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

✍ Scribed by Franco Ghelfi; Franco Bellesia; Luca Forti; Gianluca Ghirardini; Romano Grandi; Emanuela Libertini; Maria C Montemaggi; Ugo M Pagnoni; Adriano Pinetti; Laurent De Buyck; Andrew F Parsons

• Book ID: 104209370
• Publisher: Elsevier Science
• Year: 1999
• Tongue: French
• Weight: 813 KB
• Volume: 55
• Category: Article
• ISSN: 0040-4020
• DOI: 10.1016/s0040-4020(99)00247-1

✦ Synopsis

A number of N-benzylic protecting groups and allylic substituents have been investigated for the rearrangement, promoted by CuCI-TMEDA, of N-allyl-2,2-dihaloamides to 3,4..disubstituted ylactams. An appreciable chiral induction was observed at the C-4 site when ct-phenylethylarnine was used as a chiral protecting group, while an unexpected Diels-Alder reaction occurred when using a 2furyl-methyl protection. This rearrangement has been applied to the synthesis of pilolactam, a drug with muscarinic activity.