(1H-Tetrazol-5-yl)-Allenes: Building Blocks for Tetrazolyl Heterocycles.
(1H-Tetrazol-5-yl)-allenes have been prepared for the first time, and their reactivity toward aziridines explored. Reaction of a (1-benzyl-1H-tetrazol-5-yl)-phosphonium chloride and acyl chlorides in the presence of triethylamine afforded the target allenes via Wittig reaction of the in situ generated phosphorus ylide and ketenes. 1-(1-Benzyl-1H-tetrazol-5-yl)propa-1,2-diene and 3-methyl-, 3-ethyl- and 3-benzyl derivatives undergo microwave-induced formal [3 + 2] cycloaddition with cis-N-benzyl-2-benzoyl-3-phenylaziridine, through C-N bond cleavage, to give selectively tetrasubstituted pyrroles. In contrast, with (1H-tetrazol-5-yl)-allenes bearing bulkier substituents at C-3, such as i-propyl or a tert-butyl, 4-methylenepyrrolidines were obtained exclusively via [3 + 2] cycloaddition of the in situ generated azomethine ylide. The latter allenes also gave 4-methylenepyrrolidines on reacting with cis-2-benzoyl-N-cyclohexyl-3-phenylaziridine, whereas with the other allenes, pyrroles were obtained as major products together with the formation of 4-methylenepyrrolidines. All the studied (1H-tetrazol-5-yl)-allenes reacted with N-benzyl-cis-3-phenylaziridine-2-carboxylate to give the corresponding 4-methylenepyrrolidines exclusively.
CQC and Department of Chemistry, University of Coimbra , 3004-535 Coimbra, Portugal.
Ana L
AL
Cardoso
CFisUC and Department of Physics, University of Coimbra , 3004-516 Coimbra, Portugal.
Marta S C
MS
Henriques
CFisUC and Department of Physics, University of Coimbra , 3004-516 Coimbra, Portugal.
José A
JA
Paixão
CQC and Department of Chemistry, University of Coimbra , 3004-535 Coimbra, Portugal.
Teresa M V D
TM
Pinho E Melo