近日，德国马克斯·普朗克煤炭研究所Tobias Ritter团队报道了噻蒽叶立德的卡宾转移用于环丙烷化。该研究于2026年9月30日发表在《自然》杂志上。

卡宾是反应性的二价碳中间体，可作为一碳合成子用于构建环丙烷。这类三元碳环的合成价值使化学家接受了传统和现代环丙烷化反应所需的爆炸性起始原料或中间体²所带来的危险。锍盐虽然更安全，但在环丙烷化反应中一直缺乏竞争力，因为它们通常不能作为高效的卡宾供体。在所有已报道的环丙烷化反应中，多样性可通过烯烃或卡宾伙伴之一获得，但不能同时通过两者获得；例如，若干现代反应仅限于活化烯烃，如苯乙烯。

研究组报道烷基噻蒽盐如何在概念上不同于所有其他卡宾前体，并允许卡宾转移化学，包括环丙烷的合成，其中烯烃和卡宾伙伴都可以具有多样性。噻蒽的空间位阻和低路易斯碱性可以解释噻蒽盐在环丙烷化反应中优越的反应性，因为避免了其他锍盐所存在的势能面上不期望的能量低位局部极小值。尽管反应性高，噻蒽盐仍表现出理想的安全性特征，实现了放大生产，也可通过球磨在固态下进行，而这对于许多其他环丙烷化反应来说是危险的。反应性与安全性的结合凸显了噻蒽叶立德作为金属–卡宾反应性的一般化合物类别，其应用范围超越环丙烷化，扩展至多种卡宾转移反应，包括σ键插入和σ迁移重排。

附：英文原文

Title: Carbene transfer from thianthrenium ylides for cyclopropanation

Author: Behera, Deepak, Chatterjee, Sagnik, Adorjn, ron, Wang, Chuanhao, Altun, Ahmet, Neese, Frank, Ritter, Tobias

Issue&Volume: 2026-09-30

Abstract: Carbenes are reactive divalent carbon intermediates that serve as one-carbon synthons to access cyclopropanes. The synthetic utility of these three-membered carbocycles has led chemists to accept the dangers associated with the explosive starting materials1 or intermediates2 required for both conventional and modern cyclopropanation reactions. Sulfonium salts, although safer, have not been competitive for cyclopropanation because they typically do not function as efficient carbene donors3. In all cyclopropanation reactions reported, diversity can be obtained through either the olefin or carbene partner, but not both; for example, several modern reactions are limited to activated olefins, such as styrenes4,5,6,7. Here we report how alkylthianthrenium salts differ conceptually from all other carbene precursors and allow for carbene-transfer chemistry, including the synthesis of cyclopropanes, in which both the olefin and the carbene partner can be diverse. The steric bulk and low Lewis basicity of thianthrene can rationalize the superior reactivity of the thianthrenium salts for cyclopropanation because undesired energetically low-lying local minima on the potential energy surface, as present for other sulfonium salts, are avoided. Despite high reactivity, thianthrenium salts exhibit a desirable safety profile that allows scale up, also in the solid state through ball-milling, which is dangerous with many other cyclopropanation reactions. The combination of reactivity and safety highlights thianthrenium ylides as a general compound class for metal–carbene reactivity that extends beyond cyclopropanation to diverse carbene-transfer reactions, including σ-bond insertion and sigmatropic rearrangements.

DOI: 10.1038/s41586-026-11108-z

Source: https://www.nature.com/articles/s41586-026-11108-z

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

官方网址：http://www.nature.com/

投稿链接：http://www.nature.com/authors/submit_manuscript.html