Recent Advance in Ni-Catalyzed Reductive Cross-Coupling to Construct C(sp²)-C(sp²) and C(sp²)-C(sp³) Bonds

Abstract

镍催化还原偶联反应构筑 C(sp 2)-C(sp 2)/C(sp 2)-C(sp 3)键的研究进展 李娅琼 范玉航 贾乾发 * (长江师范学院化学化工学院 重庆 408100) 摘要 亲电试剂的还原偶联反应避免了有机金属试剂的制备与使用, 对各类官能团拥有极好的兼容性, 为 CC 键的 构筑提供了一类重要的方法. 近些年来, 该反应的研究取得了突破性进展, 实现了一系列 C(sp 2)-X 与 C(sp 3)-X 亲电 试剂参与的交叉偶联反应. 主要针对镍催化亲电试剂交叉偶联反应构筑 C(sp 2)-C(sp 2)和 C(sp 2)-C(sp 3)键的研究展开 综述, 详细介绍了各种偶联反应及其反应机制.

General C(sp2)–C(sp3) Cross-Electrophile Coupling Reactions Enabled by Overcharge Protection of Homogeneous Electrocatalysts

“…Because the nucleophilic substrate is generally an organometallic species that is separately prepared from an electrophile, a more streamlined approach to C–C bond formation involves the reductive coupling of two electrophilic reagents in a cross-electrophile coupling (XEC) . Pioneering work by Périchon, − Weix, , and Gosmini, along with key advances by Gong, − Reisman, − MacMillan, and others, − has propelled this once nascent methodology to the forefront of approaches for C–C bond formation. ,,− …”

Nickel‐Catalyzed Electrochemical Reductive Relay Cross‐Coupling of Alkyl Halides to Aryl Halides

“…[1] Recently, substantial effort has also been spent on the development of nickel-catalyzed reductive cross-coupling reactions between aryl electrophiles and alkyl electrophiles, wherein organometallic reagents are avoided. [2] For instance, in 2010 Weix and co-workers reported efficient Ni-catalyzed cross-couplings of aryl halides with unactivated alkyl halides using Mn as the reductant (Scheme 1 a). [3] Inspired by this seminal work, many Ni-catalyzed reductive cross-couplings between aryl halides and alkyl halides have been developed, including asymmetric variants.…”

Synergistic Catalyst–Mediator Pairings for Electroreductive Cross-Electrophile Coupling Reactions

“…Cross-electrophile coupling (XEC) to form C–C bonds directly from alkyl and aryl halides has developed into a reliable alternative to cross-coupling reactions that rely on preformed organometallic substrates. − Recent examples of XEC reactions performed in the industry further emphasize the importance of the methodology. − While these reactions are classically performed with powdered metal reductants, efforts have been directed toward the development of photoredox ,− and electrochemical ,,− XEC processes that could provide complementary reactivity and improve scalability.…”