手性结构单元广泛存在于天然产物及具有生物活性的药物分子中，对人类的生产生活有重要的作用。手性化合物的合成有多种方法，其中不对称催化氢化因其原子经济性、环境友好性、高效高对映选择性、操作简单等优点成为科学家研究的热点。不对称催化氢化的关键是手性配体的合成，本论文主要设计合成了一类二茂铁骨架的螺环手性膦配体，并将其应用在了几类不饱和化合物的不对称氢化反应中，取得了显著的结果。 一、设计合成了二茂铁骨架螺环手性膦配体f-spiroPhos。 二、发展了高效高对映选择性催化体系Ir-(R,R)-f-spiroPhos，不对称催化氢化β-乙酰胺基硝基烯烃化合物，以优秀的对映选择性（91%-99.9% ee）获得了相应的手性β-氨基硝基烃类化合物。首次实现了铱催化的二烷基β-乙酰胺基硝基烯烃化合物的高效高对映选择性不对称氢化，即使在克级规模下，产率及ee值仍保持不变。 三、主要研究了α,β-不饱和腈类化合物的不对称催化氢化。在温和的条件下，应用[Rh(COD)Cl]2/(R,R)-f-spiroPhos催化体系同时实现了对(E/Z)-3-芳基-3-烷基，3,3-二芳基，3,3-二烷基α,β-不饱和腈类化合物的高效高对映选择性不对称催化氢化，ee值高达99.9%，转化数达10000，并对该反应的机理进行了推测。该方法还被成功应用到天然产物芳姜黄酮及抗抑郁药物茚达曲林中间体的不对称催化合成。 四、主要开展了在没有任何添加剂存在下的β,β-二取代不饱和羧酸化合物的不对称氢化反应研究。应用[Rh(COD)Cl]2/(R,R)-f-spiroPhos催化体系实现了一系列β,β-二取代不饱和羧酸的不对称氢化，以高达99.3% ee的优秀对映选择性合成了系列手性羧酸，同时将此方法应用在了β,β-二取代不饱和醛、γ,γ-二取代烯丙醇的不对称氢化反应中，获得了优异的对映选择性。我们将通过该方法合成的手性羧酸化合物成功应用于抗抑郁药物茚达曲林中间体的合成，高效高对映选择性地合成了目标产物。 五、发展了一种高效高对映选择性不对称催化氢化α,β-不饱和砜化合物的新方法。应用[Rh(COD)2]BF4/(R,R)-f-spiroPhos催化体系对(E/Z)-3-芳基-3-烷基-不饱和砜，(E/Z)-3,3-二芳基不饱和砜，苯并环状α,β-不饱和砜及苯并噻吩氧化物进行了不对称氢化研究，通过系统地条件优化，发现该催化体系对多种底物均表现出突出的反应活性和优异的对映选择性，ee值最高可达99.4%。 六、开展了不饱和硼酸酯的不对称催化氢化研究，为手性硼酸酯及其衍生物的合成发展了高效高对映选择性的方法。经过反应条件的优化筛选，我们发现[Rh(COD)2]OTf/(S)-DTBM-Segphos催化体系在(Z)-β,β-二取代不饱和硼酸酯和(Z)-α,β-二取代不饱和硼酸酯的不对称催化氢化反应中均表现出了优秀的催化活性和对映选择性，以高达98% ee的对映选择性合成了多种手性硼酸酯类化合物，并成功将氢化产物转化为相应的具有应用价值的手性醇、手性胺以及其他多种手性化合物。

Chiral building blocks, which are widely present in numerous natural products and biologically active pharmaceutical molecules, are necessary for human’s life and production. Many methods have been developed for the synthesis of enantiomerically pure compounds. Due to the greatest advantages of atom-economic, environmentally friendly, highly efficient enantioselective and simple operation, asymmetric catalytic hydrogenation has drawn much attention from chemists. The design and synthesis of a novel chiral ligand is crucial to asymmetric hydrogenation reaction. Hence, our group designed and synthesized a chiral phosphine ligand containing ferrocene and spiro skeleton, and applied it in asymmetric hydrogenation of several kinds of unsaturated compounds, gave to excellent enantioselectivities. Part one: We designed and synthesized ferrocene-based chiral spiro phosphine ligand, f-spiroPhos. Part two: A highly e?cient Ir-(R,R)-f-spiroPhos catalyzed enantioselective hydrogenation of β-acylamino nitroolefins has been developed. This reaction provides straightforward access to chiral β-amino nitroalkanes including chiral dialkyl β-amino nitroalkanes in high yields and excellent enantioselectivities (91%-99.9% ee). Under optimized reaction conditions, substrate with gram level scale was smoothly hydrogenated providing the corresponding product in excellent yield almost without any loss of enantioselectivity. Part three: A highly e?cient enantioselective hydrogenation of α,β-unsaturated nitriles catalyzed by [Rh(COD)Cl]2/(R,R)-f-spiroPhos complex has been developed. Under mild conditions, a wide range of α,β-unsaturated nitriles including the (E)- and (Z)-isomers of 3-alkyl-3-aryl, 3,3-diaryl, and 3,3-dialkyl α,β-unsaturated nitriles were hydrogenated to the corresponding chiral nitriles with excellent enantioselectivities (up to 99.9% ee) and high turnover numbers (TON up to 10,000). A plausible mechanism of this transformation was also proposed. Furthermore, this method was successfully applied to the enantioselective preparation of natural product (S)-(+)-ar-turmerone and the intermediate of anti-depressant drug indatraline. Part four: An additive-free enantioselective hydrogenation of β,β-disubstituted unsaturated carboxylic acids catalyzed by the [Rh(COD)Cl]2/(R,R)-f-spiroPhos complex has been developed. A wide scope of β,β-disubstituted unsaturated carboxylic acids were hydrogenated to the corresponding chiral carboxylic acids with excellent enantioselectivities (up to 99.3% ee). This catalyst system also exhibited good enantioselectivity for the asymmetric hydrogenation of β,β-disubstituted unsaturated aldehydes and γ,γ-disubstituted allyl alcohols, providing straightforward access to chiral alcohols. The chiral carboxylic acids were successfully applied to the synthesis of the pharmaceutical molecule indatraline in excellent yield almost without any loss of enantioselectivity. Part five: A highly efficient and enantioselective [Rh(COD)2]BF4/(R,R)-f-spiroPhos complex catalyzed asymmetric hydrogenation of a series of unsaturated sulfones has been developed. With Rh-(R,R)-f-spiroPhos catalyst and under mild conditions, a wide range of unsaturated sulfones including both (E)- and (Z)-isomers of 3-alkyl-3-aryl, 3,3-diaryl, cyclic, α,β-unsaturated sulfones and benzo[b]thiophene 1,1-dioxide were hydrogenated to the corresponding chiral sulfones with excellent enantioselectivities (up to 99.4% ee). Part six: A highly enantioselective [Rh(COD)2]OTf/(S)-DTBM-Segphos catalyzed asymmetric hydrogenation of α,β-unsaturated borates has been developed. This reaction provides access to chiral borates and its derivative in excellent enantioselectivities. Both (Z)-β,β-disubstituted and (Z)-α,β-disubstituted borates can be hydrogenated providing chiral borates with excellent enantioselectivities, up to 98% ee. In addition, the chiral borates were successfully transformed to chiral alcohol, chiral amine and other important chiral compounds in excellent enantioselectivity.