Thermolysis of (1R,2R)-1,2-Dideuteriocyclobutane. An Application of Vibrational Circular Dichroism to Kinetic Analysis

Article abstract of DOI:10.1021/ja00275a028

The relative rates of geometric isomerization to racemization have been studied for the title compound by using a combination of infrared (IR) and vibrational circular dichroism (VCD) spectroscopies, respectively.The results are interpreted with a kinetic and mechanistic scheme which parallels that used by Berson, Pedersen, and Carpenter on a similar study of chiral cyclopropane-d2 thermolysis.Relative rates of isomerization to stereomutation of 1.5+/-0.4 were obtained which can be interpreted to be consistent with a mechanism best described by random methylene rotation in tetramethylene-d2.This is the first application of VCD to kinetic analysis, and the advantages of IR techniques over the more usually employed UV spectroscopies to this type of basic mechanistic problem are illustrated.