{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,28]],"date-time":"2026-09-28T04:55:27Z","timestamp":1790571327144,"version":"4.1.0"},"reference-count":45,"publisher":"Wiley","issue":"6","license":[{"start":{"date-parts":[[2025,1,9]],"date-time":"2025-01-09T00:00:00Z","timestamp":1736380800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"},{"start":{"date-parts":[[2025,1,9]],"date-time":"2025-01-09T00:00:00Z","timestamp":1736380800000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"funder":[{"DOI":"10.13039\/100010661","name":"Horizon 2020 Framework Programme","doi-asserted-by":"publisher","award":["769599"],"award-info":[{"award-number":["769599"]}],"id":[{"id":"10.13039\/100010661","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100000266","name":"Engineering and Physical Sciences Research Council","doi-asserted-by":"publisher","award":["EP\/X021858"],"award-info":[{"award-number":["EP\/X021858"]}],"id":[{"id":"10.13039\/501100000266","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100000266","name":"Engineering and Physical Sciences Research Council","doi-asserted-by":"publisher","award":["EP\/W007517"],"award-info":[{"award-number":["EP\/W007517"]}],"id":[{"id":"10.13039\/501100000266","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Angew Chem Int Ed"],"published-print":{"date-parts":[[2025,2,3]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>\n                    Organofluorine compounds are vital across multiple sectors, hence highly selective methods to install fluorine are of considerable importance. The deoxyfluorination of alcohols is a key approach to prepare organofluorine compounds, however, a highly secondary (2\u00b0)\u2010selective deoxyfluorination of alcohols has not been realized to date. Herein, we report that borane\u2010mediated deoxyfluorination results in high 2\u00b0\u2010selectivity in inter\u2010 and intra\u2010molecular competition reactions versus primary (1\u00b0), tertiary (3\u00b0) and even benzylic (Bn) alcohols. This is an operationally simple method using only commercial reagents (e.g., Et\n                    <jats:sub>3<\/jats:sub>\n                    N\u2009\u22c5\u20093HF) that starts from the alcohol which is converted to the\n                    <jats:italic>O<\/jats:italic>\n                    \u2010alkyl\u2010\n                    <jats:italic>N<\/jats:italic>\n                    \u2010H\u2010isourea in situ. The origin of the high 2\u00b0\u2010selectivity was elucidated to be due to the relative barriers to carbodiimide elimination from the\n                    <jats:italic>O<\/jats:italic>\n                    \u2010alkyl\u2010\n                    <jats:italic>N<\/jats:italic>\n                    \u2010(BR\n                    <jats:sub>2<\/jats:sub>\n                    )\u2010isoureas. As the selectivity controlling step does not involve fluoride, this borane\u2010mediated approach can be applied to other nucleophiles, as demonstrated by 2\u00b0\u2010selective deoxychlorination using HCl occurring in preference to substitution of 1\u00b0 and Bn analogues. This borane\u2010mediated nucleophilic substitution therefore provides a new approach to circumvent the selectivity limitations inherent in classical S\n                    <jats:sub>N<\/jats:sub>\n                    2 and S\n                    <jats:sub>N<\/jats:sub>\n                    1 type reactions.\n                  <\/jats:p>","DOI":"10.1002\/anie.202418495","type":"journal-article","created":{"date-parts":[[2024,12,23]],"date-time":"2024-12-23T11:03:26Z","timestamp":1734951806000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":6,"title":["Borane\u2010Mediated Highly Secondary Selective Deoxyfluorination of Alcohols"],"prefix":"10.1002","volume":"64","author":[{"given":"Dominic R.","family":"Willcox","sequence":"first","affiliation":[{"name":"EaStCHEM School of Chemistry University of Edinburgh  Edinburgh EH9 3FJ UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Nojus","family":"Cironis","sequence":"additional","affiliation":[{"name":"EaStCHEM School of Chemistry University of Edinburgh  Edinburgh EH9 3FJ UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Laura","family":"Winfrey","sequence":"additional","affiliation":[{"name":"EaStCHEM School of Chemistry University of Edinburgh  Edinburgh EH9 3FJ UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sven","family":"Kirschner","sequence":"additional","affiliation":[{"name":"EaStCHEM School of Chemistry University of Edinburgh  Edinburgh EH9 3FJ UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Gary S.","family":"Nichol","sequence":"additional","affiliation":[{"name":"EaStCHEM School of Chemistry University of Edinburgh  Edinburgh EH9 3FJ UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Stephen P.","family":"Thomas","sequence":"additional","affiliation":[{"name":"EaStCHEM School of Chemistry University of Edinburgh  Edinburgh EH9 3FJ UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9975-8302","authenticated-orcid":false,"given":"Michael J.","family":"Ingleson","sequence":"additional","affiliation":[{"name":"EaStCHEM School of Chemistry University of Edinburgh  Edinburgh EH9 3FJ UK"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2025,1,9]]},"reference":[{"key":"e_1_2_7_1_1","doi-asserted-by":"publisher","DOI":"10.1039\/B711844A"},{"key":"e_1_2_7_2_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.3c01824"},{"key":"e_1_2_7_3_1","doi-asserted-by":"publisher","DOI":"10.1038\/s43586-021-00042-1"},{"key":"e_1_2_7_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jmedchem.9b01877"},{"key":"e_1_2_7_5_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201206566"},{"key":"e_1_2_7_6_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsomega.0c00830"},{"key":"e_1_2_7_7_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.5b00392"},{"key":"e_1_2_7_8_1","doi-asserted-by":"publisher","DOI":"10.1039\/D1QO00952D"},{"key":"e_1_2_7_9_1","doi-asserted-by":"publisher","DOI":"10.1055\/s-0036-1590881"},{"key":"e_1_2_7_10_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr500706a"},{"key":"e_1_2_7_11_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr5002386"},{"key":"e_1_2_7_12_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.5b06307"},{"key":"e_1_2_7_13_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo00893a007"},{"key":"e_1_2_7_14_1","doi-asserted-by":"publisher","DOI":"10.1021\/ol902039q"},{"key":"e_1_2_7_15_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jfluchem.2013.05.019"},{"key":"e_1_2_7_16_1","doi-asserted-by":"publisher","DOI":"10.1038\/ncomms13320"},{"key":"e_1_2_7_17_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja3125405"},{"key":"e_1_2_7_18_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b01523"},{"key":"e_1_2_7_19_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.joc.3c01558"},{"key":"e_1_2_7_20_1","doi-asserted-by":"publisher","DOI":"10.1039\/b211424k"},{"key":"e_1_2_7_21_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202001015"},{"key":"e_1_2_7_22_1","doi-asserted-by":"publisher","DOI":"10.1039\/j19660001584"},{"key":"e_1_2_7_23_1","doi-asserted-by":"publisher","DOI":"10.1039\/D2SC00303A"},{"key":"e_1_2_7_24_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.3c08373"},{"key":"e_1_2_7_25_1","doi-asserted-by":"publisher","DOI":"10.1039\/C6CC05168E"},{"key":"e_1_2_7_26_1","doi-asserted-by":"publisher","DOI":"10.1021\/ol200129q"},{"key":"e_1_2_7_27_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.tetlet.2014.12.044"},{"key":"e_1_2_7_28_1","doi-asserted-by":"publisher","DOI":"10.1002\/cber.19901231004"},{"key":"e_1_2_7_29_1","unstructured":"Note HF can also be generated from reaction of the N\u2212H unit in the isourea with F-BBN."},{"key":"e_1_2_7_30_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja0124109"},{"key":"e_1_2_7_31_1","volume-title":"in Encyclopedia of Reagents for Organic Synthesis","author":"Hara S.","year":"2005"},{"key":"e_1_2_7_32_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.2c00086"},{"key":"e_1_2_7_33_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.oprd.1c00465"},{"key":"e_1_2_7_34_1","unstructured":"Note the use of less DIC relative to alcohol (2\u2005equiv. DIC relative to 3\u2005equiv. of alcohol in total) again was used to avoid any activation of the 3\u00b0 alcohol."},{"key":"e_1_2_7_35_1","doi-asserted-by":"publisher","DOI":"10.1039\/p29960000973"},{"key":"e_1_2_7_36_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(01)82158-4"},{"key":"e_1_2_7_37_1","doi-asserted-by":"publisher","DOI":"10.1039\/b203389p"},{"key":"e_1_2_7_38_1","doi-asserted-by":"publisher","DOI":"10.1002\/cber.19821150603"},{"key":"e_1_2_7_39_1","doi-asserted-by":"publisher","DOI":"10.1021\/om070090h"},{"key":"e_1_2_7_40_1","doi-asserted-by":"publisher","DOI":"10.1002\/cphc.202000244"},{"key":"e_1_2_7_41_1","unstructured":"The fluoride affinity of F-BBN is 152\u2005kJ\/mol while the fluoride affinity of EtO-BBN at 92\u2005kJ\/mol is significantly lower (see Figure\u2005S99 and associated text for more details). This fluoride affinity appears to be too low to be an effective phase transfer agent for CsF into CPME\/benzene but it is sufficient to be an effective phase transfer agent for [NMe4]F with these solvents at higher temperatures. This is consistent with the lower lattice enthalpy of [NMe4]F versus CsF."},{"key":"e_1_2_7_42_1","doi-asserted-by":"publisher","DOI":"10.1039\/C9CP06869D"},{"key":"e_1_2_7_43_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jctc.8b01176"},{"key":"e_1_2_7_44_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.tet.2020.131114"},{"key":"e_1_2_7_45_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.3c01462"}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.202418495","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/anie.202418495","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.202418495","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,9,28]],"date-time":"2026-09-28T04:06:05Z","timestamp":1790568365000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.202418495"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2025,1,9]]},"references-count":45,"journal-issue":{"issue":"6","published-print":{"date-parts":[[2025,2,3]]}},"alternative-id":["10.1002\/anie.202418495"],"URL":"https:\/\/doi.org\/10.1002\/anie.202418495","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2025,1,9]]},"assertion":[{"value":"2024-09-25","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2025-01-09","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202418495"}}