Abstract
Oximes of 5,5-disubstituted 1-azapenta-1,4-dien-3-ones 3 underwent 1,5-cyclization reactions yielding
indenole derivatives 4 in moderate to good
yields upon treatment with an excess of trifluoromethanesulfonic
acid. Similarly, the hydrazone 3g led to
indenole 4f upon protonation. The reaction
could also be successfully applied to the synthesis of benzo[b]cyclopenta[d]thiophene 5 starting
from 3f. Products of a competing aza-Nazarov
reaction were not observed. The reaction mechanism is explained
by assuming the involvement of dicationic intermediates, generated
by superelectrophilic solvation, similar to that of known Nazarov
and aza-Nazarov-type transformations. Quantum chemical calculations
of reaction energies and activation barriers are discussed with
respect to the experimental results.
Key words
cyclization - carbocations - penta-1,4-dien-3-ones - indenoles - quantum chemical calculations
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