Publication Date:
2014-01-14
Description:
Bicyclo[3.1.1]heptâ2âene was first prepared and well identified in 1972. In 1974, the degenerate thermal isomerization involving 1â d â and 3â d âbicyclo[3.1.1]heptâ2âene was approached successfully, as one of the two deuteriumâlabeled structures was selected, heated, and equilibrated. There has been no further study of this degenerate isomerization. Here, a detailed outline of reaction trajectories for d 2 âlabeled bicyclo[3.1.1]heptâ2âenes is given that will establish the four independent kinetic parameters needed for 20 linking paths between six d 2 âspecies. The use of racemates, eliminating chiral separations and dissections, provides degenerate isomerization paths providing this method with general utility. Copyright © 2014 John Wiley & Sons, Ltd. The use of racemic doubly deuteriumâlabeled species can be used to obtain, for the first time, the full set of four unique rate constants for the degenerate rearrangements of d 2 âbicyclo[3.1.1]heptâ2âene. The expectations for deuterium isotope 1 Î effects on 13C NMR chemical shifts are tabulated and show that it can be used to quantify the isotopomers and monitor the reactions as they progress.
Print ISSN:
0894-3230
Electronic ISSN:
1099-1395
Topics:
Chemistry and Pharmacology
,
Physics
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