Bicyclic strained allenes : incorporation of an allene unit into alpha-pinene and benzonorbornadiene

Kılbaş, Benan
The synthesis of cyclic allenes with eight or less skeletal C-atoms, known as highly strained organic compounds, has for the past decades attracted increasing interest. The first part of study describes an investigation aimed at the incorporation of an allene unit into a natural compound, being α-pinene, by using β-elimination method. The two double-bond isomers 310 and 299b were synthesized as key compounds. Treatment of 310 with t-BuOK resulted in the formation of ketone 308 and diene 313. For the formation of 308, the cyclic allene 300 was proposed as an intermediate. Treatment of 299b, with t-BuOK gave arise to the diene 313 and the dimerization product 322. On the basis of density-functional-theory (DFT) calculations on the allene 300 and the alkyne 320, the formation of the latter as the intermediate was excluded. In the second part of study, the stability of endo-carbene 304 was investigated. Previous studies indicated, during the formation of intermediate 264, no exo-carbene 330 structure could be optimized in its free carbene form. At this point, we were curious about the stability of endo-cyclopropylidene 304 not discussed before in literature. First, addition of bromofluorocarbene to anti-7-ethylbenzonorbornadiene (352) was aimed to isolate the endo-adduct 302b. However, no carbene addition reaction was observed caused by pyramidalization on double bond respect to the methoxy derivative, 363b. Therefore, the bromine was introduced to C-7 carbon atom. Treatment of 302a with MeLi in the presence of furan, gave furan adduct 306a confirmed the formation of allene 305a as a reactive intermediate. Theoretical calculations showed endo-carbene 304a was optimized in the free carbene form . However, it readily isomerizes to allene 305a afforded furan adduct 306a.
Citation Formats
B. Kılbaş, “Bicyclic strained allenes : incorporation of an allene unit into alpha-pinene and benzonorbornadiene,” Ph.D. - Doctoral Program, Middle East Technical University, 2009.