{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,15]],"date-time":"2025-10-15T17:02:45Z","timestamp":1760547765468,"version":"build-2065373602"},"reference-count":48,"publisher":"Wiley","issue":"16","license":[{"start":{"date-parts":[[2004,6,30]],"date-time":"2004-06-30T00:00:00Z","timestamp":1088553600000},"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":[[2004,8,20]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Reaction of <jats:italic>in<\/jats:italic>,<jats:italic>in<\/jats:italic>\u2010phosphite <jats:bold>1<\/jats:bold> with thiophosphoryl azide <jats:bold>2<\/jats:bold> affords <jats:italic>in<\/jats:italic>,<jats:italic>in<\/jats:italic>\u2010dithiophosphate <jats:bold>3<\/jats:bold>, <jats:italic>in<\/jats:italic>,<jats:italic>in<\/jats:italic>\u2010thiophosphate\u2013imidophosphate <jats:bold>4<\/jats:bold>, and <jats:italic>in<\/jats:italic>,<jats:italic>in<\/jats:italic>\u2010phosphite\u2013imidophosphate <jats:bold>5<\/jats:bold>. Compounds <jats:bold>4<\/jats:bold> and <jats:bold>5<\/jats:bold> are the first examples of the modification of <jats:italic>in<\/jats:italic>\u2010bridgehead positions in macrobicyclic compounds with groups larger than methyl. The benzaldehyde arms of the <jats:italic>in<\/jats:italic>\u2010substituent in <jats:bold>4<\/jats:bold> and <jats:bold>5<\/jats:bold> jut out of the cage bars. In <jats:bold>4<\/jats:bold> they are trapped between the macrocyclic arms to give the NMR spectra of a <jats:italic>C<\/jats:italic><jats:sub>s<\/jats:sub>\u2010symmetric solution\u2010state structure. In contrast, in <jats:bold>5<\/jats:bold> the benzaldehyde arms can move between the gaps of the cage. This results in <jats:sup>1<\/jats:sup>H and <jats:sup>13<\/jats:sup>C NMR spectra which are consistent for a compound with <jats:italic>C<\/jats:italic><jats:sub>3<jats:italic>v<\/jats:italic><\/jats:sub> symmetry. <jats:italic>In<\/jats:italic>,<jats:italic>out<\/jats:italic>\u2010diimidophosphate <jats:bold>7<\/jats:bold> is obtained in moderate yield by reaction of <jats:italic>in<\/jats:italic>,<jats:italic>out<\/jats:italic>\u2010phosphite <jats:bold>6<\/jats:bold> with thiophosphoryl azide <jats:bold>2<\/jats:bold>. Its <jats:italic>in<\/jats:italic>\u2010benzaldehyde moieties are not fixed between the cage arms, but can freely move from one gap to the next as is indicated by NMR measurements.<\/jats:p>","DOI":"10.1002\/chem.200400204","type":"journal-article","created":{"date-parts":[[2004,6,30]],"date-time":"2004-06-30T10:18:36Z","timestamp":1088590716000},"page":"4011-4016","source":"Crossref","is-referenced-by-count":11,"title":["Staudinger Reaction at <i>in<\/i>\u2010Bridgehead Positions of Phosphorus Macrobicyclic Compounds"],"prefix":"10.1002","volume":"10","author":[{"given":"Ingmar","family":"Bauer","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Margit","family":"Gruner","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Sigrid","family":"Goutal","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Wolf D.","family":"Habicher","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2004,8,12]]},"reference":[{"key":"e_1_2_5_1_2","unstructured":"\u00a0"},{"key":"e_1_2_5_2_2","doi-asserted-by":"publisher","DOI":"10.1007\/978-3-322-92788-0"},{"key":"e_1_2_5_3_2","doi-asserted-by":"publisher","DOI":"10.1007\/978-3-322-94013-1"},{"volume-title":"Macrocyclic Chemistry: Aspects of Organic and Inorganic Supramolecular Chemistry","year":"1992","author":"Dietrich B.","key":"e_1_2_5_4_2"},{"volume-title":"Principles and Methods in Supramolecular Chemistry","year":"1999","author":"Schneider H.\u2010J.","key":"e_1_2_5_5_2"},{"volume-title":"Supramolecular Chemistry","year":"2000","author":"Steed J. 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