SOLVENT EFFECTS ON DIELS-ALDER REACTIONS - A SEMIEMPIRICAL STUDY

被引：20

作者：

CATIVIELA, C

DILLET, V

GARCIA, JI

MAYORAL, JA

RUIZLOPEZ, MF

SALVATELLA, L

机构：

[1] UNIV ZARAGOZA, CSIC, INST CIENCIA MAT ARAGON, DEPT QUIM ORGAN, E-50009 ZARAGOZA, SPAIN

[2] UNIV NANCY 1, CHIM THEOR LAB, CNRS, URA 510, F-54506 VANDOEUVRE LES NANCY, FRANCE

来源：

JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM | 1995年 / 331卷 / 1-2期

关键词：

D O I：

10.1016/0166-1280(94)03795-M

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Semi-empirical calculations (AM1 and PM3) have been used in the framework of the Self-Consistent Reaction Field (SCRF) and supermolecule models in order to analyse solvent effects on the Diels-Alder reactions of cyclopentadiene and 2-methyl-1,3-butadiene (isoprene) with acrylonitrile, acrolein, methyl vinyl ketone, and methyl acrylate. Both SCRF and supermolecule models describe correctly the effect of the solvent on endo/exo selectivities. Supermolecule calculations are suitable to explain the influence of hydrogen bonding on activation barriers, but fail to explain the effect of strong HBD solvents on para/meta regioselectivity.

引用

页码：37 / 50

页数：14

共 46 条

[1] CORRELATION OF SOLVENT EFFECTS ON STEREOSELECTIVITIES OF DIELS-ALDER REACTIONS BY MEANS OF LINEAR FREE ENERGY RELATIONSHIPS - A NEW EMPIRICAL MEASURE OF SOLVENT POLARITY [J].