近日，南方科技大学刘柳团队报道了铝氧化还原催化实现炔烃环三聚。该研究于2026年2月11日发表在《自然》杂志上。

铝在地壳中的含量超过8%，是含量最丰富的金属元素。从历史上看，铝催化主要利用了其稳定的+III氧化态相关的固有路易斯酸性。由于其独特的低电负性（1.61，在p区元素中最低）以及不存在惰性对效应，铝在参与催化氧化还原转化方面面临着巨大的内在挑战。

研究组报道了一种低价态铝物种卡巴唑基铝烯的氧化还原催化能力，其可完成一个完整的Al(I)/Al(III)催化循环，包括氧化加成、双插入、分子内异构化和还原消除，这些都是传统过渡金属催化中特有的基本反应步骤。利用这种Al(I)/Al(III)氧化还原循环，研究组实现了对炔烃的高效且区域选择性的雷佩环三聚反应，生成了多种苯衍生物，周转率高达2290。

通过X射线晶体学和量子化学分析，研究组阐明了咔唑配体框架内的动态氮几何结构如何精确地调节铝的配位环境，从而促进了催化循环。这项工作从根本上推进了主族氧化还原催化的概念理解。它还为未来催化剂设计和以铝氧化还原转化为中心的可持续合成方法奠定了令人信服的基础。

附：英文原文

Title: Aluminium redox catalysis enables cyclotrimerization of alkynes

Author: Zhang, Xin, Liu, Liu Leo

Issue&Volume: 2026-02-11

Abstract: Aluminium comprises over 8% of Earth’s crust and is the most abundant metallic constituent1. Historically, aluminium catalysis has predominantly exploited the inherent Lewis acidity associated with its stable +III oxidation state2. Owing to its uniquely low electronegativity (1.61)—the lowest among p-block elements—and the absence of an inert-pair effect, aluminium presents formidable intrinsic challenges for engaging in catalytic redox transformations. Here we report the redox catalytic capability of a low-valent aluminium species, carbazolylaluminylene3, which carries out a complete Al(I)/Al(III) catalytic cycle encompassing oxidative addition, double insertion, intramolecular isomerization and reductive elimination—fundamental mechanistic steps conventionally exclusive to transition-metal catalysis. Leveraging this Al(I)/Al(III) redox cycle, we achieve highly efficient and regioselective Reppe cyclotrimerization of alkynes4,5, producing diverse benzene derivatives with a turnover number of up to 2,290. Through X-ray crystallographic and quantum chemical analyses, we elucidate how the dynamic nitrogen geometry within the carbazolyl ligand framework precisely modulates the aluminium coordination environment, thereby facilitating the catalytic cycle. This work fundamentally advances the conceptual understanding of main-group redox catalysis. It further sets a compelling precedent for future catalyst design and sustainable synthetic methodologies centred on aluminium redox transformations.

DOI: 10.1038/s41586-025-09941-9

Source: https://www.nature.com/articles/s41586-025-09941-9