Mechanisms of the PtCl2-Catalyzed Intramolecular Cyclization of   o-Isopropyl-Substituted Aryl Alkynes for the Synthesis of Indenes and   Comparison of Three sp(3) C-H Bond Activation Modes

doi:10.1021/jo500839c

CORC > 北京大学 > 化学与分子工程学院

	Mechanisms of the PtCl2-Catalyzed Intramolecular Cyclization of o-Isopropyl-Substituted Aryl Alkynes for the Synthesis of Indenes and Comparison of Three sp(3) C-H Bond Activation Modes
	Wang, Yi ; Liao, Wei ; Huang, Genping ; Xia, Yuanzhi ; Yu, Zhi-Xiang
刊名	journal of organic chemistry
	2014
关键词	1,5-HYDRIDE TRANSFER/RING CLOSURE METAL-CATALYZED HYDROARYLATION POLARIZABLE CONTINUUM MODEL 3+2 CYCLOADDITION REACTIONS SOLVATION FREE-ENERGIES TERMINAL ALKYNES VINYLIDENE COMPLEXES DENSITY FUNCTIONALS HYDROGEN SHIFT CHEMISTRY
DOI	10.1021/jo500839c
英文摘要	Chatani and He respectively reported an efficient way to synthesize indenes through PtCl2 catalyzed sp(3) C-H bond activation. Interestingly, the R group (R = H or Br) in the alkyne moiety of the substrates in Chatani's experiments migrates to the C3 position in indenes, whereas the R group (R = Ar) stays in the original C2 position of final indenes in He's experiments. DFT calculations indicated that there are two competing pathways a and c for the cyclization reaction. Pathway a involves [1,2]-R migration, [1,5]-H shift, and 4 pi-electrocyclization, giving the indenes with the R group at the C3 position. Pathway c takes place through irreversible [1,5]-H shift/cyclization and [1,2]-H shift, generating indenes with the R group at the C2 position. DFT calculations found that, when R = H or Br, pathway a is favored. When R = alkyl group, the [1,2]-R migration is difficult and pathway c is preferred. When R = Ar, DFT calculations predicted and experiments verified that both pathways a and c occur to give two indene products. Comparison of different models of sp(3) C H activations has been presented to guide further understanding and prediction of new C-H bond activations.; http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000337871100030&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=8e1609b174ce4e31116a60747a720701 ; Chemistry, Organic; SCI(E); PubMed; 14; ARTICLE; yuzx@pku.edu.cn; 12; 5684-5696; 79
语种	英语
内容类型	期刊论文
源URL	[http://ir.pku.edu.cn/handle/20.500.11897/189715]
专题	化学与分子工程学院
推荐引用方式 GB/T 7714	Wang, Yi,Liao, Wei,Huang, Genping,et al. Mechanisms of the PtCl2-Catalyzed Intramolecular Cyclization of o-Isopropyl-Substituted Aryl Alkynes for the Synthesis of Indenes and Comparison of Three sp(3) C-H Bond Activation Modes[J]. journal of organic chemistry,2014.
APA	Wang, Yi,Liao, Wei,Huang, Genping,Xia, Yuanzhi,&Yu, Zhi-Xiang.(2014).Mechanisms of the PtCl2-Catalyzed Intramolecular Cyclization of o-Isopropyl-Substituted Aryl Alkynes for the Synthesis of Indenes and Comparison of Three sp(3) C-H Bond Activation Modes.journal of organic chemistry.
MLA	Wang, Yi,et al."Mechanisms of the PtCl2-Catalyzed Intramolecular Cyclization of o-Isopropyl-Substituted Aryl Alkynes for the Synthesis of Indenes and Comparison of Three sp(3) C-H Bond Activation Modes".journal of organic chemistry (2014).