Trichloromethyltrimethylsilane, sodium formate, and dimethylformamide: a mild, efficient, and general method for the preparation of trimethylsilyl-protected 2,2,2-trichloromethylcarbinols from aldehydes and ketones.
New conditions for the preparation of trimethylsilyl-protected 2,2,2-trichloromethylcarbinols 2 from aldehydes and ketones are reported. Compounds 2, which are important intermediates in organic synthesis, were obtained in excellent yields by use of a combination of trichloromethyltrimethylsilane (TMSCCl3), and a catalytic amount of sodium formate (HCOONa) in dimethylformamide (DMF). Substrates bearing highly sensitive protecting groups have been successfully subjected to our conditions. We also describe a one-pot procedure that gives direct access to 2,2,2-trichloromethylcarbinols 3. This methodology avoids the use of strong bases usually required for the synthesis of 3 (Wyvratt et al. J. Org. Chem. 1987, 52, 944; Aggarwal and Mereu, J. Org. Chem. 2000, 65, 7211).
Kister
Jérémy
J
Laboratoire de Synthèse Bio-Organique, UMR 7175--LC1, Faculté de Pharmacie, Université Louis Pasteur, 74 Route du Rhin, BP 24, 67401 Illkirch Graffenstaden, France.
Mioskowski
Charles
C
D000447:Aldehydes / Q000737:chemistry*; D002384:Catalysis; D017606:Chlorine Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D005561:Formates / Q000737:chemistry*; D007659:Ketones / Q000737:chemistry*; D000432:Methanol / Q000138:chemical synthesis / Q000737:chemistry*; D008745:Methylation; D015394:Molecular Structure; D012997:Solvents; D014297:Trimethylsilyl Compounds / Q000737:chemistry*
D000447:Aldehydes; D017606:Chlorine Compounds; D005561:Formates; D007659:Ketones; D012997:Solvents; D014297:Trimethylsilyl Compounds; C520713:trichloromethyltrimethylsilane; C030544:formic acid; D000432:Methanol