Metal enolates of alpha-CF3 ketones: theoretical guideline, direct generation, and synthetic use.
The difficulty as well as the significance of the direct generation of metal enolates of alpha-CF(3) ketones cannot be easily understood by chemists unfamiliar with F. In sharp contrast to the sunny side of non-F, hydrocarbon chemistry, F chemistry has long been overshadowed. Metal enolates of carbonyl compounds are synthetically important in C-C bond-forming reactions. However, the metal enolates of fluorinated carbonyl compounds have been severely limited to alpha-F metal enolates. Alpha-CF(3) metal enolates have generally been recognized as unstable and difficult to prepare because of the facile beta-M-F elimination. However, we have developed a direct generation and synthetic application of alpha-CF(3) metal enolates. Therefore, the present results regarding the direct generation and synthetic use of metal enolates of alpha-CF(3) ketones might be recognized as a real breakthrough for the general use of metal enolates in F chemistry.
Mikami
Koichi
K
Department of Applied Chemistry, Tokyo Institute of Technology, Meguro-ku, Tokyo 152-8552. kmikami@o.cc.titech.ac.jp
Itoh
Yoshimitsu
Y
D002384:Catalysis; D003512:Cyclohexanones / Q000737:chemistry; D005461:Fluorine / Q000737:chemistry; D005466:Fluorocarbons / Q000138:chemical synthesis* / Q000737:chemistry; D005609:Free Radicals / Q000737:chemistry; D007659:Ketones / Q000138:chemical synthesis* / Q000737:chemistry; D008094:Lithium / Q000737:chemistry; D008670:Metals / Q000737:chemistry*; D008956:Models, Chemical; D008958:Models, Molecular; D008968:Molecular Conformation; D015394:Molecular Structure; D011437:Propylamines / Q000737:chemistry; D013237:Stereoisomerism; D014025:Titanium / Q000737:chemistry
D003512:Cyclohexanones; D005466:Fluorocarbons; D005609:Free Radicals; D007659:Ketones; D008670:Metals; D011437:Propylamines; D005461:Fluorine; C025096:titanium tetrachloride; D008094:Lithium; C007442:diisopropylamine; D014025:Titanium