学与生命科学学院 [2]南京工业大学制药与生命科学学院南京210009 [3]南京工业大学制药与生命科学学院 [4]中国科学院上海有机化学研究所

出　　处：《有机化学》2008年第4期638-643,共6页Chinese Journal of Organic Chemistry

基　　金：国家科技部973基金(No.9732003CB716000)资助项目.

摘　　要：利用易得的光学纯N-甲基氨基醇与1,2-双(二氯磷)乙烷缩合合成了一类新的具有C2对称轴的氮磷-氧磷配体(R,R)-双噁唑啉磷乙烷(BOAPE)1～4.该类配体不仅具有C2对称结构和刚性五元环,还具有富电子特性,利用500MHz进行了1HNMR,31PNMR,13CNMR表征.与这些配体配位形成的Rh配合物用于N-苯甲酰基脱氢丙氨酸衍生物和α-功能化酮不对称加氢,分别可以得到99%和98%的ee.这类配体比它们相对应的非C2对称的氮磷-氧磷化合物(AMPP)配体具有更高的对映选择性.在这四个新的配体中配体(R,R)-Ph-BOAPE(2)的催化性能最优.催化剂[Rh(COD)(R,R)-Ph-BOAPE]BF4的半反应周期t1/2和周转频率(TOF)在N-苯甲酰基肉桂酸甲酯的不对称加氢反应中分别为12min和6.5min-1.A new class of C2-symmetric （R,R）-bis（oxazaphospholano）ethane （BOAPE） 1-4 was synthesized by the condensation reaction of readily available optically active amino alcohols with 1,2-bis（dichlorophosphino）ethane. These new ligands bear not only C2-symmetry axis but also a rigid ring. They were characterized by ^1H NMR, ^31p NMR and ^13C NMR spectra. The enantioselective yields were obtained by Rh complex catalyzed asymmetric catalytic hydrogenation of N-benzoyldehydroamino acid derivatives and α-functionalized ketones in up to 99% ee and 98% ee, respectively. This new class of （R,R）-BOAPE gave much higher efficiency and enantionselectivity than their corresponding non C2-asymmetric aminophosphine phosphinite （AMPP）. Among these ligands, （R,R）-Ph-BOAPE （2） was the best one. The t1/2 and turnover of frequency （TOF） of the catalyst [Rh（COD）（R,R）-Ph-BOAPE]BF4 for the asymmetric hydrogenation of methyl N-benzoyl cinnamate were 12 min and 6.5 min^-1, respectively.

关 键 词：(R R)-BOAPE C2对称 不对称加氢 

分 类 号：O643.32[理学—物理化学]