有机硼衍生物是药物化学、生物活性分子和材料化学中的多功能基础单元，也是有机合成化学中的重要中间体，可以通过交叉耦合和氧化反应等方便地构筑C-O, C-N, C-C, C-H及C-X键，进而形成更为复杂的分子，因此被广泛应用于有机化学中。烯烃的硼氢化是构建含硼化合物颇具代表性的方法，其中过渡金属催化的C=C的不对称催化硼氢化因其优秀的化学和区域选择性以及广泛的官能团相容性等特点引起了化学工作者的广泛关注。虽然人们已经开发了许多手性色满化合物的合成方法，但是依然存在合成步骤较多、选择性低以及反应条件苛刻等问题。2H-色烯的不对称催化硼氢化也是合成手性色满类化合物的一种高效、简捷的方法，而且迄今为止，2H-色烯类底物的不对称催化硼氢化一直没有得到很好地解决，一直缺少适用于该类底物的高效催化体系。 本论文针对2H-色烯类底物的不对称催化硼氢化问题，以期开发适用于此类底物的催化剂，能很好地得到手性3-硼酸酯色满化合物，为手性色满化合物的合成开辟一条新的路径。 在2H-色烯类底物的不对称催化硼氢化研究中，我们发现在2H-色烯中不仅C=C双键与苯环的共轭效应使得在催化硼氢化期间遇到高能垒而降低反应活性，而且活泼氧因其可能与硼氢化试剂相互作用，无法给出令人满意的催化活性和手性诱导结果。所以目前为止适用于二氢苯并吡喃类底物的不对称催化硼氢化的高效催化体系非常缺乏。我们研究发现：Cu-(S,R)-DuanPhos络合物在2H-色烯类烯烃的不对称催化硼氢化反应中，能够表现出较高的催化活性和优异的对映选择性。经过对反应条件的系统优化，最终我们建立了较理想的反应条件，获得了令人满意的催化活性和对映选择性。在这种反应条件下，一系列2H-色烯类烯烃经过不对称催化硼氢化得到了对应的光学硼化物，对映选择性高达96% ee。此外，我们还对硼氢化产物进行了一系列官能团的转化，得到了相应地具有重要应用价值的包括手性醇在内的光学活性产物对映选择性能够基本保持不变。本论文开展了2H-色烯类化合物的不对称催化硼氢化相关研究，找到了适合此类化合物的高效催化体系，提供了一种直接合成手性3-硼酸酯色满化合物的方法，并进行了包括手性醇在内的相关转化实验, 且对映选择性不变。该工作不但拓宽了不对称催化硼氢化反应的研究领域，也丰富了手性色满化合物的合成方法。

Organoboranes are versatile synthetic intermediates for the preparation of a wide range of organic molecules in pharmaceutical and synthesis chemistry. An increasing effort has been devoted to the efficient synthesis of organoboron compounds, since the resulting C-B bond can be transformed with retention of configuration into C-O, C-N, C-C, and C-halogen bonds. Transition metal-catalyzed boration of unsaturated C=C bonds is an attractive method to produce the organoboron derivatives with defined regio- and stereochemistry, which has been the subject of extensive research. In recent decades, many methods of synthesizing chiral chromans have been reported, but some problems such as more synthetic steps, poor enantioselectivity and difficult reaction conditions exist. Thus far, excellent catalyst employed in the asymmetric hydroboration of 2H-chromenes has not yet been developed. Therefore, the development of efficient methods for the synthesis of chiral remains an urgent problem to be solved. This paper committed to find excellent catalysts which can efficiently and high enantioselectivity asymmetric hydroboration of 2H-chromenes to produce a means for obtaining chiral chroman compounds. In this paper, the asymmetric hydroboration of 2H-chromenes will be researched. To the best of our knowledge, there is scarce example on the enantioselective hydroboration of 2H-chromenes reported. The catalyzed enantioselective hydroboration of 2H-chromenes still remains a challenge. This is possibly attributed to the high energy barrier encountered during the conjugation of the C=C double bond with phenyl ring, as well as the interaction of the oxygen atom with the borated reagent which maybe has a negative effect on the hydroboration. Thus far, the investigation on asymmetric hydroboration of 2H-chromenes is still in its infancy. Both the efficient catalyst and substrate scope is limited. Herein we report an efficient copper catalyzed asymmetric hydroboration of 2H-chromenes using a chiral diphosphine ligand (S,R)-DuanPhos to afford a series of chiral chromans with high yields and enantioselectivities, up to 96% ee. In addition, chiral borylated chromans are versatile synthetic intermediates that can be easily converted to numerous other useful derivatives in high yield without any loss of enantioselectivity. In this thesis, an efficient asymmetric hydroboration of 2H-chromenes to afford chiral chromans with high yields and enantioselectivities has been realized. This strategy provides a straightforward approach to important chiral 3-boryl chromans, which can be readily converted to various useful compounds including chiral alcohols. It not only broadens the research field of asymmetric catalytic borohydride reaction, but also enriches the synthesis method of chiral chromans compounds.