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

	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 1; Liao, Wei 1; Huang, Genping 2; Xia, Yuanzhi 2; Yu, Zhi-Xiang 1
刊名	JOURNAL OF ORGANIC CHEMISTRY
	2014-06-20
卷号	79 期号:12 页码:5684-5696
ISSN号	0022-3263
DOI	10.1021/jo500839c
文献子类	Article
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.
WOS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
WOS研究方向	Chemistry
语种	英语
出版者	AMER CHEMICAL SOC
WOS记录号	WOS:000337871100030
内容类型	期刊论文
源URL	[http://cas-ir.dicp.ac.cn/handle/321008/167336]
专题	大连化学物理研究所_中国科学院大连化学物理研究所
通讯作者	Yu, Zhi-Xiang
作者单位	1.Peking Univ, Minist Educ, Key Lab Bioorgan Chem & Mol Engn, Beijing Natl Lab Mol Sci BNLMS,Coll Chem, Beijing 100871, Peoples R China 2.Wenzhou Univ, Coll Chem & Mat Engn, Wenzhou 325035, Zhejiang, Peoples R China
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,2014,79(12):5684-5696.
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,79(12),5684-5696.
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 79.12(2014):5684-5696.