{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,5,6]],"date-time":"2026-05-06T14:59:46Z","timestamp":1778079586605,"version":"3.51.4"},"reference-count":65,"publisher":"Beilstein Institut","license":[{"start":{"date-parts":[[2017,11,23]],"date-time":"2017-11-23T00:00:00Z","timestamp":1511395200000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0"},{"start":{"date-parts":[[2017,11,23]],"date-time":"2017-11-23T00:00:00Z","timestamp":1511395200000},"content-version":"am","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0"},{"start":{"date-parts":[[2017,11,23]],"date-time":"2017-11-23T00:00:00Z","timestamp":1511395200000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Beilstein J. Org. Chem."],"accepted":{"date-parts":[[2017,10,25]]},"abstract":"<jats:p>The title molecules are sought in connection with various synthetic applications. The aliphatic fluorous alcohols R<jats:sub>f<\/jats:sub><jats:italic><jats:sub>n<\/jats:sub><\/jats:italic>CH<jats:sub>2<\/jats:sub>OH (R<jats:sub>f<\/jats:sub><jats:italic><jats:sub>n<\/jats:sub><\/jats:italic> = CF<jats:sub>3<\/jats:sub>(CF<jats:sub>2<\/jats:sub>)<jats:italic><jats:sub>n<\/jats:sub><\/jats:italic><jats:sub>\u20131<\/jats:sub>; <jats:italic>n<\/jats:italic> = 11, 13, 15) are converted to the triflates R<jats:sub>f<\/jats:sub><jats:italic><jats:sub>n<\/jats:sub><\/jats:italic>CH<jats:sub>2<\/jats:sub>OTf (Tf<jats:sub>2<\/jats:sub>O, pyridine; 22\u201361%) and then to R<jats:sub>f<\/jats:sub><jats:italic><jats:sub>n<\/jats:sub><\/jats:italic>CH<jats:sub>2<\/jats:sub>I (NaI, acetone; 58\u201369%). Subsequent reactions with NaOCl\/HCl give iodine(III) dichlorides R<jats:sub>f<\/jats:sub><jats:italic><jats:sub>n<\/jats:sub><\/jats:italic>CH<jats:sub>2<\/jats:sub>ICl<jats:sub>2<\/jats:sub> (<jats:italic>n<\/jats:italic> = 11, 13; 33\u201381%), which slowly evolve Cl<jats:sub>2<\/jats:sub>. The ethereal fluorous alcohols CF<jats:sub>3<\/jats:sub>CF<jats:sub>2<\/jats:sub>CF<jats:sub>2<\/jats:sub>O(CF(CF<jats:sub>3<\/jats:sub>)CF<jats:sub>2<\/jats:sub>O)<jats:italic><jats:sub>x<\/jats:sub><\/jats:italic>CF(CF<jats:sub>3<\/jats:sub>)CH<jats:sub>2<\/jats:sub>OH (<jats:italic>x<\/jats:italic> = 2\u20135) are similarly converted to triflates and then to iodides, but efforts to generate the corresponding dichlorides fail. Substrates lacking a methylene group, R<jats:sub>f<\/jats:sub><jats:italic><jats:sub>n<\/jats:sub><\/jats:italic>I, are also inert, but additions of TMSCl to bis(trifluoroacetates) R<jats:sub>f<\/jats:sub><jats:italic><jats:sub>n<\/jats:sub><\/jats:italic>I(OCOCF<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub> appear to generate R<jats:sub>f<\/jats:sub><jats:italic><jats:sub>n<\/jats:sub><\/jats:italic>ICl<jats:sub>2<\/jats:sub>, which rapidly evolve Cl<jats:sub>2<\/jats:sub>. The aromatic fluorous iodides 1,3-R<jats:sub>f6<\/jats:sub>C<jats:sub>6<\/jats:sub>H<jats:sub>4<\/jats:sub>I, 1,4-R<jats:sub>f6<\/jats:sub>C<jats:sub>6<\/jats:sub>H<jats:sub>4<\/jats:sub>I, and 1,3-R<jats:sub>f10<\/jats:sub>C<jats:sub>6<\/jats:sub>H<jats:sub>4<\/jats:sub>I are prepared from the corresponding diiodides, copper, and