π-Strain-induced electrophilicity in small cycloalkynes:: A DFT analysis of the polar cycloaddition of cyclopentyne towards enol ethers

被引：26

作者：

Domingo, LR

Pérez, P

Contreras, R

机构：

[1] Univ Valencia, Inst Ciencia Mol, Unidad Invest Quim Organ Teor, E-46100 Burjassot, Spain

[2] Univ Andres Bello, Fac Ecol & Recursos Nat, Dept Ciencias Quim, Santiago 275, Chile

[3] Univ Chile, Fac Ciencias, Dept Quim, Santiago 653, Chile

来源：

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY | 2006年 / 2006卷 / 02期

关键词：

cycloadditions; cycloalkynes; density functional calculations; electrophilicity; strain;

D O I：

10.1002/ejoc.200500466

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Small cycloalkynes possess a pi-strain-induced electrophilicity related to the bending of the C-SP3-C-SP-C-SP bond angle. For cyclopentyne and benzyne, the electrophilicity index defined in the context of density functional theory gives a coherent rationale for the reactivity of these cycloalkynes, which may act as electrophiles in polar cycloaddition. reactions toward enol ethers. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006).

引用

页码：498 / 506

页数：9

共 46 条

[1] The reaction of cyclopentyne with ethene: Concerted vs stepwise mechanism?
Bachrach, SM
Gilbert, JC
[J]. JOURNAL OF ORGANIC CHEMISTRY, 2004, 69 (19) : 6357 - 6364
[2] DFT study of the cycloaddition reactions of strained alkynes
Bachrach, SM
Gilbert, JC
Laird, DW
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (27) : 6706 - 6707
[3] Barone V, 1998, J COMPUT CHEM, V19, P404, DOI 10.1002/(SICI)1096-987X(199803)19:4<404::AID-JCC3>3.0.CO
[4] 2-W
[5] DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE
BECKE, AD
[J]. JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) : 5648 - 5652
[6] REDUCTION OF ARYL HALIDES BY LITHIUM DIALKYLAMIDES
BENKESER, RA
DEBOER, CE
[J]. JOURNAL OF ORGANIC CHEMISTRY, 1956, 21 (03) : 281 - 284
[7] A new integral equation formalism for the polarizable continuum model: Theoretical background and applications to isotropic and anisotropic dielectrics
Cances, E
Mennucci, B
Tomasi, J
[J]. JOURNAL OF CHEMICAL PHYSICS, 1997, 107 (08) : 3032 - 3041
[8] Ab initio study of solvated molecules: A new implementation of the polarizable continuum model
Cossi, M
Barone, V
Cammi, R
Tomasi, J
[J]. CHEMICAL PHYSICS LETTERS, 1996, 255 (4-6) : 327 - 335
[9] A DFT analysis of the strain-induced regioselective[2+2]cycloaddition of benzyne possessing fused four-membered ring
Domingo, LR
Pérez, P
Contreras, R
[J]. LETTERS IN ORGANIC CHEMISTRY, 2005, 2 (01) : 68 - 73
[10] Origin of the synchronicity on the transition structures of polar Diels-Alder reactions.: Are these reactions [4+2] processes?
Domingo, LR
Aurell, MJ
Pérez, P
Contreras, R
[J]. JOURNAL OF ORGANIC CHEMISTRY, 2003, 68 (10) : 3884 - 3890

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