近日，德国马克斯·普朗克研究所Tobias Ritter团队报道了烯烃的脱羧烷基化。2026年4月29日出版的《自然》杂志发表了这项成果。

烯烃是合成化学中广泛应用的重要官能团，在聚合物、洗涤剂、农用化学品及药物生产中具有关键作用。当与亲电试剂反应时，烯烃通常发生加成反应而非取代反应。因此，化学家的工具库中并不存在通过母体烯烃直接构建取代烯烃的直观逆合成切断策略。例如，将三取代烯烃转化为四取代烯烃，或对复杂烯烃进行后期烷基化，将能够构建当前难以合成的分子。烯烃交叉复分解反应可对适当取代的烯烃进行形式上的烷基化，但其非对映选择性和烯烃-烷基组合受限于特定情形，且内烯或环状烯烃等多类烯烃难以通过现有方法实现烷基化。

研究组报道了以羧酸为烷基来源的烯烃区域选择性与非对映选择性C−H烷基化反应——羧酸来源广泛且结构多样。该方法的突破在于实现了一种极性脱羧烷基化路径，与当前基于羧酸衍生物的自由基介导C−C键形成模式截然不同，其关键是通过先前未被重视的途径，从氧化还原活性酯中获得稳定的烷基锌中间体。通过钯催化的烷基锌物种与由烯烃衍生的烯基噻蒽鎓盐的交叉偶联反应，即可高非对映选择性地获得取代烯烃。该转化适用于环状、无环、末端、内部、单取代、双取代及三取代烯烃，并可引入多样化的烷基基团。

附：英文原文

Title: Decarboxylative alkylation of alkenes

Author: Roy, Triptesh Kumar, Tamborini, Federico Maria, Petzold, Roland, Fu, Jianhan, Tang, Yiben, Ritter, Tobias

Issue&Volume: 2026-04-29

Abstract: Alkenes are widely used functional groups in synthetic chemistry, important for producing polymers, detergents, agrochemicals and pharmaceuticals. When treated with electrophiles, alkenes typically undergo addition, not substitution, reactions1. As a consequence, the intuitive retrosynthetic disconnection to form a substituted alkene from the parent alkene does not exist in the toolbox of the chemist. For example, conversion of tri-substituted into tetra-substituted alkenes, or late-stage alkylation of complex alkenes, would provide access to molecules that are currently difficult to construct. Alkene cross-metathesis can formally alkylate appropriately substituted alkenes, but diastereoselectivity and alkene–alkyl combinations are restricted to specific cases2, and several classes of alkenes, such as internal or cyclic alkenes, cannot be readily alkylated with known methods3. Here we report a formal regio- and diastereoselective CH alkylation of alkenes with carboxylic acids as alkyl source, readily available in large diversity. Key to the development is a polar decarboxylative alkylation that deviates from the current model of radical-mediated CC bond formation from carboxylic acid derivatives, enabled by a previously unappreciated access to persistent alkylzinc intermediates from redox-active esters. A Pd-catalysed cross-coupling of the alkylzinc species with alkenyl thianthrenium salts accessed from alkenes affords the substituted alkenes in high diastereoselectivity. The transformation offers alkylation of cyclic, acyclic, terminal, internal, mono-substituted, di-substituted and tri-substituted alkenes with diverse alkyl groups.

DOI: 10.1038/s41586-026-10463-1

Source: https://www.nature.com/articles/s41586-026-10463-1