The development of metal-catalysed cross-coupling reactions between one electrophilic and one organometallic nucleophilic partner has revolutionized the practice of chemical synthesis, with coupling reactions between sp² centres now commonplace in both academic and industrial research. Methods to allow coupling of sp³ centres are rapidly being developed, with many recent advances even enabling control of the absolute configuration of newly formed stereogenic centres. The related cross-electrophile couplings have not been developed as thoroughly owing to the challenge of obtaining cross-selectivity between two substrates with similar reactivity. However, the discovery of improved methods to address this challenge has led to significant recent progress. The development of enantioselective cross-electrophile coupling reactions is an emerging area of research. Both stereoconvergent and stereospecific variants have been reported for the synthesis of a range of products containing tertiary stereogenic centres. Many of these transformations build on lessons learnt from traditional (electrophile–nucleophile) cross-couplings of alkyl electrophiles. For example, all enantioselective transformations described to date use a nickel catalyst. Continued progression is likely to provide strategic disconnections for asymmetric synthesis of natural products and medicinal agents.

一个亲电子分子和一个有机金属亲核分子之间金属催化的交叉偶联反应的发展彻底改变了化学合成的实践，sp ²中心之间的偶联反应在学术和工业研究中都变得司空见惯。允许sp ³偶联的方法中心正在迅速发展，最近取得了许多进步，甚至可以控制新组建的立体定位中心的绝对配置。由于在具有相似反应性的两个底物之间获得交叉选择性的挑战，相关的交叉亲电子偶联尚未得到充分开发。然而，发现解决该挑战的改进方法导致了近期的重大进展。对映选择性交叉亲电子偶联反应的发展是一个新兴的研究领域。已经报道了立体收敛变体和立体特异性变体都用于合成包含叔立体发生中心的一系列产物。这些转化中的许多转化都是基于从烷基亲电体的传统（亲电体-亲核体）交叉偶联中汲取的教训。例如，迄今为止描述的所有对映选择性转化均使用镍催化剂。持续的发展可能会为天然产物和药物的不对称合成提供战略性的脱节。