THEORETICAL AND EXPERIMENTAL STUDIES OF THE DIELS-ALDER DIMERIZATIONS OF SUBSTITUTED CYCLOPENTADIENES

被引:37
作者
FROESE, RDJ
ORGAN, MG
GODDARD, JD
STACK, TDP
TROST, BM
机构
[1] UNIV GUELPH,DEPT CHEM & BIOCHEM,GUELPH WATERLOO CTR GRAD WORK CHEM,GUELPH,ON N1G 2W1,CANADA
[2] STANFORD UNIV,DEPT CHEM,STANFORD,CA 94035
关键词
D O I
10.1021/ja00149a016
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Diels-Alder dimerizations of a series of substituted cyclopentadienes have been studied. Experimentally, preparation of 1-oxaspiro[2.4]hepta-4,6-diene results in immediate formation of the Diels-Alder dimer with two adducts formed in a ratio of 3:1. Two substituted spiroheptadiene systems gave similar results. Theoretically, transition states for four different isomers were located leading to the four dimer minima of 1-oxaspiro[2.4]hepta-4,6-diene. The transition state associated with the lowest of the four energetic barriers leads to the isomer with the same connectivity as the major isomer obtained in the dimerization of 2,2-dimethyl-1-oxaspiro[2.4]hepta-4,6-diene (structure confirmed by X-ray diffraction analysis). Unsymmetric transition states at the HF/6-31G(d) level were predicted for three additional endo species with the energy barriers decreasing in the following order: spiro[2.4] hepta-4, 6-diene > cyclopentadiene > 1-oxaspiro[2.4]hepta-4,6-diene > 1,2-dioxaspiro[2.4]hepta-4,6-diene. The barrier to forming the dimer of spiro[2.4]hepta-4,6-diene is predicted to be approximately 5 kcal/mol greater than that for forming the cyclopentadiene dimer and about 13 kcal/mol greater than the barrier to formation of the dimer of 1-oxaspirol[2.4]-hepta-4,6-diene.
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页码:10931 / 10938
页数:8
相关论文
共 90 条
[41]  
Frisch M.J., 1992, GAUSSIAN 92 REVISION
[42]   TRANSITION-STATE STRUCTURE VARIATION IN THE DIELS-ALDER REACTION FROM SECONDARY DEUTERIUM KINETIC ISOTOPE EFFECTS - THE REACTION OF A NEARLY SYMMETRICAL DIENE AND DIENOPHILE IS NEARLY SYNCHRONOUS [J].
GAJEWSKI, JJ ;
PETERSON, KB ;
KAGEL, JR .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (18) :5545-5546
[43]   SIGMA-PI INTERACTION AS A CONTROLLING FACTOR IN THE STEREOSELECTIVITY OF ADDITION-REACTIONS [J].
GLEITER, R ;
PAQUETTE, LA .
ACCOUNTS OF CHEMICAL RESEARCH, 1983, 16 (09) :328-334
[44]   A CORRELATION OF REACTION RATES [J].
HAMMOND, GS .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1955, 77 (02) :334-338
[45]   EVIDENCE FOR NON-BIRADICALOID TRANSITION-STATES IN DIELS-ALDER REACTIONS [J].
HANCOCK, RA ;
WOOD, BF .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1988, (05) :351-353
[46]   INFLUENCE OF POLARIZATION FUNCTIONS ON MOLECULAR-ORBITAL HYDROGENATION ENERGIES [J].
HARIHARA.PC ;
POPLE, JA .
THEORETICA CHIMICA ACTA, 1973, 28 (03) :213-222
[47]   EFFECT OF D-FUNCTIONS ON MOLECULAR-ORBITAL ENERGIES FOR HYDROCARBONS [J].
HARIHARAN, PC ;
POPLE, JA .
CHEMICAL PHYSICS LETTERS, 1972, 16 (02) :217-+
[48]   Studies in gaseous polymerizations [J].
Harkness, JB ;
Kistiakowsky, GB ;
Mears, WH .
JOURNAL OF CHEMICAL PHYSICS, 1937, 5 (09) :682-694
[49]  
Hartree DR, 1928, P CAMB PHILOS SOC, V24, P111
[50]   The wave mechanics of an atom with a non-Coulomb central field Part I theory and methods [J].
Hartree, DR .
PROCEEDINGS OF THE CAMBRIDGE PHILOSOPHICAL SOCIETY, 1928, 24 :89-110