title: Enantioselective divergent synthesis of (-)-cis-α- and (-)-cis-γ-irone by using Wilkinson's catalyst.
abstract: A simple, efficient synthesis is reported for (-)-cis-α- and (-)-cis-γ-irone, two precious constituents of iris oils, in ≥99 % diastereomeric and enantioselective ratios. The two routes diverge from a common intermediate prepared from (-)-epoxygeraniol. Of general interest in this approach is the installation of the enone moiety of irones through a NHCAu(I) -catalyzed Meyer-Schuster-like rearrangement of a propargylic benzoate and the use of Wilkinson's catalyst for the stereoselective hydrogenation of a prostereogenic exocyclic double bond to secure the critical cis stereochemistry of the alkyl groups at C2 and C6 of the irones. The stereochemical aspects of this reaction are rationally supported by DFT calculation of the conformers of the substrates undergoing the hydrogenation and by a modeling study of the geometry of the rhodium η(2) complexes involved in the diastereodifferentiation of the double bond faces. Thus, computational investigation of the η(2) intermediates formed in the catalytic cycle of prostereogenic alkene hydrogenation by using Wilkinson's catalyst could be highly predictive of the stereochemistry of the products.
authors.affiliation: Dipartimento di Chimica, Sezione Chimica Organica, Università degli Studi di Pavia, Via Taramelli 12, 27100 Pavia (Italy).
authors.forename: Serena
authors.initials: S
authors.lastname: Bugoni
authors.forename: Debora
authors.initials: D
authors.lastname: Boccato
authors.forename: Alessio
authors.initials: A
authors.lastname: Porta
authors.forename: Giuseppe
authors.initials: G
authors.lastname: Zanoni
authors.forename: Giovanni
authors.initials: G
authors.lastname: Vidari
mesh_terms: D002384:Catalysis; D006865:Hydrogenation; D008958:Models, Molecular; D045792:Norisoprenoids / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D045792:Norisoprenoids
keywords: Wilkinson’s catalyst; fragrances; hydrogenation; terpenoids; total synthesis