Cyclo-1,3-dien-5-ynes with ring sizes from 10 to 14 (6a-e) have been prepar
ed for the first time by using a five-step synthesis starting from the alky
nols 7a-e. The final ring-closure was achieved by McMurry coupling of the a
lpha,omega -dialdehvdes 12a-e with the complex TiCl3(DME)(1.5). Thermal iso
merization of the cyclodienynes leads to the corresponding benzocycloalkene
s, and it has been shown that the ring size has a considerable influence on
the temperature necessary for thermocylization.