Time-Dependent Divergent Synthesis via Photochemical Rearrangement.

IF 16.9 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Shu-Ya Wen,Yuchen Zhang,Jun-Jie Chen,Xiao-Song Xue,Huan-Ming Huang
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引用次数: 0

Abstract

Divergent synthesis is a powerful and economical approach in synthetic chemistry and materials science. However, achieving precise control over divergent reactions using only reaction time as a variable is still rare. Herein, we show a time-dependent photochemical rearrangement driven by energy transfer catalysis under visible light. Remarkably, by simply adjusting the reaction time, we can selectively synthesize two distinct types of fluorinated strained rings using the same photocatalyst. Mechanistic experiments and computational studies reveal that this photochemical rearrangement follows a kinetically controlled pathway, involving a sequence of steps: diradical formation, 1,4-aryl migration, and 1,3-diradical formation. Interestingly, when the reaction time is extended, the newly formed difluoromethyl cyclopropanes can reversibly revert to the starting materials. This indicates that the final product is not simply kinetically or thermodynamically favored in the ground state potential energy surface. Instead, the excited state introduces additional complexity to the situation, as the starting materials are then fully converted into 1,1-difluorocyclopropanes through an excited-state thermodynamic control pathway-defined as the product distribution being governed by the relative thermodynamic stabilities of intermediates on the excited-state potential energy surface (PES), in contrast to conventional ground-state thermodynamic control, which relies on singlet ground-state PES stabilities under thermal conditions.
光化学重排的时变发散合成。
发散合成是合成化学和材料科学中一种强大而经济的方法。然而,仅使用反应时间作为变量来实现对发散反应的精确控制仍然很少见。在此,我们展示了在可见光下由能量转移催化驱动的时间依赖性光化学重排。值得注意的是,通过简单地调整反应时间,我们可以使用相同的光催化剂选择性地合成两种不同类型的氟化应变环。机械实验和计算研究表明,这种光化学重排遵循动力学控制的途径,涉及一系列步骤:二自由基形成,1,4-芳基迁移和1,3-二自由基形成。有趣的是,当反应时间延长时,新生成的二氟甲基环丙烷可以可逆地还原为起始物质。这表明最终产物在基态势能面不只是动力学或热力学上有利。相反,激发态给情况带来了额外的复杂性,因为起始材料随后通过激发态热力学控制途径完全转化为1,1-二氟环丙烷——与传统的基态热力学控制相比,激发态热力学控制途径定义为由激发态势能面(PES)上中间体的相对热力学稳定性控制的产物分布。它依赖于单线态基态PES在热条件下的稳定性。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
CiteScore
26.60
自引率
6.60%
发文量
3549
审稿时长
1.5 months
期刊介绍: Angewandte Chemie, a journal of the German Chemical Society (GDCh), maintains a leading position among scholarly journals in general chemistry with an impressive Impact Factor of 16.6 (2022 Journal Citation Reports, Clarivate, 2023). Published weekly in a reader-friendly format, it features new articles almost every day. Established in 1887, Angewandte Chemie is a prominent chemistry journal, offering a dynamic blend of Review-type articles, Highlights, Communications, and Research Articles on a weekly basis, making it unique in the field.
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