Concerning Attempts To Synthesize out-Bicyclotetradec-1-ene Derivatives

Article abstract of DOI:10.1021/jo00052a024

The keto aldehydes 4-<6-oxo-1-(tetrahydropyranyloxy)cyclodecyl>butanal (17), (E)-4-(6-oxocyclodec-1-enyl)butanal (24), and 4-(6-oxocyclodecylidene)butanal (7) have been synthesized.No bicyclo<4.4.4>tetradecadienes were found in the products from the zero-valent titanium reductive cyclization of compound 24.Instead, products arising from transannular reactions of the cyclodecyl ring system were isolated. 1,6-Divinylbicyclo<4.4.0>decane (32) was obtained from the reductive cyclization of keto enal 7.The most plausible route for its formation is through a Cope rearrangement of a bicyclo<4.4.4>tetradecene derivative, suggesting that an out-bicyclo<4.4.4>tetradecenylbistitanium pinacolate 8 intervened.