Mechanistic twist of the [8+2] cycloadditions of dienylisobenzofurans   and dimethyl acetylenedicarboxylate: Stepwise [8+2] versus   [4+2]/[1,5]-vinyl shift mechanisms revealed through a theoretical and   experimental study

doi:10.1021/ja072203u

CORC > 北京大学 > 化学与分子工程学院

	Mechanistic twist of the [8+2] cycloadditions of dienylisobenzofurans and dimethyl acetylenedicarboxylate: Stepwise [8+2] versus [4+2]/[1,5]-vinyl shift mechanisms revealed through a theoretical and experimental study
	Chen, Yuanyuan ; Ye, Siyu ; Jiao, Lei ; Liang, Yong ; Sinha-Mahapatra, Dilip K. ; Herndon, James W. ; Yu, Zhi-Xiang
刊名	journal of the american chemical society
	2007
关键词	DIELS-ALDER REACTION DENSITY-FUNCTIONAL THEORY ELECTRON-RICH HEPTAFULVENES INVERSE RING POLARIZATION UNRESTRICTED HARTREE-FOCK AB-INITIO THERMAL REARRANGEMENTS PERICYCLIC-REACTIONS COPE REARRANGEMENTS ACTIVATION BARRIERS
DOI	10.1021/ja072203u
英文摘要	Recently, it was reported that both dienylfurans and dienylisobenzofurans could react with dimethyl acetylenedicarboxylate (DMAD) to give [8+2] cycloadducts. Understanding these [8+2] reactions will aid the design of additional [8+2] reactions, which have the potential for the synthesis of 10-membered and larger carbocycles. The present Article is aimed to understand the detailed mechanisms of the originally reported [8+2] cycloaddition reaction between dienylisobenzofurans and alkynes at the molecular level through the joint forces of computation and experiment. Density functional theory calculations at the (U)B3LYP/6-31+G(d) level suggest that the concerted [8+2] pathway between dienylisobenzofurans and alkynes is not favored. A stepwise reaction pathway involving formation of a zwitterionic intermediate for the [8+2] reactions between dienylisobenzofurans that contain electron-donating methoxy groups present in their diene moieties and DMAD has been predicted computationally. This pathway is in competition with a Diels-Alder [4+2] reaction between the furan moieties of dienylisobenzofurans and DMAD. When there is no electron-donating group present in the diene moieties of dienylisobenzofurans, the [8+2] reaction occurs through an alternative mechanism involving a [4+2] reaction between the furan moiety of the tetraene and DMAD, followed by a [1,5]-vinyl shift. This computationally predicted novel mechanism was supported experimentally.; Chemistry, Multidisciplinary; SCI(E); PubMed; 35; ARTICLE; 35; 10773-10784; 129
语种	英语
内容类型	期刊论文
源URL	[http://ir.pku.edu.cn/handle/20.500.11897/197970]
专题	化学与分子工程学院
推荐引用方式 GB/T 7714	Chen, Yuanyuan,Ye, Siyu,Jiao, Lei,et al. Mechanistic twist of the [8+2] cycloadditions of dienylisobenzofurans and dimethyl acetylenedicarboxylate: Stepwise [8+2] versus [4+2]/[1,5]-vinyl shift mechanisms revealed through a theoretical and experimental study[J]. journal of the american chemical society,2007.
APA	Chen, Yuanyuan.,Ye, Siyu.,Jiao, Lei.,Liang, Yong.,Sinha-Mahapatra, Dilip K..,...&Yu, Zhi-Xiang.(2007).Mechanistic twist of the [8+2] cycloadditions of dienylisobenzofurans and dimethyl acetylenedicarboxylate: Stepwise [8+2] versus [4+2]/[1,5]-vinyl shift mechanisms revealed through a theoretical and experimental study.journal of the american chemical society.
MLA	Chen, Yuanyuan,et al."Mechanistic twist of the [8+2] cycloadditions of dienylisobenzofurans and dimethyl acetylenedicarboxylate: Stepwise [8+2] versus [4+2]/[1,5]-vinyl shift mechanisms revealed through a theoretical and experimental study".journal of the american chemical society (2007).