R<jats:sub>f<\/jats:sub><jats:italic><jats:sub>n<\/jats:sub><\/jats:italic>I (110\u2013130 \u00b0C, 50\u201360%), and afford quite stable R<jats:sub>f<\/jats:sub><jats:italic><jats:sub>n<\/jats:sub><\/jats:italic>C<jats:sub>6<\/jats:sub>H<jats:sub>4<\/jats:sub>ICl<jats:sub>2<\/jats:sub> species upon reaction with NaOCl\/HCl (80\u201389%). Iodinations of 1,3-(R<jats:sub>f6<\/jats:sub>)<jats:sub>2<\/jats:sub>C<jats:sub>6<\/jats:sub>H<jats:sub>4<\/jats:sub> and 1,3-(R<jats:sub>f8<\/jats:sub>CH<jats:sub>2<\/jats:sub>CH<jats:sub>2<\/jats:sub>)<jats:sub>2<\/jats:sub>C<jats:sub>6<\/jats:sub>H<jats:sub>4<\/jats:sub> (NIS or I<jats:sub>2<\/jats:sub>\/H<jats:sub>5<\/jats:sub>IO<jats:sub>6<\/jats:sub>) give 1,3,5-(R<jats:sub>f6<\/jats:sub>)<jats:sub>2<\/jats:sub>C<jats:sub>6<\/jats:sub>H<jats:sub>3<\/jats:sub>I and 1,2,4-(R<jats:sub>f8<\/jats:sub>CH<jats:sub>2<\/jats:sub>CH<jats:sub>2<\/jats:sub>)<jats:sub>2<\/jats:sub>C<jats:sub>6<\/jats:sub>H<jats:sub>3<\/jats:sub>I (77\u201393%). The former, the crystal structure of which is determined, reacts with Cl<jats:sub>2<\/jats:sub> to give a 75:25 ArICl<jats:sub>2<\/jats:sub>\/ArI mixture, but partial Cl<jats:sub>2<\/jats:sub> evolution occurs upon work-up. The latter gives the easily isolated dichloride 1,2,4-(R<jats:sub>f8<\/jats:sub>CH<jats:sub>2<\/jats:sub>CH<jats:sub>2<\/jats:sub>)<jats:sub>2<\/jats:sub>C<jats:sub>6<\/jats:sub>H<jats:sub>3<\/jats:sub>ICl<jats:sub>2<\/jats:sub> (89%). The relative thermodynamic ease of dichlorination of these and other iodine(I) compounds is probed by DFT calculations.<\/jats:p>","DOI":"10.3762\/bjoc.13.246","type":"journal-article","created":{"date-parts":[[2017,11,23]],"date-time":"2017-11-23T09:01:58Z","timestamp":1511427718000},"page":"2486-2501","source":"Crossref","is-referenced-by-count":6,"title":["Syntheses, structures, and stabilities of aliphatic and aromatic fluorous iodine(I) and iodine(III) compounds: the role of iodine Lewis basicity"],"prefix":"10.3762","volume":"13","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-6369-8923","authenticated-orcid":false,"given":"Tathagata","family":"Mukherjee","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Soumik","family":"Biswas","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7044-1712","authenticated-orcid":false,"given":"Andreas","family":"Ehnbom","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Subrata K","family":"Ghosh","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Ibrahim","family":"El-Zoghbi","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Nattamai","family":"Bhuvanesh","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5702-0091","authenticated-orcid":false,"given":"Hassan S","family":"Bazzi","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7012-4872","authenticated-orcid":false,"given":"John A","family":"Gladysz","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"2086","published-online":{"date-parts":[[2017,11,23]]},"reference":[{"key":"ref1","volume-title":"Handbook of Fluorous Chemistry","year":"2004"},{"key":"ref2","volume-title":"Fluorous, Chemistry. 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