The influence of benzylic protection and allylic substituents on the CuCl-TMEDA catalyzed rearrangement of N-allyl-N-benzyl-2,2-dihaloamides to gamma-lactams. Application to the stereoselective synthesis of pilolactam.

Authors
Ghelfi, F Bellesia, F Forti, L Ghirardini, G Grandi, R Libertini, E Montemaggi, MC Pagnoni, UM Pinetti, A De Buyck, L Parsons, AF
Citation
F. Ghelfi et al., The influence of benzylic protection and allylic substituents on the CuCl-TMEDA catalyzed rearrangement of N-allyl-N-benzyl-2,2-dihaloamides to gamma-lactams. Application to the stereoselective synthesis of pilolactam., TETRAHEDRON, 55(18), 1999, pp. 5839-5852
Citations number
30
Categorie Soggetti
Chemistry & Analysis","Organic Chemistry/Polymer Science
Journal title
TETRAHEDRON
ISSN journal
00404020 → ACNP
Volume
55
Issue
18
Year of publication
1999
Pages
5839 - 5852
Database
ISI
SICI code
0040-4020(19990430)55:18<5839:TIOBPA>2.0.ZU;2-E
Abstract
A number of N-benzylic protecting groups and allylic substituents have been investigated for the rearrangement, promoted by CuCl-TMEDA, of N-allyl-2,2 -dihaloamides to 3,4-disubstituted gamma-lactams. An appreciable chiral ind uction was observed at the C-4 site when alpha-phenylethylamine was used as a chiral protecting group, while an unexpected Diels-Alder reaction occurr ed when using a 2-furyl-methyl protection. This rearrangement has been appl ied to the synthesis of pilolactam, a drug with muscarinic activity. (C) 19 99 Elsevier Science Ltd. All rights reserved.