144656-97-3Relevant academic research and scientific papers
Ring expansion by tandem double Tebbe-Claisen technology
Paquette, Leo A.,Philippo, Christophe M. G.,Vo, Nha Huu
, p. 1356 - 1365 (2007/10/02)
2-Cyclohexenone rings that form part of a larger structural assembly are amenable to peracid oxidation with formation of an epoxy lactone.These intermediates are readily transformed under acidic, basic, or neutral conditions to ring-contracted aldehydo lactones, which are then subjected to condensation with a slight excess of Tebbe reagent.These conditions result in methylenation of carbonyl groups and set the stage for operation of a Claisen rearrangement.When the latter is catalyzed by Tribal, the sigmatropic process occurs at room temperature.With systems typified by 17 and 24, the isomerization is complete within 15 min.The pre sence of a proximate angular methyl group as in 9b, 29, and 37 exerts a retarding kinetic effect.In such examples, a period of 6 h is required to achieve completion.Swern oxidation completes the conversion to the 4-cyclooctenones, where the two carbons stemming from the Tebbe reagent are inserted bewtween the original carbonyl and α-olefinic carbons.The overall process is tolerant of ether functionality and additional sites of unsaturation.
