A solution to the anti-Bredt olefin synthesis problem

• 成果类型: Article
• 署名作者: Mcdermott, Luca; Walters, Zach G.; French, Sarah A.; Clark, Allison M.; Ding, Jiaming; Kelleghan, Andrew V.; Houk, K. N.; Garg, Neil K.
• 署名单位: University of California System; University of California Los Angeles
• 刊物名称: SCIENCE
• ISSN/ISSBN: 0036-9361
• DOI: 10.1126/science.adq3519
• 发表日期: 2024-11-01
• 关键词: diels-alder reaction; basis-sets; bridgehead; DESIGN; activation; generation; chemistry; arynes; route; RULE

摘要

The pi-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 pi-bond. Although pi-bond-containing compounds with bent geometries are well utilized in synthetic chemistry, the corresponding leveraging of pi-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 pi-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 pi-bonds.