Department of Chemistry, Pohang University of Science and Technology (POSTECH), Pohang 37673, Republic of Korea.
Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141, Republic of Korea.
J Am Chem Soc. 2021 Jan 20;143(2):1069-1077. doi: 10.1021/jacs.0c11750. Epub 2021 Jan 4.
We report a copper-catalyzed enatiotopic-group-selective allylation of -diborylalkanes with allyl bromides. The combination of copper(I) bromide and H-BINOL derived phosphoramidite ligand proved to be the most effective catalytic system to provide various enantioenriched homoallylic boronate esters, containing a boron-substituted stereogenic center that is solely derived from -diborylalkanes, in good yields with high enantiomeric ratios under mild conditions. Experimental and theoretical studies have been conducted to elucidate the reaction mechanism, revealing how the enatiotopic-group-selective transmetalation of -diborylalkanes with chiral copper complex occurs to generate chiral α-borylalkyl-copper species for the first time. Additional synthetic applications to the synthesis of various chiral building blocks are also included.
我们报告了一种铜催化的对映选择性 -二硼烷与烯丙基溴的烯丙基化反应。溴化亚铜和 H-BINOL 衍生的手性磷酰胺配体的组合被证明是最有效的催化体系，可以在温和条件下以高对映选择性和良好的收率提供各种手性高烯丙基硼酸酯，其中包含一个硼取代的手性中心，该中心仅源自 -二硼烷。进行了实验和理论研究以阐明反应机理，首次揭示了 -二硼烷与手性铜配合物的对映选择性转金属化如何发生，以生成手性 α-硼烷基-铜物种。还包括对各种手性砌块合成的其他合成应用。
