A general approach to iridoids by applying a new Julia olefination and a tandem anion-radical-carbocation crossover reaction. Issue 40 (21st September 2016)

• Record Type: Journal Article
• Authors: Řehová, Lucie; Dračínský, Martin; Jahn, Ullrich
• Is Part Of: Organic & biomolecular chemistry. Volume 14:Issue 40(2016)
• Page Start: 9612
• Page End: 9621
• Publication Date: 2016-09-21
• Subjects: Chemistry, Organic -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1039/c6ob01599a
• Languages: English
• ISSNs: 1477-0520

Abstract

Abstract : An efficient asymmetric approach to dihydronepetalactone and dolicholactone is presented featuring a Julia olefination and an anion–radical–cation crossover reaction. Abstract : A unified, asymmetric approach to the total synthesis of naturally occurring iridoids is presented. The synthesis features a recently discovered ortho → α transmetalation of alkyl aryl sulfone carbanions, thus enabling Julia reactions, by which so far hardly accessible disilylated olefins have been obtained. A subsequent tandem alkoxycarbonylation/oxidative radical cyclization afforded substituted cyclopentane building blocks with high diastereoselectivity. These compounds serve as unique central intermediates for short access to dihydronepetalactone, dolicholactone and potentially other iridoids.