Halogen-bond-assisted radical remote difunctionalization of bicyclo[1.1.1]butane skeletons†

IF 9.3 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry Pub Date : 2024-11-15 DOI:10.1039/D4GC05166A

Hui Liu, Zhenda Fu, Xingwei Li and Songjie Yu

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引用次数: 0

Abstract

Transition-metal-free radical remote difunctionalization of bicyclo[1.1.1]butane skeletons in both two- and three-component fashions is presented. The reactions proceed via halogen-bond-assisted polyfluoroalkyl radical addition to newly designed 1-vinylbicyclo[1.1.1]pentanes, followed by strain-release-driven C–C bond cleavage to generate a strained cyclobutylmethyl radical. In the two-component reaction, iodine atom transfer to the resulting cyclobutylmethyl radical with polyfluoroiodides forms a broad array of strained 1,6-polyfluorocarboiodinated products, while boron atom transfer with bis(catecholato)diboron releases various strained 1,6-polyfluorocarboborylated products in the three-component reaction. This redox-neutral reaction features mild conditions, ease of operation, high atom economy, functional group tolerance, and a broad substrate scope, and offers a practical and sustainable approach for the synthesis of a range of challenging polyfluoroalkylated cyclobutane skeletons containing iodine and boron as versatile transformation handles for further useful derivatizations.

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双环[1.1.1]丁烷骨架的卤素键辅助自由基远程双官能化

介绍了以双组分和三组分方式对双环[1.1.1]丁烷骨架进行的无过渡金属自由基远程双官能化反应。这些反应通过卤素键辅助的多氟烷基自由基加成到新设计的 1-乙烯基双环[1.1.1]戊烷，然后通过应变释放驱动的 C-C 键裂解生成应变环丁基甲基自由基。在双组分反应中，碘原子与多氟碘化物转移到生成的环丁基甲基自由基上，形成一系列广泛的应变 1,6-多氟羰基碘化产物，而在三组分反应中，硼原子与双（邻苯二酚）二硼转移释放出各种应变 1,6-多氟羰基化产物。这种氧化还原中性反应具有条件温和、操作简便、原子经济性高、官能团耐受性强、底物范围广等特点，为合成一系列具有挑战性的多氟烷基化环丁烷骨架提供了一种实用且可持续的方法。

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来源期刊

Green Chemistry 化学-化学综合

CiteScore

16.10

自引率

7.10%

发文量

677

审稿时长

1.4 months

期刊介绍： Green Chemistry is a journal that provides a unique forum for the publication of innovative research on the development of alternative green and sustainable technologies. The scope of Green Chemistry is based on the definition proposed by Anastas and Warner (Green Chemistry: Theory and Practice, P T Anastas and J C Warner, Oxford University Press, Oxford, 1998), which defines green chemistry as the utilisation of a set of principles that reduces or eliminates the use or generation of hazardous substances in the design, manufacture and application of chemical products. Green Chemistry aims to reduce the environmental impact of the chemical enterprise by developing a technology base that is inherently non-toxic to living things and the environment. The journal welcomes submissions on all aspects of research relating to this endeavor and publishes original and significant cutting-edge research that is likely to be of wide general appeal. For a work to be published, it must present a significant advance in green chemistry, including a comparison with existing methods and a demonstration of advantages over those methods.