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The initially formed \u03b1\u2010fluoro alkoxides undergo subsequent intramolecular ring closure when heated. We demonstrated the versatility of the method through the isolation of 16 mono\u2010 and polyfluoroepoxide products. These compounds provide unique entry points for further diversification via either fluoride migration coupled with ring opening, or defluorinative functionalization reactions, the latter of which can be used as a late\u2010stage method to install select bioactive moieties. The reaction sequences described herein provide a pathway to functionalize the commonly observed products formed from 1,2\u2010addition into carbonyl electrophiles<\/jats:p>","DOI":"10.1002\/chem.202203578","type":"journal-article","created":{"date-parts":[[2022,12,7]],"date-time":"2022-12-07T11:41:03Z","timestamp":1670413263000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":4,"title":["Preparation and Functionalization of Mono\u2010 and Polyfluoroepoxides via Fluoroalkylation of Carbonyl Electrophiles"],"prefix":"10.1002","volume":"29","author":[{"given":"Shuo","family":"Guo","sequence":"first","affiliation":[{"name":"Department of Chemistry University of Michigan Willard Henry Dow Laboratory  930 North University Ave. Ann Arbor MI 48109 USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Wei","family":"Sun","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Michigan Willard Henry Dow Laboratory  930 North University Ave. Ann Arbor MI 48109 USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Joseph W.","family":"Tucker","sequence":"additional","affiliation":[{"name":"Medicine Design Pfizer Inc.: Eastern Point Rd.  Groton CT. 06340 USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Kevin D.","family":"Hesp","sequence":"additional","affiliation":[{"name":"Medicine Design Pfizer Inc.: Eastern Point Rd.  Groton CT. 06340 USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1296-1445","authenticated-orcid":false,"given":"Nathaniel K.","family":"Szymczak","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Michigan Willard Henry Dow Laboratory  930 North University Ave. Ann Arbor MI 48109 USA"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2022,12,29]]},"reference":[{"key":"e_1_2_7_1_1","doi-asserted-by":"publisher","DOI":"10.1039\/B610213C"},{"key":"e_1_2_7_2_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jmedchem.5b00258"},{"key":"e_1_2_7_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jmedchem.7b01788"},{"key":"e_1_2_7_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsomega.0c00830"},{"key":"e_1_2_7_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.5b00392"},{"key":"e_1_2_7_6_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr4002879"},{"key":"e_1_2_7_7_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.cclet.2022.06.001"},{"key":"e_1_2_7_8_1","doi-asserted-by":"publisher","DOI":"10.1039\/B711844A"},{"key":"e_1_2_7_9_1","doi-asserted-by":"publisher","DOI":"10.1038\/s43586-021-00042-1"},{"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":"10.1039\/D1CS00360G"},{"key":"e_1_2_7_12_1","volume-title":"Emerging Fluorinated Motifs","author":"Han E. 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