Gem-Difluorocyclopropenes as Versatile β-Monofluorinated Three-sp2Carbon Sources for Cp*Rh(III)-Catalyzed [4 + 3] Annulation: Experimental Development and Mechanistic Insight

doi:10.1021/acscatal.1c04508

	*Gem-Difluorocyclopropenes as Versatile β-Monofluorinated Three-sp2Carbon Sources for CpRh(III)-Catalyzed [4 + 3] Annulation: Experimental Development and Mechanistic Insight**
	Xu, Huiying1,2,3 ; Chen, Weijie 1,2,3; Bian, Mengyao 1,2,3; Xu, Hongtao4,5 ; Gao, Hui 1,2,3; Wang, Ting 1,2,3; Zhou, Zhi 1,2,3; Yi, Wei 1,2,3
	2021-12-03
发表期刊	ACS CATALYSIS (IF:11.3[JCR-2023],12.6[5-Year])
ISSN	2155-5435
EISSN	2155-5435
卷号	11 期号:23 页码:14694-14701
发表状态	已发表
DOI	10.1021/acscatal.1c04508
摘要	Cp*Rh(III)-catalyzed [4 + 3] annulation of N-methoxy amides for the direct assembly of seven-numbered 2H-azepin-2-one frameworks has been realized with gem-difluorocyclopropenes acting as innovative β-monofluorinated three sp2 carbon sources. Either annular arylamides or linear acrylamides with the embedment of various functional groups, including DNA-tagged substrates, were found to be compatible with the established [4 + 3] reaction mode. A redox-neutral Rh(III)-Rh(V)-Rh(III) catalytic cycle, specifically via HOAc-assisted tandem site-/regioselective oxidative addition/reductive elimination/C-F bond cleavage-enabled ring-scission involving the unprecedented olefinic C(sp2)-C(sp2) bond cleavage, has been deduced based on experimental and computational mechanistic studies. Taken together, our findings not only identified gem-difluorocyclopropenes as potent and efficient coupling partners for C-H activation development but also provided a sound basis for the organic integration of transition-metal-catalyzed C-H functionalization with cyclopropene and fluorine chemistries. © 2021 American Chemical Society.
关键词	Activation analysis Amides Catalysis Transition metals 2h-azepin-2-one Aryl amide Bond cleavages C-H functionalization Carbon source Experimental development Gem-difluorocyclopropenes Mechanistics Methoxy [4 + 3] annulation
URL	查看原文
收录类别	EI ; SCIE ; SCI
语种	英语
资助项目	NSFC[21877020,22007020] ; Guangdong Natural Science Funds for Distinguished Young Scholar[2017A030306031] ; China Postdoctoral Science Foundation[2019M662854] ; Natural Science Foundation of Guangdong Province[
WOS研究方向	Chemistry
WOS类目	Chemistry, Physical
WOS记录号	WOS:000753063400039
出版者	American Chemical Society
EI入藏号	20214911275310
EI主题词	Rhodium compounds
EI分类号	531 Metallurgy and Metallography ; 802.2 Chemical Reactions ; 804.1 Organic Compounds
原始文献类型	Article in Press
引用统计	正在获取...
文献类型	期刊论文
条目标识符	https://kms.shanghaitech.edu.cn/handle/2MSLDSTB/135725
专题	生命科学与技术学院免疫化学研究所_特聘教授组_抗体设计学实验室
通讯作者	Zhou, Zhi; Yi, Wei
作者单位	1.Guangzhou Med Univ, Key Lab Mol Target & Clin Pharmacol, Guangzhou 511436, Guangdong, Peoples R China 2.Guangzhou Med Univ, State Key Lab Resp Dis, Sch Pharmaceut Sci, Guangzhou 511436, Guangdong, Peoples R China 3.Guangzhou Med Univ, Affiliated Hosp 5, Guangzhou 511436, Guangdong, Peoples R China 4.ShanghaiTech Univ, Shanghai Inst Adv Immunochem Studies, Shanghai 201210, Peoples R China 5.ShanghaiTech Univ, Sch Life Sci & Technol, Shanghai 201210, Peoples R China
推荐引用方式 GB/T 7714	Xu, Huiying,Chen, Weijie,Bian, Mengyao,et al. Gem-Difluorocyclopropenes as Versatile β-Monofluorinated Three-sp2Carbon Sources for Cp*Rh(III)-Catalyzed [4 + 3] Annulation: Experimental Development and Mechanistic Insight[J]. ACS CATALYSIS,2021,11(23):14694-14701.
APA	Xu, Huiying.,Chen, Weijie.,Bian, Mengyao.,Xu, Hongtao.,Gao, Hui.,...&Yi, Wei.(2021).Gem-Difluorocyclopropenes as Versatile β-Monofluorinated Three-sp2Carbon Sources for Cp*Rh(III)-Catalyzed [4 + 3] Annulation: Experimental Development and Mechanistic Insight.ACS CATALYSIS,11(23),14694-14701.
MLA	Xu, Huiying,et al."Gem-Difluorocyclopropenes as Versatile β-Monofluorinated Three-sp2Carbon Sources for Cp*Rh(III)-Catalyzed [4 + 3] Annulation: Experimental Development and Mechanistic Insight".ACS CATALYSIS 11.23(2021):14694-14701.