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Carbenes in polycyclic systems: generation and fate of potential adamantane‐1,3‐dicarbenes
Author(s) -
Klaić Lada,
Alešković Marija,
Veljković Jelena,
MlinarićMajerski Kata
Publication year - 2008
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.1319
Subject(s) - chemistry , adamantane , thermal decomposition , carbene , salt (chemistry) , benzonitrile , sodium , intramolecular force , medicinal chemistry , sodium salt , diazo , hydrogen atom abstraction , photodissociation , photochemistry , organic chemistry , hydrogen , inorganic chemistry , catalysis
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 CC 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 ‐Bu 3 SnH 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 21 . Finally, the synthetic pathways of novel tosylhydrazone derivatives 4 , 5 , 6 and their corresponding sodium salts, as well as bis‐diazocompound 7 are described. Copyright © 2008 John Wiley & Sons, Ltd.