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Of general interest in this approach are the photoisomerization of an <jats:italic>endo<\/jats:italic> trisubstituted cyclohexene double bond to an <jats:italic>exo<\/jats:italic> vinyl group and the installation of the enone side chain through a [(NHC)Au<jats:sup>I<\/jats:sup>]\u2010catalyzed Meyer\u2013Schuster\u2010like rearrangement. This required a careful investigation of the mechanism of the gold\u2010catalyzed reaction and a judicious selection of reaction conditions. In fact, it was found that the Meyer\u2013Schuster reaction may compete with the oxy\u2010Cope rearrangement. Gold\u2010based catalytic systems can promote either reaction selectively. In the present system, the mononuclear gold complex [Au(IPr)Cl], in combination with the silver salt AgSbF<jats:sub>6<\/jats:sub> in 100:1 butan\u20102\u2010one\/H<jats:sub>2<\/jats:sub>O, proved to efficiently promote the Meyer\u2013Schuster rearrangement of propargylic benzoates, whereas the digold catalyst [{Au(IPr)}<jats:sub>2<\/jats:sub>(\u03bc\u2010OH)][BF<jats:sub>4<\/jats:sub>] in anhydrous dichloromethane selectively promoted the oxy\u2010Cope rearrangement of propargylic alcohols.<\/jats:p>","DOI":"10.1002\/chem.201502382","type":"journal-article","created":{"date-parts":[[2015,8,28]],"date-time":"2015-08-28T05:19:33Z","timestamp":1440739173000},"page":"14068-14074","source":"Crossref","is-referenced-by-count":15,"title":["Competitive Gold\u2010Promoted Meyer\u2013Schuster and oxy\u2010Cope Rearrangements of 3\u2010Acyloxy\u20101,5\u2010enynes: Selective Catalysis for the Synthesis of (+)\u2010(<i>S<\/i>)\u2010\u03b3\u2010Ionone and (\u2212)\u2010(2<i>S<\/i>,6\u2009<i>R<\/i>)\u2010<i>cis<\/i>\u2010\u03b3\u2010Irone"],"prefix":"10.1002","volume":"21","author":[{"given":"Serena","family":"Bugoni","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Valentina","family":"Merlini","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Alessio","family":"Porta","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sylvain","family":"Gaillard","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Giuseppe","family":"Zanoni","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Steven 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