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Competitive gold-promoted Meyer-Schuster and oxy-Cope rearrangements of 3-acyloxy-1,5-enynes : selective catalysis for the synthesis of (+)-(S)-gamma-ionone and (-)-(2S,6R)-cis-gamma-irone

(2015) CHEMISTRY-A EUROPEAN JOURNAL. 21(40). p.14068-14074
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Abstract
We report a simple, highly stereoselective synthesis of (+)-(S)-gamma-ionone and (-)-(2S,6R)-cis-gamma-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)(mu-OH)][BF4] in anhydrous dichloromethane selectively promoted the oxy-Cope rearrangement of propargylic alcohols.
Keywords
fragrances, gold, homogeneous catalysis, sigmatropic rearrangement, terpenoids, ALPHA-CYCLOGERANIUM ACIDS, CIS-GAMMA-IRONE, ENANTIOSELECTIVE SYNTHESIS, OLFACTORY EVALUATION, FRAGRANCE CHEMISTRY, PROPARGYLIC ESTERS, KARAHANA LACTONE, ENANTIOMERS, IONONES, DAMASCONE

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Chicago
Bugoni, Serena, Valentina Merlini, Alessio Porta, Sylvain Gaillard, Giuseppe Zanoni, Steven Nolan, and Giovanni Vidari. 2015. “Competitive Gold-promoted Meyer-Schuster and oxy-Cope Rearrangements of 3-acyloxy-1,5-enynes : Selective Catalysis for the Synthesis of (+)-(S)-gamma-ionone and (-)-(2S,6R)-cis-gamma-irone.” Chemistry-a European Journal 21 (40): 14068–14074.
APA
Bugoni, S., Merlini, V., Porta, A., Gaillard, S., Zanoni, G., Nolan, S., & Vidari, G. (2015). Competitive gold-promoted Meyer-Schuster and oxy-Cope rearrangements of 3-acyloxy-1,5-enynes : selective catalysis for the synthesis of (+)-(S)-gamma-ionone and (-)-(2S,6R)-cis-gamma-irone. CHEMISTRY-A EUROPEAN JOURNAL, 21(40), 14068–14074.
Vancouver
1.
Bugoni S, Merlini V, Porta A, Gaillard S, Zanoni G, Nolan S, et al. Competitive gold-promoted Meyer-Schuster and oxy-Cope rearrangements of 3-acyloxy-1,5-enynes : selective catalysis for the synthesis of (+)-(S)-gamma-ionone and (-)-(2S,6R)-cis-gamma-irone. CHEMISTRY-A EUROPEAN JOURNAL. 2015;21(40):14068–74.
MLA
Bugoni, Serena, Valentina Merlini, Alessio Porta, et al. “Competitive Gold-promoted Meyer-Schuster and oxy-Cope Rearrangements of 3-acyloxy-1,5-enynes : Selective Catalysis for the Synthesis of (+)-(S)-gamma-ionone and (-)-(2S,6R)-cis-gamma-irone.” CHEMISTRY-A EUROPEAN JOURNAL 21.40 (2015): 14068–14074. Print.
@article{8168289,
  abstract     = {We report a simple, highly stereoselective synthesis of (+)-(S)-gamma-ionone and (-)-(2S,6R)-cis-gamma-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)(mu-OH)][BF4] in anhydrous dichloromethane selectively promoted the oxy-Cope rearrangement of propargylic alcohols.},
  author       = {Bugoni, Serena and Merlini, Valentina and Porta, Alessio and Gaillard, Sylvain and Zanoni, Giuseppe and Nolan, Steven and Vidari, Giovanni},
  issn         = {0947-6539},
  journal      = {CHEMISTRY-A EUROPEAN JOURNAL},
  keyword      = {fragrances,gold,homogeneous catalysis,sigmatropic rearrangement,terpenoids,ALPHA-CYCLOGERANIUM ACIDS,CIS-GAMMA-IRONE,ENANTIOSELECTIVE SYNTHESIS,OLFACTORY EVALUATION,FRAGRANCE CHEMISTRY,PROPARGYLIC ESTERS,KARAHANA LACTONE,ENANTIOMERS,IONONES,DAMASCONE},
  language     = {eng},
  number       = {40},
  pages        = {14068--14074},
  title        = {Competitive gold-promoted Meyer-Schuster and oxy-Cope rearrangements of 3-acyloxy-1,5-enynes : selective catalysis for the synthesis of (+)-(S)-gamma-ionone and (-)-(2S,6R)-cis-gamma-irone},
  url          = {http://dx.doi.org/10.1002/chem.201502382},
  volume       = {21},
  year         = {2015},
}

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