笼型光催化下的可见光诱导[2π+2σ]环加成对精确双环[2.1.1]己烷结构的影响

IF 16.9 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Angewandte Chemie International Edition Pub Date : 2025-10-04 DOI:10.1002/anie.202517394

Yanke Hao, Jie Chen, Zhiwei Jiao, Cheng‐Yong Su

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引用次数: 0

摘要

在光活性金属-有机笼（PMOC）催化下，在易得的查尔酮和1,3 -二取代双环[1.1.0]丁烷（BCBs）之间进行了可见光诱导的非对映选择性[2π+2σ]光环加成反应。这种受限的超分子催化方法能够高效合成具有药学意义的双环[2.1.1]己烷（BCH）生物同分酯，具有显著的原子经济性和优异的非对映选择性，只需要0.1 mol%的催化剂负载。这种有机转化的成功源于PMOC作为纳米反应器的协同作用，通过主客体相互作用结合了选择性底物预组织，高效的Ru（II）介导的三重态能量转移，以及纳米空间限制效应，精确控制[2π+2σ]环化几何形状，同时防止竞争性同二聚化。

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Visible‐Light‐Induced [2π+2σ] Cycloaddition Enabled by Cage‐Confined Photocatalysis for Precise Bicyclo[2.1.1]Hexane Construction

We disclose a visible‐light‐induced, diastereoselective [2π+2σ] photocycloaddition between readily available chalcones and 1,3‐disubstituted bicyclo[1.1.0]butanes (BCBs) promoted by photoactive metal–organic cage (PMOC). This confined supramolecular catalysis method enables efficient synthesis of pharmaceutically relevant bicyclo[2.1.1]hexane (BCH) bioisosteres with remarkable atom economy and excellent diastereoselectivities, necessitating only 0.1 mol% catalyst loading. The success of this organic transformation arises from the synergistic action of the PMOC as a nanoreactor to combine selective substrate preorganization through host–guest interactions, efficient Ru(II)‐mediated triplet energy transfer, and nano‐spatial confinement effect that precisely control [2π+2σ] cyclization geometry while preventing competitive homodimerization.

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来源期刊

Angewandte Chemie International Edition 化学-化学综合

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.