A theoretical analysis of the conformational behaviour of substituted methylenecyclohexanes

被引：2

作者：

Mawhinney, RC

Muchall, HM ^{[1
]}

Lessard, J

机构：

[1] Concordia Univ, Dept Chem & Biochem, Montreal, PQ H4B 1R6, Canada

[2] Univ Sherbrooke, Dept Chim, Sherbrooke, PQ J1K 2R1, Canada

来源：

CANADIAN JOURNAL OF CHEMISTRY | 2003年 / 81卷 / 10期

关键词：

conformational analysis; methylenecyclohexanes; anomeric effect; unsaturation effect;

D O I：

10.1139/V03-137

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The use of the PBE0 hybrid density functional theory method in conjunction with the COSMO solvation model allowed us to reproduce, both qualitatively and quantitatively, the experimentally observed conformational compositions of 2-substituted and 2,7-disubstituted methylenecyclohexanes. An analysis revealed several different interactions that influence the overall equilibrium. It was found that the endo (general) anomeric effect plays a significant role in the equilibrium and that the "unsaturation effect" possibly comprises two effects.

引用

页码：1101 / 1107

页数：7

共 41 条

[1] Toward reliable density functional methods without adjustable parameters: The PBE0 model
Adamo, C
Barone, V
[J]. JOURNAL OF CHEMICAL PHYSICS, 1999, 110 (13) : 6158 - 6170
[2] ATOMS IN MOLECULES
BADER, RFW
[J]. ACCOUNTS OF CHEMICAL RESEARCH, 1985, 18 (01) : 9 - 15
[3] Baes C.F., 1976, HYDROLYSIS CATIONS
[4] Barone V, 1998, J COMPUT CHEM, V19, P404, DOI 10.1002/(SICI)1096-987X(199803)19:4<404::AID-JCC3>3.0.CO
[5] 2-W
[6] A new definition of cavities for the computation of solvation free energies by the polarizable continuum model
Barone, V
Cossi, M
Tomasi, J
[J]. JOURNAL OF CHEMICAL PHYSICS, 1997, 107 (08) : 3210 - 3221
[7] Kohn-Sham density functional theory: Predicting and understanding chemistry
Bickelhaupt, FM
Baerends, EJ
[J]. REVIEWS IN COMPUTATIONAL CHEMISTRY, VOL 15, 2000, 15 : 1 - 86
[8] Carballeira L, 2000, J COMPUT CHEM, V21, P462, DOI 10.1002/(SICI)1096-987X(20000430)21:6<462::AID-JCC5>3.0.CO
[9] 2-Z
[10] Electronic delocalization contribution to the anomeric effect evaluated by computational methods
Cortés, F
Tenorio, J
Collera, O
Cuevas, G
[J]. JOURNAL OF ORGANIC CHEMISTRY, 2001, 66 (09) : 2918 - 2924

← 1 2 3 4 5 →