| 17580903 |
Butova ED, Fokin AA, Schreiner PR: Beyond the corey reaction: one-step diolefination of cyclic ketones. J Org Chem. 2007 Jul 20;72(15):5689-96. Epub 2007 Jun 20.
The reactivities of the cyclic ketones cycloheptanone, cyclodecanone, and cycloundecanone with dimethylsulfoxonium methylide generated from trimethylsulfoxonium iodide and base (NaH) were studied in diglyme at 130 degrees C. Oxiranes, which primarily form via the Corey reaction, lead to ring expansions to give oxetanes and oxacyclopentanes when an excess of dimethylsulfoxonium methylide is used. The Corey reaction is suppressed in the presence of excess of base, and 1,3-terminal dienes form instead (we term this reaction the Yurchenko diolefination). Our mechanistic proposal involves the deprotonation of the betaine that forms after the attack of dimethylsulfoxonium methylide on the carbonyl group of the ketone. The key step of the diolefination reaction involves a [2,3]-sigmatropic rearrangement of the ylide to a gamma-unsaturated sulfoxide with a barrier of 9.9 kcal/mol (DeltaH298, MP2/cc-pVDZ, for the cycloheptane derivative). The elimination of sulfenic acid from the gamma-unsaturated sulfoxide in the terminal step of the diolefination is associated with a higher barrier (17.3 kcal/mol) but is strongly accelerated in the presence of base. The reactivity of cyclic ketones in the Yurchenko reaction depends on the ring size; medium-sized cyclodecanone is less reactive than either cycloheptanone or cyclododecanone. |
31(0,1,1,1) |