含氮手性及外消旋配体与铑络合物在苯乙酮不对称氢转移反应中的应用

Application of the Catalysts Consisting of Optically Active Ligand, Racemic Ligand,Chiral Activator and Rhodium Complex in the Hydride Transfer Reductive Reaction of Acetophenone

将由手性配体(1S,2S)-N-对甲苯磺酰基-1,2-二苯基乙二胺与铑金属络合物二-μ-氯-二(1,5-环辛二烯)二铑;外消旋配体(±)-1,1'-联-2-萘胺、手性活化剂(1S,2S)-1,2-二苯基乙二胺与铑金属络合物二-μ-氯-二(1,5-环辛二烯)二铑组成的两种催化剂体系用于催化苯乙酮的不对称氢化反应.由气相色谱法及旋光测定法对反应物的转化率及产物的光学纯度分析的结果表明,手性配体和铑金属络合物组成的手性配体催化体系对苯乙酮的转化率为5.11%,产物的光学纯度为72.16%;而外消旋配体、手性活化剂与铑金属络合物组成的外消旋配体催化体系对苯乙酮的转化率为42.84%,产物的光学纯度为16.17%,由此说明手性配体催化体系较外消旋配体催化体系表现出更高的光学选择性.

Both the catalyst system consisting of optically active ligand(1S,2S) -N-p-toluenesulfonyl-1,(2-diphenylethylenediamine) ((S,S)-TsDPEN),rhodium complex bis(cycloocta-1,5-diene)-μ,μ'-dichlorodirhodium [RhClC_8H_(12)]_2 and the catalyst system consisting of racemic ligand (±)-2,2'-diamino-1,1'-binaphthyl,rhodium complex bis(cycloocta-1,5-diene)-μ,μ'-dichlorodirhodium,chiral activator(1S,2S)-1,2-diphenyl ethylenediamine were used to catalyze the hydride transfer reductive reaction of acetophenone. The products were characterized and analyzed by gas chromatograph and polarimeter. The results showed that the ((S,S)-TsDPEN)/[RhClC_8H_(12)]_2 catalyst system catalyzed the reaction to give phenylethanol in 72.16% EE and 5.11% conversion of acetophenone; while the (±)-2,2'-diamino-1,1'-binaphthyl/[RhClC_8H_(12)]_2/((S,S)-DPEN) catalyst system catalyzed the reaction to give 1-phenylethanol in 16.7% EE and 42.84% conversion of acetophenone, the ((S,S)-TsDPEN)/[RhClC_8H_(12)]_2 catalyst system showed better stereoselectivity.