Zhu Yulei, Jia Jie, Song Xiangyu, Gong Chunyu, Xia Ying
West China School of Public Health and West China Fourth Hospital, West China-PUMC C. C. Chen Institute of Health, State Key Laboratory of Biotherapy, Sichuan University Chengdu 610041 China
Chem Sci. 2024 Jul 27;15(34):13800-6. doi: 10.1039/d4sc03624g.
Metathesis reactions have been established as a powerful tool in organic synthesis. While great advances were achieved in double-bond metathesis, like olefin metathesis and carbonyl metathesis, single-bond metathesis has received less attention in the past decade. Herein, we describe the first C(sp)-O/C(sp)-F bond formal cross metathesis reaction between -difluorinated cyclopropanes (-DFCPs) and epoxides under rhodium catalysis. The reaction involves the formation of a highly electrophilic fluoroallyl rhodium intermediate, which is capable of reacting with the oxygen atom in epoxides as weak nucleophiles followed by C-F bond reconstruction. The use of two strained ring substrates is the key to the success of the formal cross metathesis, in which the double strain release accounts for the driving force of the transformation. Additionally, azetidine also proves to be a suitable substrate for this transformation. The reaction offers a novel approach for the metathesis of C(sp)-O and C(sp)-N bonds, presenting new opportunities for single-bond metathesis.
复分解反应已成为有机合成中的一种强大工具。虽然在双键复分解反应中取得了巨大进展，如烯烃复分解反应和羰基复分解反应，但单键复分解反应在过去十年中受到的关注较少。在此，我们描述了在铑催化下，-二氟环丙烷（-DFCPs）与环氧化物之间首次发生的C(sp)-O/C(sp)-F键形式的交叉复分解反应。该反应涉及形成一种高亲电的氟代烯丙基铑中间体，它能够与环氧化物中的氧原子作为弱亲核试剂发生反应，随后进行C-F键重构。使用两种张力环底物是形式交叉复分解反应成功的关键，其中双重张力释放是转化的驱动力。此外，氮杂环丁烷也被证明是这种转化的合适底物。该反应为C(sp)-O和C(sp)-N键的复分解提供了一种新方法，为单键复分解反应带来了新机遇。
