摘要/Abstract

过渡金属催化的偶联反应是构筑C-C键的高效方法，在有机合成中得到了广泛的应用.然而，相对于Heck反应、Negishi偶联与Suzuki偶联等构筑C（sp²）-C（sp²）键的反应，过渡金属催化的构筑C（sp³）-C（sp³）键的偶联反应较难进行，发展较晚.近年来，烷基-烷基C-C键偶联反应受到广泛的重视，一些高效催化剂被开发出来，其中镍催化剂展示出独特的催化活性和选择性.本文将综述镍催化烷基-烷基C-C键偶联反应最新研究进展，主要包括烷基亲电试剂与金属有机试剂交叉偶联反应、导向基参与的C（sp³）-H键活化的偶联反应、镍-光反应催化剂协同催化偶联反应、烷基亲电试剂与亲电试剂的还原偶联反应和镍催化烯烃加成反应等.
关键词: 镍催化剂, C(sp³)-C(sp³)键构筑, 交叉偶联反应, 烯烃加成反应, 不对称合成
Transition metal-catalyzed coupling reactions are powerful synthetic methods for the C-C bond formation. Many coupling reactions such as Heck reaction, Negishi coupling, and Suzuki coupling have been widely applied in the syntheses of pharmaceuticals, functional materials and fine chemicals. In those coupling reactions, a C(sp²)-C(sp²) bond is formed in high efficiency and selectivity. However, in contrast to the C(sp²)-C(sp²) couplings, the C(sp³)-C(sp³) couplings are more difficult and develop late. Because the C(sp³)-C(sp³) bonds are ubiquitous in organic compound, the C(sp³)-C(sp³) bond formation is the central task of research in organic chemistry. In the past two decades, a great effort has been devoted to the development of cross-coupling reactions between alkyls to construct C(sp³)-C(sp³) bonds and impressive progress has been achieved. Among the transition metal catalysts that have been used in the construction of C(sp³)-C(sp³) bonds, nickel was found to be a preferable one, exhibiting unique activity and selectivity. Nickel catalysts promote the activation of alkyl electrophiles via radical catalytic cycles and inhibit and/or manipulate β-H elimination reactions. Nickel has several variable valence states and can flexibly participate in tandem reactions and reductive cross-coupling reactions. All these characteristic natures contribute to the success of nickel catalysts in the construction of C(sp³)-C(sp³) bonds. In this review, we will describe the advances on the nickel-catalyzed C(sp³)-C(sp³) bond-forming reactions. The main contents of this review include:the cross-coupling of alkyl electrophiles with organometallic reagents; the coupling involving a C(sp³)-H bond activation in the presence of directing group; the coupling co-catalyzed by nickel and photocatalyst; the reductive coupling of two alkyl electrophiles; and the additions of nucleophiles or electrophiles to alkenes such as hydroalkylation and difunctionalization of alkenes. The review will focus on the latest developments of nickel-catalyzed alkyl coupling reactions in the past two decades. The mechanisms of each reaction are discussed in detail for understanding the reactions.
Key words: nickel catalysis, C(sp³)-C(sp³) bond formation, cross-coupling, addition reactions of olefins, asymmetric synthesis


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