0000000001145565
AUTHOR
Carolin Heescher
1,2-Asymmetric Induction in Diastereoselective Zwitterionic Aza-Claisen Rearrangements: Key Steps in Optically Active Alkaloid Synthesis
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 f…
CCDC 926977: Experimental Crystal Structure Determination
Related Article: Carolin Heescher, Dieter Schollmeyer and Udo Nubbemeyer|2013|Eur.J.Org.Chem.|2013|4399|doi:10.1002/ejoc.201300389
CCDC 926976: Experimental Crystal Structure Determination
Related Article: Carolin Heescher, Dieter Schollmeyer and Udo Nubbemeyer|2013|Eur.J.Org.Chem.|2013|4399|doi:10.1002/ejoc.201300389