| The increasing demand of producing enantiomerically pure pharmaceuticals, agrochemicals, flavors, and other fine chemicals, has facilitated the development of asymmetric catalytic technologies. Among all asymmetric catalytic methods, asymmetric hydrogenation utilizing molecular hydrogen to produce prochiral olefins, ketone and imines became one of the most efficient methods for constructing chiral compounds. But the high cost of ligands blocked the commercial application of asymmetric catalytic hydrogenation. The development of aminophospine-phosphinite (AMPP) ligands with highly enantioselectiviy and low cost and application in asymmetric catalytic hydrogenation had important practical value for the construction of economic available technological platform and the advance of preparation of the chiral compounds and the industrialization of chiral technology.The second amino alcohols were the key feedstock for AMPP ligands. A new synthetic route of second amino alcohols was developed by "one-step" reduction of carbonyl and carboxyl group utilizing NaBH4/I2 after N-acylization to reduce the preparation cost of second amino alcohols from α-amino acids. The new rigid chiral amino alcohol (S)-Ticol (3-hydroxygenmethyl-1,2,3,4-tetrahydroisoquininone ) was synthesized by chemoenzymatic method. Then (SO -TIAMPP and a series of BPEBOP C2-symmetric bis(phphospholano)ethane bearing bis(oxzaphosphlidine) were first designed and synthesized. The corresponding Rh-AMPP homogeneous catalysts were synthesized and applied in asymmetric hydrogenation. The Hproline and Theronine were supported by Merrifield resin using solid-phase technology. Heterogeneous chiral catalysts were prepared. Their catalytic properties were studied.Firstly, a series of primary amino alcohols were prepared respectively by utilizing NaBH4/H2SO4 and NaBH4/I2 reductive systems and Ru/C catalytic hydrogenation. And the synthetic method of second amino alcohols was thoroughly studied. These chiral amino alcohols were the raw materials for the preparation of new AMPP ligands with low cost and high enantioselectivity. L-prolinol was prepared via NaBH4/I2 reduction system with 88.4% yield. The new synthetic method ofN-substituted amino alcohols was also developed by "one-step" reduction to carbonyl group and carboxyl group with the yields about 70-75% after N-acylization by alkali method, acid method and supersonic wave. The new method' yields exceeded the old method' by 10-20%. Optically pure (S)-1,2,3,4-tetrahydroisoquininone-S-carboxylic acid (Tic) was achieved by chemoenzymatic synthesis with 49.1% and 99.5% e.e. Novel rigid N-heterocyclic amino alcohol (5)-Ticol was synthesized via NaBH4/I2 system with the 77% yield. The synthesis of (S)-Tic and (S)-Ticol was not reported in the previous literatures.Secondly, a series of corresponding AMPP ligands were prepared. Beyond the synthesis of N-Methyl-PGlyNOPP, ProNOPP, etc., the new N-hetercyclic six-membered ligand (S)-TIAMPP was achieved using (S)-Ticol and PPh2Cl at the presence of triethylamine, which was characterized by 1HNMR, 13CNMR, 31PNMR. The best yield 70.2% was obtained under the optimum condition. On the illumination of the structure of excellent ligand BPE, new C2-symmetric AMPP ligands (S,S)-Me-BPEPBOP, (R,R)-Ph-BPEPBOP, (R,R)-Phe-BPEPBOP and (S,S)-Pro-BPE-BOP from N-ethyl derivatives of alaninol, phenylglyninol, phenylaninol, prolinol were first designed and synthesized.Thirdly, a new rigid chiral rhodium-AMPP catalysts [Rh(COD)((S)-TIAMPP)]+ BF4- was prepared, and its enantioselectivity and activity were both studied with the over 95% converting yield and 85%-96% e.e in the asymmetric Rh-catalyzed hydrogenation of methyl-N-benzoyl-cinamate. Studies on catalytic activities of different non-C2-symmetric chiral catalysts showed that the rigidity of ligands increased the enantioselectivity about 10-15% more. Novel C2-symmetric chiral AMPP catalysts were first prepared and their catalytic properties were studied. We found that the symmetric property of ligands in the chiral AMPP-Rh catalysts had obvious effect on the enantioselectivity. Especially, the chiral catalysts 4n and 4o had much more catalytic activity and enantioselectivity than their corresponding non-C2-symmetric AMPP-Rh catalysts with respectively 97% e.e and 95% e.e in the asymmetric hydrogenation of methyl-N-benzoyl-ccinamate. Chiral catalyst 4o respectively offered 97% e.e and 95% e.e in the asymmetric hydrogenation ofa-amino-acetophenone and ethyl acetoacetate. This type of chiral catalysts would have promising prospect in the field of asymmetric catalytic hydrogenation.The D-alanine preparation process via asymmetric Rh-catalyzed hydrogention was studied. The optimized process of asymmetric hydrogenation of N-acetyl-dehy-droalanine catalyzed by chiral catalysts 4n resulted 100% converting yield and 95% e.e under the conditions of S/C=100, 1.0MPa, 40℃, the substrate concentration 0.03M, THF as solvent for 4h.The heterogenization of the chiral homogeneous ligands was originally developed by solide-phase syntheitic technology. HPAMPP and ThrAMPP-supproted -Merrifield resins were obtained with 81% and 80% supporting yield, respectively. The chiral HPAMPP-Merriefield-rhodium and ThrAMPP-Merrifield-resin-rhodium catalysts were applied in the asymmetric hydrogenation of N-acetyl-dehydroalanine. The former converting yield was 100%, the average e.e value was 89% in three parallel experiments; and the later average converting yield was 88%, the e.e value was 80% under the condition of S/C100, 40℃, 1.0MPa, THF as solvent. Preparation cost of D-alanine by chiral heterogeneous catalysts supported by Merrifield resin could be lower for the recycling of chiral catalysts. This method would have a promising potential in the near future.Finally, based on the synthesis of highly effective and low-cost AMPP ligands and studies on the homogeneous and heterogeneous asymmetric hydrogenation, the prospect of application of asymmetric catalytic hydrogenation in the industry and proposal were put forth in the thesis.
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