美国加州大学洛杉矶分校的Neil K. Garg研究组报道了反布雷特烯烃合成问题的解决方法。2024年11月1日出版的《科学》杂志发表了这项成果。

研究人员表示，不饱和有机分子中的π键通常与具有良好定义的几何形状有关，这些几何形状在不同的结构环境中是保守的。然而，这些几何形状可以被扭曲，导致π键的反应性增强。虽然具有弯曲几何形状的含π键化合物，在合成化学中得到了很好的应用，但具有扭曲或金字塔化结构的，含π键化合物的相应应用还不发达。

课题组报道了一项可能是最臭名昭著的一类含有π键的几何扭曲分子——反Bredt烯烃（ABO）的研究。自1924年以来，ABO就已经为人所知，传统观点认为ABO很难或不可能获得。研究组为这个长期存在的问题提供了解决方案。他们的研究还强调了对某些化合物的策略操纵，这些化合物由于几何约束π键的存在，而显示出相当大的扭曲。

附：英文原文

Title: A solution to the anti-Bredt olefin synthesis problem

Author: Luca McDermott, Zach G. Walters, Sarah A. French, Allison M. Clark, Jiaming Ding, Andrew V. Kelleghan, K. N. Houk, Neil K. Garg

Issue&Volume: 2024-11-01

Abstract: The π-bonds in unsaturated organic molecules are typically associated with having well-defined geometries that are conserved across diverse structural contexts. Nonetheless, these geometries can be distorted, leading to heightened reactivity of the π-bond. Although π-bond–containing compounds with bent geometries are well utilized in synthetic chemistry, the corresponding leveraging of π-bond–containing compounds that display twisting or pyramidalization remains underdeveloped. We report a study of perhaps the most notorious class of geometrically distorted molecules that contain π-bonds: anti-Bredt olefins (ABOs). ABOs have been known since 1924, and conventional wisdom maintains that ABOs are difficult or impossible to access. We provide a solution to this long-standing problem. Our study also highlights the strategic manipulation of compounds that display considerable distortion arising from the presence of geometrically constrained π-bonds.

DOI: adq3519

Source: https://www.science.org/doi/10.1126/science.adq3519