0466461 - ÚOCHB 2017 RIV GB eng J - Journal Article
Řehová, Lucie - Dračínský, Martin - Jahn, Ullrich
A general approach to iridoids by applying a new Julia olefination and a tandem anion-radical-carbocation crossover reaction.
Organic & Biomolecular Chemistry. Roč. 14, č. 40 (2016), s. 9612-9621. ISSN 1477-0520. E-ISSN 1477-0539
R&D Projects: GA ČR GAP207/11/1598
Grant - others:COST(XE) CM1201
Institutional support: RVO:61388963
Keywords : stereoselective Favorskii rearrangement * stereocontrolled synthesis * (+)-iridomyrmecin
Subject RIV: CC - Organic Chemistry
Impact factor: 3.564, year: 2016
http://pubs.rsc.org/en/content/articlehtml/2016/ob/c6ob01599a

A unified, asymmetric approach to the total synthesis of naturally occurring iridoids is presented. The synthesis features a recently discovered ortho → alpha 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.
Permanent Link: http://hdl.handle.net/11104/0264745