Abstract: | The two double‐bond isomers 3‐iodo‐2,6,6‐trimethylbicyclo3.1.1]hept‐2‐ene ( 6b ) and 3‐iodo‐4,6,6‐trimethylbicyclo3.1.1]hept‐2‐ene ( 11 ) were synthesized by reacting 2,6,6‐trimethylbicyclo3.1.1]heptan‐3‐one ( 9 ) with hydrazine, followed by treatment with I2 in the presence of Et3N. Treatment of 11 with t‐BuOK as base in diglyme at 220° resulted in the formation of 9 and 6,6‐dimethyl‐4‐methylidenebicyclo3.1.1]hept‐2‐ene ( 12 ). For the formation of 9 , the cyclic allene 7 is proposed as an intermediate. Treatment of the second isomer, 6b , with t‐BuOK at 170° gave rise to the diene 12 and the dimerization product 17 . The underlying mechanism of this transformation is discussed. On the basis of density‐functional‐theory (DFT) calculations on the allene 7 and the alkyne 15 , the formation of the latter as the intermediate was excluded. |