Sequential C–F bond functionalizations of trifluoroacetamides and acetates via spin-center shifts

doi:10.1126/science.abg0781

GSTDTAP > 气候变化

DOI	10.1126/science.abg0781
	Sequential C–F bond functionalizations of trifluoroacetamides and acetates via spin-center shifts
	You-Jie Yu; Feng-Lian Zhang; Tian-Yu Peng; Chang-Ling Wang; Jie Cheng; Chen Chen; Kendall N. Houk; Yi-Feng Wang
	2021-03-19
发表期刊	Science
出版年	2021
英文摘要	It is often useful in pharmaceutical or agrochemical research to modify the properties of carbon compounds by appending one or more fluorine atoms. However, the methods used to prepare mono-, di-, or trifluorocarbon centers tend to differ from each other in inconvenient ways. Yu et al. developed a radical reaction that can successively remove one or two fluorine atoms from trifluoromethyl groups adjacent to amides or esters. The mechanism relies on a spin-center shift after attack at the carbonyl oxygen by a boryl radical. Science , this issue p. [1232][1] Defluorinative functionalization of readily accessible trifluoromethyl groups constitutes an economical route to partially fluorinated molecules. However, the controllable replacement of one or two fluorine atoms while maintaining high chemoselectivity remains a formidable challenge. Here we describe a general strategy for sequential carbon-fluorine (C–F) bond functionalizations of trifluoroacetamides and trifluoroacetates. The reaction begins with the activation of a carbonyl oxygen atom by a 4-dimethylaminopyridine-boryl radical, followed by a spin-center shift to trigger the C–F bond scission. A chemoselectivity-controllable two-stage process enables sequential generation of difluoro- and monofluoroalkyl radicals, which are selectively functionalized with different radical traps to afford diverse fluorinated products. The reaction mechanism and the origin of chemoselectivity were established by experimental and computational approaches. [1]: /lookup/doi/10.1126/science.abg0781
领域	气候变化 ; 资源环境
URL	查看原文
引用统计
文献类型	期刊论文
条目标识符	http://119.78.100.173/C666/handle/2XK7JSWQ/319933
专题	气候变化资源环境科学
推荐引用方式 GB/T 7714	You-Jie Yu,Feng-Lian Zhang,Tian-Yu Peng,等. Sequential C–F bond functionalizations of trifluoroacetamides and acetates via spin-center shifts[J]. Science,2021.
APA	You-Jie Yu.,Feng-Lian Zhang.,Tian-Yu Peng.,Chang-Ling Wang.,Jie Cheng.,...&Yi-Feng Wang.(2021).Sequential C–F bond functionalizations of trifluoroacetamides and acetates via spin-center shifts.Science.
MLA	You-Jie Yu,et al."Sequential C–F bond functionalizations of trifluoroacetamides and acetates via spin-center shifts".Science (2021).