[摘要]:Catalyzed and uncatalyzed rearrangement reactions of terpenoids play a major role in lab. and industrial-scale synthesis of fine chems. Herein, we present our results on the thermally induced isomerization of pinane (1). Investigation of the thermal behavior of (+)-cis- (1a) and (-)-trans-pinane (1b) in a flow-type reactor reveals significant differences in both reactivity and selectivity concerning the formation of (-)-b-citronellene (2) and (+)-isocitronellene (3) as main products. Possible explanations for these results are discussed on the basis of reaction mechanism and ground-state geometries for 1a and 1b. To identify side reactions caused from ene cyclizations of 2 and 3, addnl. pyrolysis expts. were conducted that enabled the identification of almost all compds. in the network of C10H18-hydrocarbon products formed from 1.