title: A general approach to iridoids by applying a new Julia olefination and a tandem anion-radical-carbocation 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.
authors.affiliation: Institute of Organic Chemistry and Biochemistry, Czech Academy of Sciences, Flemingovo náměstí 2, 16610 Prague 6, Czech Republic. jahn@uochb.cas.cz.
authors.forename: Lucie
authors.initials: L
authors.lastname: Řehová
authors.affiliation: Institute of Organic Chemistry and Biochemistry, Czech Academy of Sciences, Flemingovo náměstí 2, 16610 Prague 6, Czech Republic. jahn@uochb.cas.cz.
authors.forename: Martin
authors.initials: M
authors.lastname: Dračínský
authors.affiliation: Institute of Organic Chemistry and Biochemistry, Czech Academy of Sciences, Flemingovo náměstí 2, 16610 Prague 6, Czech Republic. jahn@uochb.cas.cz.
authors.forename: Ullrich
authors.initials: U
authors.lastname: Jahn