中文摘要：

手性有机硼化合物在有机合成、医药、材料等诸多领域中有广泛的应用，发展该类化合物的高效合成方法一直广受关注．此前，我们发展了过渡金属催化卡宾对硼氢键（B—H）的插入反应，并实现了α-重氮酯对B—H键的不对称插入反应．本文以手性螺环双嗯唑啉配体和铜的络合物作为催化剂，首次实现了“．重氮酮对膦-硼烷加合物的B—H键不对称插入反应，获得了较高的收率和高达83％ee的对映选择性．该研究成果是为数不多的以α-重氮酮作为卡宾前体的不对称杂原子氢键插入反应，为手性α-硼取代酮化合物这类新的有机硼化合物的合成提供了有效方法．

英文摘要：

Chiral organoboron compounds are widely used in organic synthesis, materials science, medicine, and other fields, and the development of methodologies for the synthesis of these compounds is a highly active and rewarding area of research. Enantioselective transition-metal-catalyzed carbenoid insertion into heteroatom-hydrogen （X--H） bonds is an effi- cient strategy for the formation of carbon-heteroatom （C--X） bonds and related chiral centers. The enantioselective bo- ron-hydrogen （B--H） bond insertion reaction provides an ideal approach to chiral organoboron compounds. In our previous study, we developed a copper-catalyzed asymmetric B--H bond insertion reaction of a-diazoesters with phosphine-borane adducts with high yields and high enantioselectivities. Herein, we report the first enantioselective B--H bond insertion reac- tion of a-diazoketones, another readily available carbene precursors. Firstly, various borane adducts were evaluated, and di- methylphosphine-borane gave the best result. Then, the reaction conditions were carefully optimized, and Cu（MeCN）4PF6/（Ray,Sy,S）-Ph-SpiroBOX proved to be the most efficient catalyst. Under optimal reaction conditions, the sub- strate scope of the reaction was investigated. A variety of a-diazoketones underwent the B--H bond insertion reaction af- fording the desired a-borylketones in good yields with moderate to good enantioselectivities （up to 83% ee）. This reaction represents one of the few enantioselective X--H insertion reactions using a-diazoketones as carbene precursors. A typical procedure for the enantioselective copper-catalyzed B--H bond insertion of a-diazoketones is as follows： The powered Cu（MeCN）4PF6 （5.6 mg, 0.015 mmol, 5 mol%） and （Ra,S,S）-Ph-SpiroBOX （4a, 9.2 mg, 0.018 mmol, 6 mol%） were intro- duced into an oven-dried Sehlenk tube in an argon-filled glovebox. After CH2C12 （3 mL） was injected into the Schlenk tube, the solution was stirred at 25 ℃ under the argon atmosphere for 2 h. Then dimethylphosphin