A mechanistic rationale for the mode selectivity in the intramolecular Cyclization of ethylene-tethered iminoketenimines:: [2+2] versus [4+2] stepwise cycloadditions

被引：10

作者：

Alajarín, M ^{[1
]}

Sánchez-Andrada, P ^{[1
]}

Vidal, A ^{[1
]}

Tovar, F ^{[1
]}

机构：

[1] Univ Murcia, Fac Quim, Dept Quim Organ, E-30100 Murcia, Spain

来源：

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY | 2004年 / 2004卷 / 12期

关键词：

ab initio and density functional; calculations; cumulenes; cycloaddition; reaction mechanisms; Schiff bases;

D O I：

10.1002/ejoc.200400093

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A stepwise mechanism, via a zwitterionic intermediate, has been established by ab initio and DFT calculations for the intramolecular cyclization of N-(3-azabut-3-enyl)ketenimine into its corresponding [2+2] cycloadduct. The control of the mode selectivity ([2+2] versus [4+2] cycloaddition) in the intramolecular cyclization of C-vinyl-N-(iminoethylene)ketenimines, which favors the [4+2] cycloadducts, also has been rationalized by comparing the energies calculated for both reaction pathways; the results have been confirmed by a quantitative kinetic analysis. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004).

引用

页码：2636 / 2643

页数：8

共 43 条

[21]

ESPENSON JH, 1981, CHEM KINETICS REACTI, P72

[22]

Frisch M.J., 2016, Gaussian 16 Revision C. 01. 2016, V01

[23] SEMIDIRECT ALGORITHMS FOR THE MP2 ENERGY AND GRADIENT [J].

FRISCH, MJ ;

HEADGORDON, M ;

POPLE, JA .

CHEMICAL PHYSICS LETTERS, 1990, 166 (03) :281-289

[24] A DIRECT MP2 GRADIENT-METHOD [J].

FRISCH, MJ ;

HEADGORDON, M ;

POPLE, JA .

CHEMICAL PHYSICS LETTERS, 1990, 166 (03) :275-280

[25]

GAMBARYAN NP, 1976, USP KHIM+, V45, P1251

[26]

HEHRE WJ, 1986, AB INITIO MOL ORBITA, P71

[27]

ISAACS NS, 1987, PHYSICAL ORGANIC CHE, P158

[28] Density functional theory of electronic structure [J].

Kohn, W ;

Becke, AD ;

Parr, RG .

JOURNAL OF PHYSICAL CHEMISTRY, 1996, 100 (31) :12974-12980

[29] SYNTHESIS AND REACTIONS OF KETENIMINES [J].

KROW, GR .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 1971, 10 (07) :435-&

[30] Note on an approximation treatment for many-electron systems [J].

Moller, C ;

Plesset, MS .

PHYSICAL REVIEW, 1934, 46 (07) :0618-0622

← 1 2 3 4 5 →