尽管[4+2]环加成是化学家合成工具库中最强大的工具之一,但控制[6+4]环加成的反应性和选择性已被证明极具挑战性。这种转化,特别是如果与简单的烃基底物兼容,最终可以为高价值且难以获得的10元环提供一种通用方法。
该文中,研究人员报道了高酸性和受限的亚氨基二磷酰亚胺催化剂在均相条件下不能催化该反应。然而,值得注意的是,它们可以自发沉淀出一种不溶的双螺旋形非共价有机框架,该框架作为简单二烯与肌钙蛋白[6+4]环加成反应的独特反应性和立体选择性催化剂。
附:英文原文
Title: A solid noncovalent organic double-helix framework catalyzes asymmetric [6 + 4] cycloaddition
Author: Tianyu Zheng, Nils Nthling, Zikuan Wang, Benjamin Mitschke, Markus Leutzsch, Benjamin List
Issue&Volume: 2024-08-16
Abstract: 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.
DOI: adp1127
Source: https://www.science.org/doi/10.1126/science.adp1127
Science:《科学》,创刊于1880年。隶属于美国科学促进会,最新IF:63.714
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