Cycloaddition Reaction of Vinylphenylfurans and Dimethyl   Acetylenedicarboxylate to [8+2] Isomers via Tandem [4+2]/Diradical   Alkene-Alkene Coupling/[1,3]-H Shift Reactions: Experimental Exploration   and DFT Understanding of Reaction Mechanisms

doi:10.1021/acs.joc.6b00792

CORC > 北京大学 > 化学与分子工程学院

	Cycloaddition Reaction of Vinylphenylfurans and Dimethyl Acetylenedicarboxylate to [8+2] Isomers via Tandem [4+2]/Diradical Alkene-Alkene Coupling/[1,3]-H Shift Reactions: Experimental Exploration and DFT Understanding of Reaction Mechanisms
	Chen, Kai ; Wu, Feng ; Ye, Lijuan ; Tian, Zi-You ; Yu, Zhi-Xiang ; Zhu, Shifa
刊名	JOURNAL OF ORGANIC CHEMISTRY
	2016
关键词	DIELS-ALDER REACTIONS CATALYZED 3+2 CYCLOADDITION BRIDGED 10-MEMBERED RINGS QUINODIMETHANES O-QDMS HYDROGEN SHIFT CHEMICAL-REACTIONS ORGANIC-SYNTHESIS AB-INITIO CYCLOHEPTATRIENE DERIVATIVES
DOI	10.1021/acs.joc.6b00792
英文摘要	An experimental test of designed [8 + 2] reaction of vinylphenylfuran and dimethyl acetylenedicarboxylate (DMAD) has been carried out, showing that the reaction gave unexpected addition products under different conditions. When the reaction was conducted under thermal conditions in toluene, expoxyphenanthrene, which was named as a [8 + 2] isomer, was generated. The scope of this reaction has been investigated in the present study. In addition, experiments and DFT calculations have been conducted to investigate how the reaction between vinylphenylfuran and DMAD took place. Surprisingly, the reaction did not involve the expected [8 + 2] intermediate, o-quinodimethane. Instead, the reaction starts from intermolecular Diels-Alder reactions between DMAD and the furan moiety of vinylphenylfuran, followed by unexpected intramolecular alkene-alkene coupling. This step generates a diradical species, which then undergoes [1,3]-H shift to give the experimentally observed expoxyphenanthrene. DFT calculations revealed that, the [8 + 2] cycloadduct cannot be obtained because the [1,5]-H shift process from the [1,5]-vinyl shift intermediate is disfavored kinetically compared to the [1,3]-H shift to the [8 + 2] isomer.; Ministry of Science and Technology of the People's Republic of China [2016YFA0602900]; National Natural Science Foundation of China [21672071, 21422204, 21372086, 21232001]; Guangdong Natural Science Foundation [2014A030313229, 2016A030310433]; SRF for ROCS; State Education Ministry; China Postdoctoral Science Foundation [2015M582378, 2016T90777]; Fundamental Research Funds for the Central Universities, SCUT; SCI(E); EI; PubMed; ARTICLE; yuzx@pku.edu.cn; zhusf@scut.edu.cn; 18; 8155-8168; 81
语种	英语
内容类型	期刊论文
源URL	[http://ir.pku.edu.cn/handle/20.500.11897/493163]
专题	化学与分子工程学院
推荐引用方式 GB/T 7714	Chen, Kai,Wu, Feng,Ye, Lijuan,et al. Cycloaddition Reaction of Vinylphenylfurans and Dimethyl Acetylenedicarboxylate to [8+2] Isomers via Tandem [4+2]/Diradical Alkene-Alkene Coupling/[1,3]-H Shift Reactions: Experimental Exploration and DFT Understanding of Reaction Mechanisms[J]. JOURNAL OF ORGANIC CHEMISTRY,2016.
APA	Chen, Kai,Wu, Feng,Ye, Lijuan,Tian, Zi-You,Yu, Zhi-Xiang,&Zhu, Shifa.(2016).Cycloaddition Reaction of Vinylphenylfurans and Dimethyl Acetylenedicarboxylate to [8+2] Isomers via Tandem [4+2]/Diradical Alkene-Alkene Coupling/[1,3]-H Shift Reactions: Experimental Exploration and DFT Understanding of Reaction Mechanisms.JOURNAL OF ORGANIC CHEMISTRY.
MLA	Chen, Kai,et al."Cycloaddition Reaction of Vinylphenylfurans and Dimethyl Acetylenedicarboxylate to [8+2] Isomers via Tandem [4+2]/Diradical Alkene-Alkene Coupling/[1,3]-H Shift Reactions: Experimental Exploration and DFT Understanding of Reaction Mechanisms".JOURNAL OF ORGANIC CHEMISTRY (2016).