The Kauffmann olefination is a chemical reaction to convert aldehydes and ketones to olefins with a terminal methylene group. This reaction was discovered by the German chemist Thomas Kauffmann and is related to the better known Tebbe olefination or Wittig reaction.
Formation of the reagent
During the warm-up process the formation of the active reagent occurs. nmr-experiments has shown that the active reagent is not a Schrock carbene (e.g. Tebbe-reagent).
Mechanism experiments shows that the olifination process is a sequence of cycloaddition and cycloelemination steps.
For a long time there wasn't any usage of this reaction in the synthetic organic chemistry. In the year 2002 it was used in a total synthesis of the terpene gleenol as a mild and non-basic reagent. An one-pot-protocol with an olefin metathesis step with Grubbs catalyst is also available. It is remarkable that the organometallic catalyst tolerates the inorganic reaction products.
- T. Kauffmann, M. Papenberg, R. Wieschollek, J. Sander: In Chem. Ber. 1992, 125, 143-148
- T. Kauffmann, P. Fiegenbaum, M. Papenberg, R. Wieschollek, D. Wingbermühl: In Chem. Ber. 1993, 126, 79-87
- T. Kauffmann, J. Braune, P. Fiegenbaum, U. Hansmersmann, C. Neiteler, M. Papenberg, R. Wiescholleck: In Chem. Ber. 1993, 126, 89-96
- T. Kauffmann: In Angew. Chem. 1997, 109, 1312-1329
- K. Oesterreich, D. Spitzner: In Tetrahedron 2002, 58, 4331-4334
- K. Oesterreich, I. Klein, D. Spitzner: In Synlett 2002, 1712-1714