One-pot formation of piperidine- and pyrrolidine-substituted pyridinium salts via addition of 5-alkylaminopenta-2,4-dienals to N-acyliminium ions: application to the synthesis of (±)-nicotine and analogs.
Addition of 5-alkylaminopenta-2,4-dienals onto N-acyliminium ions, generated in situ from α-hydroxycarbamates derived from pyrrolidine or piperidine, in the presence of zinc triflate, followed by dehydrative cyclization, allowed the formation of pyridinium salts substituted at their 3-position by a five- or six-membered nitrogen heterocycle. Subsequent N-dealkylation of the pyridinium moiety and deprotection of the secondary amine or reduction of the carbamate function led to (±)-nicotine and analogs.
Peixoto
Sabrina
S
Centre de Recherche de Gif, Institut de Chimie des Substances Naturelles, CNRS, Avenue de la Terrasse, 91198 Gif-sur-Yvette Cedex, France.
Nguyen
Tuan Minh
TM
Crich
David
D
Delpech
Bernard
B
Marazano
Christian
C
D000179:Acrylates / Q000737:chemistry*; D000478:Alkylation; D000588:Amines / Q000737:chemistry*; D007097:Imines / Q000737:chemistry*; D007477:Ions / Q000737:chemistry; D015394:Molecular Structure; D009538:Nicotine / Q000031:analogs & derivatives / Q000138:chemical synthesis*; D010880:Piperidines / Q000737:chemistry*; D011726:Pyridinium Compounds / Q000737:chemistry*; D011759:Pyrrolidines / Q000737:chemistry*
D000179:Acrylates; D000588:Amines; D007097:Imines; D007477:Ions; D010880:Piperidines; D011726:Pyridinium Compounds; D011759:Pyrrolidines; C032727:piperidine; D009538:Nicotine; C036658:acrylic acid; C032519:pyrrolidine