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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

Serena Bugoni, Valentina Merlini, Alessio Porta, Sylvain Gaillard, Giuseppe Zanoni, Steven Nolan UGent and Giovanni Vidari (2015) CHEMISTRY-A EUROPEAN JOURNAL. 21(40). p.14068-14074
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.
Please use this url to cite or link to this publication:
author
organization
year
type
journalArticle (original)
publication status
published
subject
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
journal title
CHEMISTRY-A EUROPEAN JOURNAL
Chem.-Eur. J.
volume
21
issue
40
pages
14068 - 14074
Web of Science type
Article
Web of Science id
000363331200030
JCR category
CHEMISTRY, MULTIDISCIPLINARY
JCR impact factor
5.771 (2015)
JCR rank
24/163 (2015)
JCR quartile
1 (2015)
ISSN
0947-6539
DOI
10.1002/chem.201502382
language
English
UGent publication?
no
classification
A1
id
8168289
handle
http://hdl.handle.net/1854/LU-8168289
date created
2016-11-24 15:50:42
date last changed
2018-01-29 12:12:29
@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},
}

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.