[Studies on reaction control and development of new practical reagents based on characteristics of reaction field].
Reaction rates and selectivities can be critically affected by the reaction field. Using a diverse set of reagents and reaction systems, the author reviews a variety of ways to control the reaction field. In the first example, we discuss 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMT-MM), which serves as an exceptionally convenient reagent for dehydrocondensation. In particular, formation of carboxamide by DMT-MM was found to take place even if water or alcohol were used as a reaction medium. Thus, chemical modification of carboxyl groups and/or amino groups of highly polar substrates, such as amino acid derivatives, peptides, glyco-chains, and nucleotides, can be simply effected by mixing them with DMT-MM in aqueous or alcoholic solvents. The author also found that a tertiary amine catalyzes the activation step of carboxylic acid with 2-chloro-4,6-dimethoxy-1,3,5-triazine (CDMT) via in situ generation of coupling reagents. Proceeding further in this direction, we determined that artificial acyltransferase and cyclotransferase could be formed by conjugation of a tertiary amine catalyst to host-molecules to mimic a substrate binding site. Finally, the micellar interface, well known for promoting hydrolysis, clearly provides a superior reaction field for dehydrocondensation. When a 1,3,5-triazine-type amphiphilic dehydrocondensing agent was used, bimolecular dehydrocondensation between amphiphilic carboxylate and amines was highly accelerated (2000-fold) in a micellar system. Spontaneous membrane fusion was induced by adoption of the micellar reaction in the ceramide synthesis at the surface of membranes. All together, these diverse findings strongly support the central importance of the reaction field in controlling reaction rates and selectivity.
Kunishima
Munetaka
M
Faculty of Pharmaceutical Sciences, Kobe Gakuin University, Kobe, Japan. kunisima@pharm.kobegakuin.ac.jp
D032701:Biomimetics; D002384:Catalysis; D002625:Chemistry, Organic; D003890:Desiccation; D015195:Drug Design; D004951:Esterification; D007202:Indicators and Reagents; D009025:Morpholines; D055601:Organic Chemistry Phenomena; D010455:Peptides / Q000138:chemical synthesis; D011108:Polymers; D014227:Triazines; D014867:Water
C467606:4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride; D007202:Indicators and Reagents; D009025:Morpholines; D010455:Peptides; D011108:Polymers; D014227:Triazines; D014867:Water