Synthesis and mechanistic study of fused 2-pyrrolines via thermolysis of 6-substituted-3,5-hexadienyl azidoformates.
J Org Chem
; 66(20): 6585-94, 2001 Oct 05.
Article
in En
| MEDLINE
| ID: mdl-11578208
ABSTRACT
Thermolysis of 3,5-hexadienyl azidoformates at 300 degrees C, 0.05 Torr, led to a fused 2-pyrroline regiospecifically, regardless of the configuration E or Z between the C-3 and C-4 double bond. Thermolysis of 6-substituted-3,5(E)-hexadienyl azidoformates yielded a kinetically controlled 2-pyrroline with cis configuration between H-1 and H-8a whereas 6-substituted-3,5(Z)-hexadienyl azidoformates produced a cis and trans mixture. The mechanism was proposed as the loss of nitrogen to form an acyl nitrene, then addition to a double bond to produce an aziridine. Finally the cleavage of the C-C bond generated a vinylazomethine ylide followed by recyclization to a fused 2-pyrroline.
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Collection:
01-internacional
Database:
MEDLINE
Language:
En
Journal:
J Org Chem
Year:
2001
Document type:
Article
Affiliation country:
China