通过对映选择性 Cu 催化的不对称 B-H 键插入反应构建硼手性化合物。

Key Laboratory of Molecule Synthesis and Function Discovery, Fujian Province University, College of Chemistry at Fuzhou University, Fuzhou, Fujian, 350108, China.

Department of Chemistry and Shenzhen Grubbs Institute, Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, Shenzhen, Guangdong, 518055, China.

Nat Commun. 2022 May 12;13(1):2624. doi: 10.1038/s41467-022-30287-7.

Compared with the well-developed carbon-stereogenic chemistry, the construction of boron-stereogenic compounds remains undeveloped and challenging. Herein, the previously elusive catalytic enantioselective construction of boron-stereogenic compounds has been achieved through enantioselective desymmetric B-H bond insertion reaction. The B-H bond insertion reaction of 2-arylpyridine-boranes with versatile diazo compounds under chiral copper catalyst can afford boron-stereogenic compounds with good to excellent enantioselectivity. Moreover, the synthetic utility of this reaction is demonstrated by the scalability and downstream transformations. DFT calculations provide insights into the reaction mechanism and the origin of stereoselectivity.

与碳立体化学的高度发达相比，硼立体化学化合物的构建仍然不发达且具有挑战性。在此，通过对映选择性去对称 B-H 键插入反应，实现了先前难以捉摸的催化对映选择性硼立体化学化合物的构建。在手性铜催化剂作用下，2-芳基吡啶硼烷与各种重氮化合物的 B-H 键插入反应可以得到具有良好到优秀对映选择性的硼立体化学化合物。此外，该反应的合成实用性通过可扩展性和下游转化得到了证明。DFT 计算为反应机制和立体选择性的起源提供了深入了解。