57606-85-6Relevant academic research and scientific papers
The 1-Aza-Cope Rearrangement
Wu, Pei-Lin,Chu, Min,Fowler, Frank W.
, p. 963 - 972 (2007/10/02)
The 1-aza-Cope rearrangement of azavinylcyclohexene derivatives were investigated.It was observed that an N-acyl substituent on the 1-aza 1,5-diene provides a sufficient driving force for this normally contrathermodynamic process.Although simple derivatives have high activation energies proceeding in relative low overall yield, a methoxy substituent at C-4 of the aza diene as well as its incorporation into strained bicyclic ring systems facilitates the 1-aza-Cope rearrangement.Because the aza diene precursors are readily available by using the Diels-Alder reaction with acrolein derivatives, this process has synthetic potential for the preparation of nitrogen heterocycles.This scheme is illustrated with the preparation of a hydrolulolidine providing a formal total synthesis of (+/-)-aspidospermine.
INTRAMOLECULAR N-ALKENYLNITRONE-ADDITIONS. REGIO- AND STEREOCHEMISTRY
Oppolzer, W.,Siles, S.,Snowden, R. L.,Bakker, B. H.,Petrzilka, M.
, p. 3497 - 3509 (2007/10/02)
Efficient intramolecular cycloadditions of N-3-alkenyl- and N-4-alkenylnitrones proceed with opposite regioselection which is modified by dipolarophile-substituent effects.Polycyclic isoxazolidines are obtained in a highly stereocontrolled fashion, consistent with an endo-addition of the Z-nitrones.
