RuCl_2[(S)-P-Phos]-[(S)-DAIPEN]催化芳香酮的不对称加氢反应

Asymmetric Hydrogenation of Aromatic Ketones Catalyzed by RuCl_2[(S)-P-Phos]-[(S)-DAIPEN]

研究了钌-双膦-二胺配合物催化剂RuCl2[(S)-P-Phos]-[(S)-DAIPEN][P-Phos:2,2′,6,6′-四甲氧基-4,4′-双(二苯基膦基)-3,3′-二吡啶,DAIPEN:1,1-二(4-甲氧苯基)-2-异丙基-1,2-乙二胺]催化芳香酮不对称加氢反应的性能,考察了不同的碱、叔丁醇钾浓度、反应溶剂、底物/催化剂摩尔比等因素对反应活性和对映选择性的影响.在苯乙酮、叔丁醇钾、催化剂的摩尔比为1000:20:1,氢气压力为2MPa,反应温度为30℃时,苯乙酮的转化率和α-苯乙醇的对映选择性(ee)分别达到了100%和88.5%,2′-溴苯乙醇的ee值可达97.1%.

A ruthenium phosphine diamine complex RuCl2[（S）-P-Phos]-[（S）-DAIPEN] [P-Phos：2,2＇,6,6＇-tetramethoxy4,4＇-bis（diphenylphosphino）-3,3＇-bipyridine,DAIPEN：1,1＇-di（4-anisyl）-2-iopropyl-1,2-ethylenediamine] for the asymmetric hydrogenation of aromatic ketones has been studied.The influences of different bases,（CH3）3COK concentration,organic solvent,and molar ratio of substrate to catalyst on activity and enantioselectivity were investigated.Under the following optimum conditions：n（ketone）：n（KOH）：n（catalyst）=1000：20：1,pH2=2 MPa and T=30 ℃,the conversion of acetophenone and the enantioselectivity （ee） of S-1-phenylethanol was 100% and 88.5%,respectively.Additionally,the ee value of 2＇-bromophenyl ethanol was 97.1%.