He Hua-Dong, Chitrakar Ravi, Cao Zhi-Wei, Wang Dao-Ming, She Li-Qin, Zhao Peng-Gang, Wu Yichen, Xu Yuan-Qing, Cao Zhong-Yan, Wang Peng
College of Chemistry and Molecular Sciences, Henan University, Kaifeng, 475004, P. R. China.
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, CAS 345 Lingling Road, Shanghai, 200032, P. R. China.
Angew Chem Int Ed Engl. 2024 Jan 2;63(1):e202313336. doi: 10.1002/anie.202313336. Epub 2023 Nov 29.
The precise control of the regioselectivity in the transition metal-catalyzed migratory hydrofunctionalization of alkenes remains a big challenge. With a transient ketimine directing group, the nickel-catalyzed migratory β-selective hydroarylation and hydroalkenylation of alkenyl ketones has been realized with aryl boronic acids using alkyl halide as the mild hydride source for the first time. The key to this success is the use of a diphosphine ligand, which is capable of the generation of a Ni(II)-H species in the presence of alkyl bromide, and enabling the efficient migratory insertion of alkene into Ni(II)-H species and the sequent rapid chain walking process. The present approach diminishes organosilanes reductant, tolerates a wide array of complex functionalities with excellent regioselective control. Moreover, this catalytic system could also be applied to the migratory hydroarylation of alkenyl azahetereoarenes, thus providing a general approach for the preparation of 1,2-aryl heteroaryl motifs with wide potential applications in pharmaceutical discovery.
在过渡金属催化的烯烃迁移氢官能化反应中，对区域选择性进行精确控制仍然是一个巨大的挑战。首次使用瞬态酮亚胺导向基团，以卤代烷作为温和的氢化物源，实现了镍催化的烯基酮与芳基硼酸的迁移β-选择性氢芳基化和氢烯基化反应。这一成功的关键在于使用了一种双膦配体，该配体能够在存在溴代烷的情况下生成Ni(II)-H物种，并能使烯烃有效地迁移插入到Ni(II)-H物种中，随后进行快速的链行走过程。目前的方法减少了有机硅烷还原剂的使用，能够耐受多种复杂官能团，并具有出色的区域选择性控制。此外，该催化体系还可应用于烯基氮杂芳基的迁移氢芳基化反应，从而为制备1,2-芳基杂芳基基序提供了一种通用方法，在药物发现中具有广泛的潜在应用。
