Aqueous Aldol Catalysis by a Nicotine Metabolite

• Published in: Journal of the American Chemical Society Vol. 124; no. 13; pp. 3220 - 3221
• Main Authors: Dickerson, Tobin J, Janda, Kim D
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 03.04.2002; Amer Chemical Soc
• Subjects: Acetone - chemistry; Benzaldehydes - chemistry; Catalysis; Chemistry; Chemistry, Multidisciplinary; Exact sciences and technology; Kinetics; Kinetics and mechanisms; Nicotine - analogs & derivatives; Nicotine - chemistry; Organic chemistry; Physical Sciences; Proline - chemistry; Pyrrolidines - chemistry; Reactivity and mechanisms; Science & Technology; Substrate Specificity; Water - chemistry; ORGANIC CATALYSIS; ANTIBODIES; MEDIA; STRATEGIES; Nitro compound; Catalytic reaction; Aliphatic compound; Experimental study; Aldol condensation; Biocatalyst; Pyridine derivatives; Homogeneous catalysis; Reaction mechanism; Benzenic compound; Kinetic parameter; Rate constant; Acetone
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja017774f

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.