French
DeutschKauffmann olefination
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
[edit]The reagent was generated in situ by conversion of different halogenides of molybdenum or tungsten with methyllithium at low temperatures (−78 °C).[1][2][3][4]
During the warm-up process the formation of the active reagent occurs. NMR-experiments have shown that the active reagent is not a Schrock carbene (e.g. Tebbe-reagent).
Mechanism
[edit]Mechanism experiments shows that the olefination process is a sequence of cycloaddition and cycloelimination steps.
Applications
[edit]For a long time this reaction had no applications in synthetic organic chemistry. In 2002 it was used in a total synthesis of the terpene gleenol as a mild and non-basic reagent in a one-pot-protocol with an olefin metathesis step with Grubbs catalyst.[5] It is remarkable that the organometallic catalyst tolerates the inorganic reaction products.
References
[edit]- ^ T. Kauffmann; M. Papenberg; R. Wieschollek; J. Sander (1992). "Organomolybdän- und Organowolfram-Reagenzien, II. über den carbonylolefinierenden μ-Methylenkomplex aus Mo2Cl10 und vier äquivalenten Methyllithium". Chem. Ber. 125: 143–148. doi:10.1002/cber.19921250123.
- ^ T. Kauffmann; P. Fiegenbaum; M. Papenberg; R. Wieschollek; D. Wingbermühl (1993). "Organomolybdän- und Organowolfram-;Reagenzien, III. Chemoselektive, nichtbasische Carbonylmethylenierungs-;Reagenzien aus MoOCl3(THF)2 und MoOCl4: Bildung, Thermolabilität, Struktur". Chem. Ber. 126: 79–87. doi:10.1002/cber.19931260114.
- ^ T. Kauffmann; J. Baune; P. Fiegenbaum; U. Hansmersmann; C. Neiteler; M. Papenberg; R. Wiescholleck (1993). "Organomolybdän- und Organowolfram-;Reagenzien, IV. über die Chemoselektivität des carbonylmethylenierenden Reagenzes aus 2 MoOCl3(THF)2 und 4 CH3Li". Chem. Ber. 126: 89–96. doi:10.1002/cber.19931260115.
- ^ T. Kauffmann (1997). "Neue Reaktionen molybdän- und wolframorganischer Verbindungen: Additiv-reduktive Carbonyldimerisierung, spontane Umwandlung von Methyl- in μ-Methylenliganden und selektive Carbonylmethylenierung". Angew. Chem. 109 (12): 1312–1329. Bibcode:1997AngCh.109.1312K. doi:10.1002/ange.19971091205.
- ^ K. Oesterreich; I. Klein; D. Spitzner (2002). "'One-pot' Reactions: Total Synthesis of the Spirocyclic Marine Sesquiterpene, (+)-Axenol". Synlett (10): 1712–1714. doi:10.1055/s-2002-34211.