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Mechanism, regioselectivity, and the kinetics of phosphine-catalyzed [3+2] cycloaddition reactions of allenoates and electron-deficient alkenes
Liang, Yong1; Liu, Song1; Xia, Yuanzhi1,2; Li, Yahong2,3; Yu, Zhi-Xiang1
2008
Source PublicationCHEMISTRY-A EUROPEAN JOURNAL
Volume14Issue:14Pages:4361-4373
SubtypeReview
AbstractWith the aid of computations and experiments, the detailed mechanism of the phosphine-catalyzed [3+2] cycloaddition reactions of allenoates and electron-deficient alkenes has been investigated. It was found that this reaction includes four consecutive processes: 1) In situ generation of a 1,3-dipole from allenoate and phosphine, 2) stepwise [3 + 2] cycloaddition, 3) a water-catalyzed [1,2]-hydrogen shift, and 4)elimination of the phosphine catalyst. In situ generation of the 1,3dipole is key to all nucleophilic phosphine-catalyzed reactions. Through a kinetic study we have shown that the generation of the 1,3-dipole is the rate-determining step of the phosphine-catalyzed [3+2] cycloaddition reaction of allenoates and electron-deficient alkenes. DFT calculations and FMO analysis revealed that an electron-withdrawing group is required in the allene to ensure the generation of the 1,3-dipole kinetically and thermodynamically. Atoms-in-molecules (AIM) theory was used to analyze the stability of the 1,3-dipole. The regioselectivity of the [3+2] cycloaddition can be rationalized very well by FMO and AIM theories. Isotopic labeling experiments combined with DFT calculations showed that the commonly accepted intramolecular [1,2]-proton shift should be corrected to a water-catalyzed [1,2]proton shift. Additional isotopic labeling experiments of the hetero-[3+2] cycloaddition of allenoates and electron-deficient imines further support this finding. This investigation has also been extended to the study of the phosphine-catalyzed [3+2] cycloaddition reaction of alkynoates as the three-carbon synthon, which showed that the generation of the 1,3-dipole in this reaction also occurs by a water-catalyzed process.
KeywordAllenes Density Functional Calculations Kinetics Phosphine Organocatalysis Reaction Mechanisms
WOS HeadingsScience & Technology ; Physical Sciences
WOS KeywordHIGHLY DIASTEREOSELECTIVE SYNTHESIS ; BAYLIS-HILLMAN REACTION ; DIELS-ALDER REACTIONS ; ORGANIC-REACTIONS ; AZOMETHINE YLIDES ; NITROGEN-HETEROCYCLES ; 4+2 ANNULATION ; DIMETHYL ACETYLENEDICARBOXYLATE ; FUNCTIONALIZED CYCLOPENTENES ; NUCLEOPHILIC CATALYSTS
Indexed BySCI
Language英语
WOS Research AreaChemistry
WOS SubjectChemistry, Multidisciplinary
WOS IDWOS:000256131800025
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Document Type期刊论文
Identifierhttp://ir.isl.ac.cn/handle/363002/5849
Collection青海盐湖研究所知识仓储
Affiliation1.Peking Univ, Coll Chem, Minist Educ, BNLMS,Key Lab Bioorgan Chem & Mol Engn, Beijing 100871, Peoples R China
2.Chinese Acad Sci, Qinghai Inst Salt Lakes, Xining 810008, Peoples R China
3.Suzhou Univ, Dept Chem & Chem Engn, Key Lab Organ Synth Jiangsu Prov, Suzhou 215006, Peoples R China
Recommended Citation
GB/T 7714
Liang, Yong,Liu, Song,Xia, Yuanzhi,et al. Mechanism, regioselectivity, and the kinetics of phosphine-catalyzed [3+2] cycloaddition reactions of allenoates and electron-deficient alkenes[J]. CHEMISTRY-A EUROPEAN JOURNAL,2008,14(14):4361-4373.
APA Liang, Yong,Liu, Song,Xia, Yuanzhi,Li, Yahong,&Yu, Zhi-Xiang.(2008).Mechanism, regioselectivity, and the kinetics of phosphine-catalyzed [3+2] cycloaddition reactions of allenoates and electron-deficient alkenes.CHEMISTRY-A EUROPEAN JOURNAL,14(14),4361-4373.
MLA Liang, Yong,et al."Mechanism, regioselectivity, and the kinetics of phosphine-catalyzed [3+2] cycloaddition reactions of allenoates and electron-deficient alkenes".CHEMISTRY-A EUROPEAN JOURNAL 14.14(2008):4361-4373.
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