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铁催化[1+1+1]环丙烷化:酯与两个卡宾的连续偶联
作者:小柯机器人 发布时间:2026/9/5 9:26:53

近日,美国斯克里普斯研究所Ryan Shenvi团队报道了铁催化[1+1+1]环丙烷化:酯与两个卡宾的连续偶联。相关论文于2026年8月27日发表在《科学》杂志上。

传统的贵金属催化受益于明确表征的内层基元步骤,即单个配合物在金属中心结合并连接底物。相比之下,贱金属催化剂最近已被证明能够通过迭代的外层反应实现交叉偶联转化,其中产物键的形成通过配体(而非金属)的连续加成实现。尽管双组分外层反应日益多样化,但类似的多组分外层偶联反应仍然罕见。

研究组描述了一种铁催化的[1+1+1]环丙醇合成方法,该方法通过两个卡宾和一个酯之间的迭代外层反应实现。该反应经无痕导向烯化,可立体、区域及化学选择性地生成硅基烯醇醚,
且能够进一步用于实现先前方法无法完成的转化。

附:英文原文

Title: Iron-catalyzed [1+1+1] cyclopropanation by sequential coupling of an ester to two carbenes

Author: Lingran Kong, Kevin Zong, Marcus Hopfengrtner, Brandon J. Orzolek, Ryan Shenvi

Issue&Volume: 2026-08-27

Abstract: Traditional precious metal catalysis benefits from well-characterized inner-sphere elementary steps in which a single complex binds and unites substrates at the metal center. By contrast, base metal catalysts have recently demonstrated competence in cross-coupling transformations through iterative outer-sphere reactions in which product bond formation occurs by serial additions to the ligand, not the metal. Despite the emerging diversity of two-component outer-sphere reactions, comparable multicomponent outer-sphere couplings remain rare. In this study, we describe an iron-catalyzed [1+1+1] synthesis of cyclopropanols through iterative outer-sphere reactions between two carbenes and an ester. This reaction initially generates silyl enol ethers stereo-, regio-, and chemoselectively through a traceless, directed olefination that can be further exploited to enable transformations unavailable to prior methods.

DOI: 10.1126/science.aej0194

Source: https://www.science.org/doi/10.1126/science.aej0194

 

期刊信息

Science:《科学》,创刊于1880年。隶属于美国科学促进会,最新IF:63.714
官方网址:https://www.sciencemag.org/
投稿链接:https://cts.sciencemag.org/scc/#/login