Cyclodecadienes transannular reactions

Highly unsaturated cyclic compounds likewise do not react to give di-or tricarboxylic acids, but tertiary monocarboxylic acids are obtained with CO/HgO by a transannular reaction with hydride transfer and formation of bi- or tricyclic systems at the bridgehead. Thus, cyclodecadiene-1,5 reacts to give a mixture of cis- and trans decalin carboxylic acid [624] and cyclododecatriene-1,5,9 reacts to give a mixture of isomeric tertiary per-hydroacenaphthene carboxylic acids. 

The reaction of A -nitrosodimethylamine with (f.ZH.S-cyclodecadiene gave a mixture of two diastereomeric amino nitrates arising from transannular cyclization of the intermediate carbon radical102. The corresponding alcohols 1 and 2 are obtained by reduction of the crude mixture with lithium aluminum hydride. 

Stereoselective transannular cyclizations to hydroazulene systems are also described. These reactions are initiated by ionization of cyclodecenol to form an allylic cation or by oxirane ring opening in cyclodecadiene monoepoxides. 

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