Zhou Jun, Wang Dong, Xu Wenhao, Hu Zihao, Xu Tao
Shanghai Key Laboratory of Chemical Assessment and Sustainability, School of Chemical Science and Engineering, Tongji University, 1239 Siping Road, Shanghai, 200092, People's Republic of China.
J Am Chem Soc. 2023 Feb 1;145(4):2081-2087. doi: 10.1021/jacs.2c13220. Epub 2023 Jan 23.
Substantial advances in enantioconvergent C(sp)-C(sp) bond formations have been made with nickel-catalyzed cross-coupling of racemic alkyl electrophiles with organometallic reagents or nickel-hydride-catalyzed hydrocarbonation of alkenes. Herein, we report an unprecedented enantioselective C(sp)-C(sp) reductive cross-coupling by the direct utilization of two different alkyl halides with dual nickel/photoredox catalysis system. This highly selective coupling of racemic α-chloroboronates and unactivated alkyl iodides furnishes chiral secondary alkyl boronic esters, which serve as useful and important intermediates in the realm of organic synthesis and enable a desirable protocol to fast construction of enantioenriched complex molecules.
在手性汇聚式C(sp) - C(sp)键形成方面已经取得了重大进展，这包括镍催化外消旋烷基亲电试剂与有机金属试剂的交叉偶联，或镍氢催化的烯烃氢化反应。在此，我们报道了一种前所未有的对映选择性C(sp) - C(sp)还原交叉偶联反应，该反应通过双镍/光氧化还原催化体系直接利用两种不同的卤代烃实现。外消旋α-氯硼酸酯与未活化的烷基碘的这种高度选择性偶联反应生成了手性仲烷基硼酸酯，它们是有机合成领域中有用且重要的中间体，并为快速构建对映体富集的复杂分子提供了理想的方案。
