芳基铋试剂的亲环境交叉偶联
近日，德国马克斯·普朗克研究所Josep Cornella团队报道了芳基铋试剂的亲环境交叉偶联。2026年4月9日出版的《自然》杂志发表了这项成果。
传统上，交叉偶联反应允许在过渡金属催化下，于芳基亲核试剂与芳基亲电试剂之间形成Ar-Ar键。迄今为止，众多已知的交叉偶联反应之所以具有高选择性，依赖于亲核和亲电偶联配偶体的特定组合，其机理基础在于亲核试剂与亲电试剂经历根本不同的催化步骤，从而在反应性上得以区分。
研究组报道了一类双亲性芳基铋试剂，它们在过渡金属催化的交叉偶联反应中可以表现为亲核试剂或亲电试剂，从根本上打破了这种反应性上的二分法。化学计量反应和机理研究表明，这种双亲反应性源于它们能够同时参与与过渡金属配合物的氧化加成和金属交换过程。通过证明单一的芳基试剂能够参与这两个经典的基本步骤，该研究挑战了长期以来的假设，即固有的键极性严格决定了交叉偶联化学中的机理角色。
附：英文原文
Title: Ambiphilic cross-coupling with aryl-bismuth reagents
Author: Roh, Byeongdo, Williams, Benedict A., Cornella, Josep
Issue&Volume: 2026-04-09
Abstract: Cross-coupling reactions traditionally permit the formation of Ar-Ar bonds between an aryl nucleophile and an aryl electrophile under transition metal catalysis1,2. The high selectivity of the myriad of couplings known to date relies on a tailored combination of nucleophilic and electrophilic coupling partners, enabled by the mechanistic distinction between nucleophiles and electrophiles, which undergo fundamentally different catalytic steps.3 Here, we report ambiphilic aryl-bismuth reagents that can behave as either nucleophiles or electrophiles in transition metal-catalysed cross-couplings, fundamentally breaking from this dichotomy in reactivity. Their ambiphilic reactivity arises from their ability to engage in both oxidative addition and transmetalation processes with transition metal complexes, as demonstrated by stoichiometric and mechanistic studies. By demonstrating that a single aryl reagent can engage in both canonical elementary steps, this work challenges the long-standing assumption that intrinsic bond polarity rigidly dictates mechanistic role in cross-coupling chemistry.
DOI: 10.1038/s41586-026-10486-8
Source: https://www.nature.com/articles/s41586-026-10486-8
期刊信息
Nature：《自然》，创刊于1869年。隶属于施普林格·自然出版集团，最新IF：69.504
投稿链接：http://www.nature.com/authors/submit_manuscript.html
