title: Lewis base catalyzed Mannich-type reactions between trimethylsilyl enol ethers and aldimines.
abstract: Lewis base catalyzed Mannich-type reaction between trimethylsilyl enol ethers and N-tosylaldimines is described. Nitrogen anions generated from amides or imides such as lithium benzamide or potassium phthalimide are found to be effective Lewis base catalysts in DMF at room temperature to afford the corresponding beta-amino carbonyl compounds in good to high yields; the oxygen anion generated from carboxylic acids such as lithium acetate was also found to be effective in dry DMF. The above-mentioned lithium acetate-catalyzed Mannich-type reaction between aldimines and various trimethylsilyl (TMS) enol ethers such as silyl ketene acetal proceeded smoothly even in water-containing DMF. Then, Lewis base catalyzed three-component Mannich-type reactions of TMS enol ether, tosylamide, and aromatic aldehyde having electron-withdrawing group such as p-nitrobenzaldehyde were investigated. The reaction proceeded smoothly to afford the corresponding beta-amino ester in good yield. Further, ammonium carboxylates such as tetrabutyl ammonium acetate or tetrabutyl ammonium benzoate were found to be more effective Lewis base catalysts in the above-mentioned Mannich-type reaction. The synthesis proceeded in various solvents at lower temperatures. The reaction between aldimines and TMS enol ethers generated from thioester and various ketones such as propiophenone or cyclohexanone also proceeded smoothly to afford the corresponding beta-amino carbonyl compounds in high yields with good to high anti-selectivities.
authors.affiliation: Center for Basic Research, The Kitasato Institute, 6-15-5 Toshima, Kita-ku, Tokyo 114-0003, Japan.
authors.forename: Hidehiko
authors.initials: H
authors.lastname: Fujisawa
authors.forename: Eiki
authors.initials: E
authors.lastname: Takahashi
authors.forename: Teruaki
authors.initials: T
authors.lastname: Mukaiyama
mesh_terms: D000085:Acetates / Q000737:chemistry; D000447:Aldehydes / Q000737:chemistry; D002384:Catalysis; D002855:Chromatography, Thin Layer; D004987:Ethers / Q000138:chemical synthesis; D007097:Imines / Q000138:chemical synthesis; D007202:Indicators and Reagents; D009682:Magnetic Resonance Spectroscopy; D008352:Mannich Bases / Q000737:chemistry*; D000644:Quaternary Ammonium Compounds / Q000737:chemistry; D013055:Spectrophotometry, Infrared; D013449:Sulfonamides / Q000737:chemistry; D014050:Toluene / Q000031:analogs & derivatives / Q000737:chemistry; D014297:Trimethylsilyl Compounds / Q000138:chemical synthesis*; D000096926:Benzenesulfonamides
chemical_list: D000085:Acetates; D000447:Aldehydes; D004987:Ethers; D007097:Imines; D007202:Indicators and Reagents; D008352:Mannich Bases; D000644:Quaternary Ammonium Compounds; D013449:Sulfonamides; D014050:Toluene; D014297:Trimethylsilyl Compounds; C009405:tetrabutylammonium; C027917:tetramethylammonium; C488804:lithium acetate; C025417:4-toluenesulfonamide; D000096926:Benzenesulfonamides