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Carbenes in polycyclic systems: generation and fate of potential adamantane-1, 3-dicarbenes

Potential formation and reactions of adamantane-1, 3-dicarbenes 1-3 generated under different conditions and from different precursors, such as sodium salt of adamantane-1, 3-dicarbaldehyde ditosylhydrazone (4a), sodium salt of 1, 3-diacetyladamantane ditosylhydrazone (5a), sodium salt of 1, 3-dibenzoyladamantane ditosylhydrazone (6a) and 1, 3-bis(diazobenzyl)adamantane (7) are reported. Carbene species generated thermally from 4a yielded bishomoadamantane (15), as a final product, via intramolecular insertion into adjacent C-C bond and formation of putative anti-Bredt olefin species, followed by hydrogen abstraction. Pyrolysis of the same sodium salt 4a in the presence of hydrogen donor n-Bu3SnH afforded 1, 3-dimethyladamantane (17). Thermal decomposition of sodium salt 5a afforded 1, 3-divinyladamantane (14). However, thermal decomposition of sodium salt 6a and diazo-precursor 7 gave benzonitrile as a sole identified product. On the contrary, photolysis of 7 afforded dimeric azine.

carbenes; polycyclic compounds; dicarbenes; azines; adamantane

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