A solid noncovalent organic double-helix framework catalyzes asymmetric [6+4] cycloaddition

• 成果类型: Article
• 署名作者: Zheng, Tianyu; Noethling, Nils; Wang, Zikuan; Mitschke, Benjamin; Leutzsch, Markus; List, Benjamin
• 署名单位: Max Planck Society
• 刊物名称: SCIENCE
• ISSN/ISSBN: 0036-12849
• DOI: 10.1126/science.adp1127
• 发表日期: 2024-08-16
• 页码: 765-770
• 关键词: diels-alder reactions; basis-sets; approximation; DESIGN

摘要

Whereas [4 + 2] cycloadditions are among the most powerful tools in the chemist's synthetic arsenal, controlling reactivity and selectivity of [6 + 4] cycloadditions has proven to be extremely challenging. Such transformations, especially if compatible with simple hydrocarbon-based substrates, could ultimately provide a general approach to highly valuable and otherwise difficult to access 10-membered rings. We report here that highly acidic and confined imidodiphosphorimidate catalysts do not catalyze this reaction under homogeneous conditions. Notably, however, they can spontaneously precipitate an insoluble and double helix-shaped noncovalent organic framework, which acts as a distinctively reactive and stereoselective catalyst of [6 + 4] cycloadditions of simple dienes with tropone.