The domino reaction between 4,6-dinitrobenzofuroxan and cyclopentadiene. Insights on the nature of the molecular mechanism

被引:32
作者
Arroyo, P [1 ]
Picher, MT [1 ]
Domingo, LR [1 ]
机构
[1] Univ Valencia, Dept Quim Organ, Inst Ciencia Mol, E-46100 Burjassot, Spain
来源
JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM | 2004年 / 709卷 / 1-3期
关键词
domino reactions; 4+2] cycloadditions; transition structures; DFT calculations;
D O I
10.1016/j.theochem.2003.10.072
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
The molecular mechanism of the domino reaction between 4,6-dinitrobenzofuroxan, 1, and cyclopentadiene, Cp, to give the adduct 11 is examined through density functional theory (DFT) calculations at B3LYP/6-31G* level. This domino reaction comprises two consecutive formally [4 + 2] cycloadditions. The first one is a two-center addition initialized by the nucleophilic attack of Cp to the more electrophilic center of 1. The subsequent cyclization can take place along two competitive channels associated to the formation of a second C-C bond yielding the formally [2 + 4] cycloadduct 9, or a C-O bond yielding the formally [4 + 2] cycloadduct 10. The second cycloaddition is a stepwise process that is initialized by the nucleophilic attack of a second molecule of Cp to 10. The energetic results are in agreement with the experiments allowing to explain the formation of the final domino adduct 11. Inclusion of solvent effects, via a polarizable continuum model, decreases the activation energies of these polar processes. A DFT analysis of the indexes of reactivity provides a sound explanation on the reactivity of 1 on this domino reaction. (C) 2004 Elsevier B.V. All rights reserved.
引用
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页码:45 / 52
页数:8
相关论文
共 45 条
[1]   SYNTHESIS OF 2-NITRO 1,3-DIENES - USEFUL INTERMEDIATES IN THE PREPARATION OF UNSATURATED 1,4-DICARBONYL COMPOUNDS [J].
BACKVALL, JE ;
KARLSSON, U ;
CHINCHILLA, R .
TETRAHEDRON LETTERS, 1991, 32 (40) :5607-5610
[2]  
Barone V, 1998, J COMPUT CHEM, V19, P404, DOI 10.1002/(SICI)1096-987X(199803)19:4<404::AID-JCC3>3.0.CO
[3]  
2-W
[4]   DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].
BECKE, AD .
JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652
[5]   RATIONALIZING THE REGIOSELECTIVITY IN POLYNITROARENE ANIONIC SIGMA-ADDUCT FORMATION - RELEVANCE TO NUCLEOPHILIC AROMATIC-SUBSTITUTION [J].
BUNCEL, E ;
DUST, JM ;
TERRIER, F .
CHEMICAL REVIEWS, 1995, 95 (07) :2261-2280
[6]  
BUNCEL E, 1984, ELECTRON DEFICIENT A, P166
[7]   A new integral equation formalism for the polarizable continuum model: Theoretical background and applications to isotropic and anisotropic dielectrics [J].
Cances, E ;
Mennucci, B ;
Tomasi, 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 [J].
Cossi, M ;
Barone, V ;
Cammi, R ;
Tomasi, J .
CHEMICAL PHYSICS LETTERS, 1996, 255 (4-6) :327-335
[9]   INTRAMOLECULAR [4+2]-CYCLOADDITIONS OF NITROALKENES WITH OLEFINS .2. [J].
DENMARK, SE ;
MOON, YC ;
CRAMER, CJ ;
DAPPEN, MS ;
SENANAYAKE, CBW .
TETRAHEDRON, 1990, 46 (21) :7373-7392
[10]   INTERMOLECULAR [4 + 2]-CYCLOADDITIONS OF NITROALKENES WITH CYCLIC OLEFINS - TRANSFORMATIONS OF CYCLIC NITRONATES [J].
DENMARK, SE ;
CRAMER, CJ ;
STERNBERG, JA .
HELVETICA CHIMICA ACTA, 1986, 69 (08) :1971-1989