Cascade Metathesis Reactions for the Synthesis of Taxane and Isotaxane Derivatives. Issue 20 (8th April 2016)

• Record Type: Journal Article
• Authors: Ma, Cong; Letort, Aurélien; Aouzal, Rémi; Wilkes, Antonia; Maiti, Gourhari; Farrugia, Louis J.; Ricard, Louis; Prunet, Joëlle
• Is Part Of: Chemistry. Volume 22:Issue 20(2016)
• Page Start: 6891
• Page End: 6898
• Publication Date: 2016-04-08
• Subjects: cyclooctenes -- enyne -- metathesis -- synthesis design -- taxanes; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201600592
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: Tricyclic isotaxane and taxane derivatives have been synthesized by a very efficient cascade ring‐closing dienyne metathesis (RCDEYM) reaction, which formed the A and B rings in one operation. When the alkyne is present at C13 (with no neighboring gem ‐dimethyl group), the RCEDYM reaction leads to 14, 15‐isotaxanes16 a, b and18 b with the gem ‐dimethyl group on the A ring. If the alkyne is at the C11 position (and thus flanked by a gem ‐dimethyl group), RCEDYM reaction only proceeds in the presence of a trisubstituted olefin at C13, which disfavors the competing diene ring‐closing metathesis reaction, to give the tricyclic core of Taxol44 . Abstract : Closing time : Isotaxane and taxane derivatives have been synthesized by cascade ring‐closing metathesis reactions. The course of the cyclization can be directed by adequately choosing the position of the alkyne and the degree of substitution of the alkene.