{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,22]],"date-time":"2026-09-22T08:34:53Z","timestamp":1790066093496,"version":"4.0.1"},"reference-count":148,"publisher":"Wiley","issue":"24","license":[{"start":{"date-parts":[[2009,5,5]],"date-time":"2009-05-05T00:00:00Z","timestamp":1241481600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2009,6,8]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p><jats:bold>Disparate sister compounds<\/jats:bold>: Despite their similarity, significantly different strategies were necessary to bring the individual members of the aspercyclide family into reach. Whereas the strained eleven\u2010membered ring of aspercyclide C (see figure) could be closed by RCM, it required the power of organochromium chemistry (Nozaki\u2013Hiyama\u2013Kishi reaction) to forge the frame of its sterically even more hindered congener aspercyclide\u2005B.<jats:boxed-text content-type=\"graphic\" position=\"anchor\"><jats:graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" mimetype=\"image\/gif\" position=\"anchor\" specific-use=\"enlarged-web-image\" xlink:href=\"graphic\/mcontent.gif\"><jats:alt-text>magnified image<\/jats:alt-text><\/jats:graphic><\/jats:boxed-text><\/jats:p><jats:p>Two different approaches to the eleven\u2010membered biaryl ether lactones of the aspercyclide family are disclosed. The core regions of these highly strained targets, which are able to interfere with the binding of immunoglobulin E to its high affinity receptor, can either be forged by ring\u2010closing olefin metathesis (RCM) or by a highly diastereoselective chromium\u2010mediated Nozaki\u2013Hiyama\u2013Kishi (NHK) reaction. Whereas the RCM approach turned out to be responsive to minor changes in the substitution pattern of the substrate, the NHK route is more generally applicable. The preparation of the required cyclization precursor <jats:bold>43<\/jats:bold> hinged on a palladium\u2010catalyzed <jats:italic>ortho<\/jats:italic>\u2010iodination reaction of 2\u2010methylbenzoic acid, an efficient copper\u2010catalyzed Ullmann coupling, and a Takai\u2013Utimoto olefination as the key steps. Moreover, the esterification of the 2,6\u2010disubstituted benzoic acid <jats:bold>34<\/jats:bold> with the sterically hindered secondary alcohol <jats:bold>37<\/jats:bold> was far from trivial. However, this and related transformations were accomplished by recourse to the corresponding acid fluorides, which provided excellent yields in cases in which the more commonly used acid chlorides or mixed anhydrides failed to afford any of the desired products.<\/jats:p>","DOI":"10.1002\/chem.200802681","type":"journal-article","created":{"date-parts":[[2009,5,5]],"date-time":"2009-05-05T12:31:16Z","timestamp":1241526676000},"page":"5956-5968","source":"Crossref","is-referenced-by-count":71,"title":["Total Synthesis of the Aspercyclides"],"prefix":"10.1002","volume":"15","author":[{"given":"Ji\u0159\u00ed","family":"Posp\u00ed\u0161il","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Christoph","family":"M\u00fcller","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Alois","family":"F\u00fcrstner","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2009,5,29]]},"reference":[{"key":"e_1_2_6_1_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.tetlet.2004.08.116"},{"key":"e_1_2_6_2_2","unstructured":"\u00a0"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1146\/annurev.immunol.17.1.931"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1016\/0952-7915(95)80047-6"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1146\/annurev.immunol.17.1.973"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.022635599"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1039\/b512877c"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.tetlet.2007.08.050"},{"key":"e_1_2_6_9_2","unstructured":"General reviews on RCM:"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar000114f"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3757(20000901)112:17<3140::AID-ANGE3140>3.0.CO;2-G"},{"key":"e_1_2_6_11_3","first-page":"3013","volume":"39","year":"2000","journal-title":"Angew. 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