Addition of organometallic reagents to chiral N-methoxylactams

• Verfasst von: Jäkel, Mascha [VerfasserIn]
• Verfasst von: Qu, Jianping [VerfasserIn]
• Verfasst von: Schnitzer, Tobias [VerfasserIn]
• Verfasst von: Helmchen, Günter [VerfasserIn]
• Titel: Addition of organometallic reagents to chiral N-methoxylactams
• Titelzusatz: enantioselective syntheses of pyrrolidines and piperidines
• Verf.angabe: Mascha Jäkel, Jianping Qu, Tobias Schnitzer, and Günter Helmchen
• E-Jahr: 2013
• Jahr: 21 October 2013
• Umfang: 10 S.
• Teil: volume:19
• Teil: year:2013
• Teil: number:49
• Teil: pages:16746-16755
• Teil: extent:10
• Fussnoten: Gesehen am 24.03.2021
• Titel Quelle: Enthalten in: Chemistry - a European journal
• Ort Quelle: Weinheim : Wiley-VCH, 1995
• Jahr Quelle: 2013
• Band/Heft Quelle: 19(2013), 49, Seite 16746-16755
• ISSN Quelle: 1521-3765
• DOI: doi:10.1002/chem.201302735
• Datenträger: Online-Ressource
• Sprache: eng
• Sach-SW: alkaloids
• Sach-SW: allylic compounds
• Sach-SW: enantioselectivity
• Sach-SW: iridium
• Sach-SW: lactams
• K10plus-PPN: 175233910X

Abstract

Enantioselective iridium-catalyzed allylic substitutions were used to prepare N-allyl hydroxamic acid derivatives that were suitable for ring-closing metathesis, giving N-methoxylactams. Reactions of these derivatives with Grignard or organolithium compounds gave hemiaminals, which could be reduced diastereoselectively via acyliminium intermediates to give cis-piperidines or cis-pyrrolidines with substituents in the 2,6- or 2,5-positions, respectively. In addition, compounds with a quaternary carbon center could be synthesized by corresponding reactions with potassium cyanide/AcOH. The procedures were applied in the syntheses of alkaloids (−)-209D and (+)-prosophylline.