Competitive Gold-Promoted Meyer-Schuster and oxy-Cope Rearrangements of 3-Acyloxy-1,5-enynes: Selective Catalysis for the Synthesis of (+)-(S)-γ-Ionone and (-)-(2S,6 R)-cis-γ-Irone.

We report a simple, highly stereoselective synthesis of (+)-(S)-γ-ionone and (-)-(2S,6R)-cis-γ-irone, two characteristic and precious odorants; the latter compound is a constituent of the essential oil obtained from iris rhizomes. Of general interest in this approach are the photoisomerization of an endo trisubstituted cyclohexene double bond to an exo vinyl group and the installation of the enone side chain through a [(NHC)Au(I)]-catalyzed Meyer-Schuster-like rearrangement. This required a careful investigation of the mechanism of the gold-catalyzed reaction and a judicious selection of reaction conditions. In fact, it was found that the Meyer-Schuster reaction may compete with the oxy-Cope rearrangement. Gold-based catalytic systems can promote either reaction selectively. In the present system, the mononuclear gold complex [Au(IPr)Cl], in combination with the silver salt AgSbF6 in 100:1 butan-2-one/H2O, proved to efficiently promote the Meyer-Schuster rearrangement of propargylic benzoates, whereas the digold catalyst [{Au(IPr)}2(µ-OH)][BF4] in anhydrous dichloromethane selectively promoted the oxy-Cope rearrangement of propargylic alcohols.

A general and concise enantioselective divergent approach to 13-alkyl-substituted ionones.

A novel enantioselective divergent route to 13-alkyl derivatives of α- and γ-ionone, important components of perfumes and fragrances, is reported. This relatively short and convenient methodology takes advantage of the use of a common intermediate, easily obtained from highly enantiomerically enriched (S)-α-ionone, which avoids the separate installation of the butenone side chain at C(6) for each analog. Olfactory evaluation of synthesized compounds reconfirmed the influence of the hydrophobic interactions of alkyl substituents at C(5) with olfactory receptors (ORs) in the chemoreception of ionones, and suggested that a synperiplanar orientation of C(13) and the lateral chain is the better geometry fitting OR's cavity.

One-pot consecutive reactions based on the synthesis of conjugated enones by the re-catalysed Meyer-Schuster rearrangement.

Re catalysis in one-pot reactions: An atom-economical, one-pot strategy that involves alkyne deprotonation and a subsequent rhenium(V)-catalysed Meyer-Schuster rearrangement of the alkynol to provide α,ß-unsaturated enones in high yield has been developed (see scheme). Subsequent in situ hydride reduction or Diels-Alder reaction of the enones provided products in good-to-high overall yields.

Biomimetic cyclization of geraniol derivatives, a useful tool in the total synthesis of bioactive monocyclic terpenoids.

This review is a detailed account of authors' work in the field of biomimetic cyclization of geraniol-like dienes. The very high regio- and enantioselectivity achieved made these elegant reactions a viable tool for the synthesis of monocyclic building blocks used in the synthesis of valued terpenoids, like the precious aroma and perfume constituents' ionones and irones.