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Rhodium(III)-Catalyzed Annulation between N-Sulfinyl Ketoimines and Activated Olefins: C-H Activation Assisted by an Oxidizing N-S Bond
Wang, Qiang1; Li, Yingzi2; Qi, Zisong1; Xie, Fang1; Lan, Yu2; Li, Xingwei1
KeywordC-h Bond Activation Rh(Iii) Catalyst N-s Bond Cleavage N-sulfinyl Imine Olefin Isoindole
Source PublicationACS CATALYSIS
2016-03-01
ISSN2155-5435
DOI10.1021/acscatal.5b02297
Volume6Issue:3Pages:1971-1980
Indexed BySCI
SubtypeArticle
WOS HeadingsScience & Technology ; Physical Sciences
WOS SubjectChemistry, Physical
WOS Research AreaChemistry
WOS KeywordSUBSTITUTED PYRIDINE-DERIVATIVES ; RHODIUM-CATALYZED SYNTHESIS ; OXYGEN-ATOM TRANSFER ; SULFONIC-ACID GROUP ; ONE-POT SYNTHESIS ; DIRECTING GROUP ; INTERNAL OXIDANT ; REGIOSELECTIVE SYNTHESIS ; INDOLE SYNTHESIS ; EFFICIENT SYNTHESIS
AbstractC-H activation under redox-neutral conditions, especially by Rh(III) catalysis, has offered attractive synthetic strategies. Previous work in redox-neutral C-H activation relied heavily on the cleavage of oxidizing N-O and N-N directing groups, and cleavable N-S bonds have been rarely used, although they may offer complementary coupling patterns. In this work, N-sulfinyl ketoimines were designed as a novel substrate for the redox-neutral coupling with different activated olefins via a Rh-catalyzed C-H activation pathway. The coupling with acrylate esters afforded 1H-isoindoles with the formation of three chemical bonds around a quaternary carbon. Furthermore, the coupling with maleimides furnished pyrrolidone-fused isoquinolines. A broad scope of substrates has been established. The mechanism of the coupling with acrylates has been studied in detail by a combination of experimental and computational methods. This coupling proceeds via imine-assisted C-H activation of the arene followed by ortho C-H olefination to afford a Rh(III) olefin hydride intermediate which, upon deprotonation, may exist in equilibrium with a Rh(I) olefin species. Cleavage of the N-S bond occurs only after C-H olefination to generate a Rh(III) imide species. DFT studies indicated that the imide group can undergo migratory insertion to produce a Rh(III) secondary alkyl which isomerizes under the assistance of acetic acid to a Rh(III) tertiary alkyl that is prone to insertion of the second acrylate.
Language英语
WOS IDWOS:000371755500067
PublisherAMER CHEMICAL SOC
Citation statistics
Cited Times:41[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Identifierhttp://cas-ir.dicp.ac.cn/handle/321008/171073
Collection中国科学院大连化学物理研究所
Corresponding AuthorLan, Yu; Li, Xingwei
Affiliation1.Chinese Acad Sci, Dalian Inst Chem Phys, Dalian 116023, Peoples R China
2.Chongqing Univ, Sch Chem & Chem Engn, Chongqing 400030, Peoples R China
Recommended Citation
GB/T 7714
Wang, Qiang,Li, Yingzi,Qi, Zisong,et al. Rhodium(III)-Catalyzed Annulation between N-Sulfinyl Ketoimines and Activated Olefins: C-H Activation Assisted by an Oxidizing N-S Bond[J]. ACS CATALYSIS,2016,6(3):1971-1980.
APA Wang, Qiang,Li, Yingzi,Qi, Zisong,Xie, Fang,Lan, Yu,&Li, Xingwei.(2016).Rhodium(III)-Catalyzed Annulation between N-Sulfinyl Ketoimines and Activated Olefins: C-H Activation Assisted by an Oxidizing N-S Bond.ACS CATALYSIS,6(3),1971-1980.
MLA Wang, Qiang,et al."Rhodium(III)-Catalyzed Annulation between N-Sulfinyl Ketoimines and Activated Olefins: C-H Activation Assisted by an Oxidizing N-S Bond".ACS CATALYSIS 6.3(2016):1971-1980.
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