Chen Jian, Wu Lifu, Song Zhiyong, Wang Yi, Li Zhenkun, Wang You, Zhu Shaolin
State Key Laboratory of Coordination Chemistry, Chemistry and Biomedicine Innovation Center (ChemBIC), Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China.
School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang 453007, China.
J Am Chem Soc. 2024 Sep 25;146(38):26223-26232. doi: 10.1021/jacs.4c07910. Epub 2024 Sep 16.
Selective functionalization of ubiquitous C-H bonds based on 1,-metal migration provides an attractive and sustainable route to access complex molecules from readily available precursors. Herein, we report a Co-catalyzed asymmetric reductive migratory Nozaki-Hiyama-Kishi (NHK) coupling between two readily available electrophiles, aryl (pseudo)halides and aldehydes, via an unprecedented through-space aryl-to-alkenyl 1,4-cobalt/hydride shift. The judicious choice of ligands is crucial for selectivity, leading to either ipso- or migratory NHK products with exquisite control of regio-, /-, and enantioselectivity. Enabled by a ligand relay catalytic strategy, this platform has been further extended to aryl-to-aryl asymmetric migratory NHK coupling. These high-value NHK adducts, including α-chiral allylic alcohols and benzyl alcohols, are readily convertible to a variety of useful synthons.
基于1，-金属迁移对普遍存在的C-H键进行选择性官能团化，为从易得的前体合成复杂分子提供了一条有吸引力且可持续的途径。在此，我们报道了一种钴催化的、两个易得亲电试剂（芳基（拟）卤化物和醛）之间的不对称还原迁移诺扎基-日向-岸部（NHK）偶联反应，该反应通过前所未有的空间芳基到烯基的1,4-钴/氢化物迁移实现。配体的明智选择对于选择性至关重要，能够以对区域选择性、非对映选择性和对映选择性的精确控制得到原位或迁移的NHK产物。通过配体接力催化策略，该平台已进一步扩展到芳基到芳基的不对称迁移NHK偶联反应。这些高价值的NHK加合物，包括α-手性烯丙醇和苄醇，很容易转化为各种有用的合成子。
