Aqueous aldol catalysis by a nicotine metabolite.
Nornicotine, an endogenous tobacco alkaloid and minor nicotine metabolite, can catalyze aldol reactions at physiological pH. Catalysis appears to be due to a covalent enamine mechanism, an unprecedented reaction with small organic molecule catalysts in aqueous buffer. Kinetic parameters for nornicotine as well as other related alkaloids were measured and demonstrate that both the pyrrolidine and pyridine rings are critical for optimal catalysis. Substrate compatibility of this catalyst and its implications in vivo are discussed.
Dickerson
Tobin J
TJ
Department of Chemistry, The Scripps Research Institute, The Skaggs Institute for Chemical Biology, 10550 North Torrey Pines Road, La Jolla, CA 92037, USA.
Janda
Kim D
KD
D000096:Acetone / Q000737:chemistry*; D001547:Benzaldehydes / Q000737:chemistry*; D002384:Catalysis; D007700:Kinetics; D009538:Nicotine / Q000031:analogs & derivatives* / Q000737:chemistry*; D011392:Proline / Q000737:chemistry; D011759:Pyrrolidines / Q000737:chemistry; D013379:Substrate Specificity; D014867:Water / Q000737:chemistry
D001547:Benzaldehydes; D011759:Pyrrolidines; D014867:Water; D000096:Acetone; C029915:4-nitrobenzaldehyde; D009538:Nicotine; C005311:nornicotine; D011392:Proline; C032519:pyrrolidine