Nickel-Catalyzed Multicomponent Coupling: Synthesis of α-Chiral Ketones by Reductive Hydrocarbonylation of Alkenes

Abstract

General experimental procedures and characterization data abd 1 H NMR, 13 C NMR, 19 F NMR, and 11 B NMR spectral data (PDF)

Recent Advance of Ketones Synthesis from Carboxylic Esters

“…2016 年, Gosmini 课题组 [49] 首次报道了以氯甲酸酯 作为羰基源, 在钴催化剂的作用下, 与原位生成的芳基 锌试剂反应, 制备对称的二芳基酮的研究(Scheme 24). 基于氯甲酸酯作为羰基源的研究, 朱少林课题组 [52] 在 2021 年发展了 NiH 催化体系下分子间的多组分偶 联反应(Scheme 25c). 该方法是以氯甲酸乙酯为羰基源, 在 Ni 催化体系下, 经连续的烯烃还原-羰基化过程, 以 高区域选择性和对映选择性实现了手性 α-芳基酮和氨 基酮的合成.…”

Ligand centered redox enabled sustainable synthesis of triazines and pyrimidines using a zinc-stabilized azo-anion radical catalyst

“…However, the inherent tendency of this class of metal ions to undergo single electron transfer processes restricts their application in chemical transformations proceeding via multi-electron redox events. 12 On the other hand, despite being scarce, expensive, and toxic, noble metals are often used to bring about many multi-electron chemical transformations, including several industrial processes, because they undergo facile two-electron redox events. In this regard, the metal–ligand cooperative catalysis using transition metal complexes of redox-active ligands as catalysts offers a simple alternative of using benign 3d-metal ions as catalysts.…”

Recent Advances in Non-Precious Metal Catalysis

“…In view of previous reports on Ni-catalyzed asymmetric reductive coupling of acid chlorides to racemic alkyl halides, which was effectively applied for the enantioselective synthesis of acyclic structures of α,α-disubstituted ketones, 3 Zhu and coworkers 4 explored allowing the in situ generated nickel hydride to undergo sequential reductive hydroformylation with unactivated alkenes, followed by enantioconvergent coupling with racemic secondary arylhalide for the formation of α-chiral ketones. Indeed, an effective Ni-catalyzed multicomponent coupling was developed using silane (diethoxymethylsilane) as the reductant, chloroformate as an effective CO source, and secondary benzyl chloride in racemic form.…”