1993
DOI: 10.1039/p29930001211
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On intramolecular dyotropy: structural effects on reaction rates, crystal structure–molecular mechanics correlations and primary deuterium kinetic isotope effects. (Parameters for intramolecular recognition)

Abstract: Previous attempts to prepare the pentacyclic triene 17 for comparison of the rate of intramolecular dyotropy with the kinetics of similar irreversible rearrangements of norbornene ring-substituted analogues had given only dyotropomer 18 with an estimated minimum ratio k,(17)/k1(5) -2 x 1 O5 at 36 "C. In the following it is shown that the steric proximity, dcH, of transferring H atoms to receptor sp2 carbons in the reaction zone cavity together with M M-calculated n-energy differences between dyotropomers can r… Show more

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Cited by 18 publications
(7 citation statements)
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“…In other words, the transformation seems to be easier for late transition states when the new C–H bond is already developed. This result agrees with kinetic and structural studies in related intramolecular (dyotropic) double hydrogen atom migrations , which indicate that changes of only 0.1–0.17 Å in the initial C···H bond length (also called precompression factor) translate into a rate spread of 10 4 s –1 . , …”
Section: Resultssupporting
confidence: 90%
“…In other words, the transformation seems to be easier for late transition states when the new C–H bond is already developed. This result agrees with kinetic and structural studies in related intramolecular (dyotropic) double hydrogen atom migrations , which indicate that changes of only 0.1–0.17 Å in the initial C···H bond length (also called precompression factor) translate into a rate spread of 10 4 s –1 . , …”
Section: Resultssupporting
confidence: 90%
“…Small changes in π-energy at the receptor π-bond, occasioned by the proximity of polarizing substituents on the adjacent methylene bridge, contribute to the modest rate-spread observed for the series of trienes 145 (about an order of magnitude). 105,106 It is also worthy of note that while primary deuterium kinetic isotope effects in the rearrangements of compounds 147 reveal unambiguous evidence for a tunneling contribution to the kinetics, the analogous dyotropy of compounds 145 shows comparatively smaller tunneling components. 105,107,108 Vogel and co-workers reported the thermally induced [ σ 2 s + σ 2 s + π 2 s ] process in the endo,endo-11-oxatetracyclododecene derivative 149 (Scheme 60), a process similar to the rearrangement observed in isodrins 145.…”
Section: Thermal Reactionsmentioning
confidence: 98%
“…105,106 It is also worthy of note that while primary deuterium kinetic isotope effects in the rearrangements of compounds 147 reveal unambiguous evidence for a tunneling contribution to the kinetics, the analogous dyotropy of compounds 145 shows comparatively smaller tunneling components. 105,107,108 Vogel and co-workers reported the thermally induced [ σ 2 s + σ 2 s + π 2 s ] process in the endo,endo-11-oxatetracyclododecene derivative 149 (Scheme 60), a process similar to the rearrangement observed in isodrins 145. 109 The thermochemical data [∆H q ) 35-39 kcal/mol and ∆S q ) 2-11 cal/(K mol)] and the deuterium labeling experiments are consistent with a concerted intramolecular mechanism involving the stereospecific 4,5-endo a 9,10-endo double hydrogen atom migration.…”
Section: Thermal Reactionsmentioning
confidence: 98%
“…A number of related structures have been determined, for example, aldrin (1,2,3,4,10,10-hexachloro-1,4,4a,5,8,8a-hexahydro-1,4:5,8-dimethanonaphthalene;DeLacy & Kennard, 1972), isodrin (1,2,3,4,10,10-hexachloro-1,4,4a,5,8,8a-hexahydro-endo-1,4-endo-5,8-dimethanonaphthalene;Kennard et al, 1979) and dechloroethoxyisodrin (endo,endo-3,5,6,11,-11-pentachloro-4-ethoxytetracyclo[6.2.1.1 3,6 .0 2,7 ]dodeca-4,9diene; Mackenzie et al, 1993).…”
Section: Commentmentioning
confidence: 99%