Controlled oligomerization of [1.1.1]propellane through radical polarity matching: selective synthesis of SF5- and CF3SF4-containing [2]staffanes.

IF 2.2 4区 化学 Q2 CHEMISTRY, ORGANIC Beilstein Journal of Organic Chemistry Pub Date : 2024-11-29 eCollection Date: 2024-01-01 DOI:10.3762/bjoc.20.259
Jón Atiba Buldt, Wang-Yeuk Kong, Yannick Kraemer, Masiel M Belsuzarri, Ansh Hiten Patel, James C Fettinger, Dean J Tantillo, Cody Ross Pitts
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Abstract

Selectivity in radical chain oligomerizations involving [1.1.1]propellane - i.e., to make [n]staffanes - has been notoriously challenging to control when n > 1 is desired. Herein, we report selective syntheses of SF5- and CF3SF4-containing [2]staffanes from SF5Cl and CF3SF4Cl, demonstrating cases whereby oligomerization is preferentially truncated after incorporation of two bicyclopentane (BCP) units. Synthetic and computational studies suggest this phenomenon can be attributed to alternating radical polarity matching. In addition, single-crystal X-ray diffraction (SC-XRD) data reveal structurally interesting features of the CF3SF4-containing [2]staffane in the solid state.

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通过自由基极性匹配控制[1.1.1]推进剂的低聚化:含SF5-和cf3sf4的[2]烷的选择性合成。
涉及[1.1.1]推进剂的自由基链寡聚反应的选择性——即制造[n]职员——在需要n > 1时一直是非常具有挑战性的。本文中,我们报道了从SF5Cl和CF3SF4Cl选择性合成含SF5-和cf3sf4的[2]staffes,证明了在加入两个双环戊烷(BCP)单元后,寡聚反应优先被截断的情况。综合和计算研究表明,这种现象可归因于交替的自由基极性匹配。此外,单晶x射线衍射(SC-XRD)数据揭示了固体状态下含cf3sf4的[2]staff的结构特征。
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来源期刊
CiteScore
4.90
自引率
3.70%
发文量
167
审稿时长
1.4 months
期刊介绍: The Beilstein Journal of Organic Chemistry is an international, peer-reviewed, Open Access journal. It provides a unique platform for rapid publication without any charges (free for author and reader) – Platinum Open Access. The content is freely accessible 365 days a year to any user worldwide. Articles are available online immediately upon publication and are publicly archived in all major repositories. In addition, it provides a platform for publishing thematic issues (theme-based collections of articles) on topical issues in organic chemistry. The journal publishes high quality research and reviews in all areas of organic chemistry, including organic synthesis, organic reactions, natural product chemistry, structural investigations, supramolecular chemistry and chemical biology.
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