25181-65-1Relevant articles and documents
1,2-asymmetric induction in diastereoselective zwitterionic aza-Claisen rearrangements: Key steps in optically active alkaloid synthesis
Heescher, Carolin,Schollmeyer, Dieter,Nubbemeyer, Udo
, p. 4399 - 4404 (2013)
The zwitterionic aza-Claisen rearrangement of optically active N-allylpyrrolidines and α-phenoxyacetyl fluorides proceeds with complete simple diastereoselectivity (internal asymmetric induction) and complete 1,2-asymmetric induction to generate a new C-C bond adjacent to a chiral C-N-Boc functionality. The resulting γ,δ-unsaturated amides were cyclised to give the corresponding pyrrolizidinones, which enabled the determination of the relative configuration of the stereotriads. Vinyl group degradation and a final lactam reduction gave an optically active analogue of (+)-petasinine (a pyrrolizidine alkaloid). Furthermore, the stereotriad-containing amides should be useful key intermediates for the total synthesis of optically active elaeocarpin (an indolizidine alkaloid). Copyright