新型水溶性手性钌催化剂的制备及应用

利用发烟硫酸磺化手性双胺双膦配体（R．R）-C6P2（NH）2]．合成了PNNP-型水溶性手性双胺双膦配体（R．R）-C6P2（NH）2（SO3Na）4]，并分别与简单的钌、铑络合物反应，制备水溶性手性钌络合物催化剂（R，R）-C6P2（NH）2（SO3Na）4RuCl2]和铑络合物催化剂（R，R）-C6P2（NH）2（SO3Na）4RhCl]．经元素分析、红外光谱和核磁共振等对手性配体及手性Ru络合物进行了结构表征．进而用这些水溶性的钌，铑络合物催化剂或水溶性手性配体与铱络合物IrHCl2（COD）]2组成的混合催化体系研究了多种芳香酮的不对称转移氢化。结果表明．在以异丙醇作为氢源时．对芳香酮的不对称转移氢化都具有较好的催化活性．与铑，铱催化体系相比，水溶性手性钌络合物催化体系具有更高的活性和对映选择性．对于苯乙酮的氢化．其转化率和对映选择性分别达到91.6％和93．0％e．e．．此外，进一步考察了反应温度和KOH用量对水溶性手性钌络合物催化苯乙酮不对称转移氢化性能的影响，并将水溶性手性钌络合物催化体系应用于多种芳香酮的不对称转移氢化，获得了高的收率和对映选择性，分别可达92．0％和96．4％e．e．．研究结果表明，水溶性手性钌络合物CR．R）-G6P2（NH）2（SO3Na）4RuCl2]是芳香酮不对称氢转移催化氢化的优良催化剂.

Synthesis and Application of a New Water-soluble Chiral Ruthenium Catalyst

The water-soluble chiral diaminodiphosphine ligand PNNP-type (R,R)-C_6P_2(NH)_2(SO_3Na)_4] was synthesized by sulfonation of chiral diaminodiphosphine ligand (R,R)-C_6P_2(NH)_2].The corresponding water-soluble chiral metal complexes (R,R)-C_6P_2(NH)_2(SO_3Na)_4RuCl_2] and (R,R)-C_6P_2(NH)_2(SO_3Na)_4RhCl] were also prepared by reaction of the water-soluble ligand and Ru or Rh complexes,respectively.These chiral ligands and metal complex were characterized by EA,IR and ~(31)P NMR.Water-soluble chiral Ru and Rh complexes,and the chiral Ir catalytic system generated in situ from iridium hydride complex IrHCl_2(COD)]_2 and (R,R)-C_6P_2(NH)_2(SO_3Na)_4] were employed in asymmetric transfer hydrogenation of acetophenone.The results showed that these catalytic systems efficiently catalyzed asymmetric transfer hydrogenation of aromatic ketones using ~iPrOH as hydrogen source.The water-soluble chiral Ru catalytic system gave the best activity and excellent enantioselectivity,with up to 91.6% yield and 93.0% e.e.respectively.In addition,reaction temperature and addition of KOH amount on the effects of asymmetric transfer hydrogenation of acetophenone were also studied.The water-soluble chiral Ru complex was further employed in asymmetric transfer hydrogenation of various aromatic ketones,up to 92% yield and 96.4% e.e.were obtained.These results showed that the water-soluble chiral Ru complex (R,R)-C_6P_2(NH)_2(SO_3Na)_4RuCl_2] was an excellent catalyst for the asymmetric transfer hydrogenation of aromatic ketones under the mild reaction conditions.