{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,2,28]],"date-time":"2026-02-28T04:29:42Z","timestamp":1772252982745,"version":"3.50.1"},"reference-count":26,"publisher":"MDPI AG","issue":"14","license":[{"start":{"date-parts":[[2021,7,19]],"date-time":"2021-07-19T00:00:00Z","timestamp":1626652800000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>We have previously clarified that the strongly electron-withdrawing CF3 group nicely affected the base-mediated proton shift of CF3-containing propargylic or allylic alcohols to afford the corresponding \u03b1,\u03b2-unsaturated or saturated ketones, respectively, which was applied this time to the Claisen rearrangement after O-allylation of the allylic alcohols with a CF3 group, followed by isomerization to the corresponding allyl vinyl ethers via the proton shift, enabling the desired rearrangement in a tandem fashion, or in a stepwise manner, the latter of which was proved to have attained an excellent diastereoselectivity with the aid of a palladium catalyst.<\/jats:p>","DOI":"10.3390\/molecules26144365","type":"journal-article","created":{"date-parts":[[2021,7,19]],"date-time":"2021-07-19T21:39:15Z","timestamp":1626730755000},"page":"4365","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Base-Mediated Claisen Rearrangement of CF3-Containing Bisallyl Ethers"],"prefix":"10.3390","volume":"26","author":[{"given":"Yoko","family":"Hamada","sequence":"first","affiliation":[{"name":"Division of Applied Chemistry, Institute of Engineering, Tokyo University of Agriculture and Technology, 2-24-16 Nakamachi, Koganei 184-8588, Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Rio","family":"Matsunaga","sequence":"additional","affiliation":[{"name":"Division of Applied Chemistry, Institute of Engineering, Tokyo University of Agriculture and Technology, 2-24-16 Nakamachi, Koganei 184-8588, Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Tomoko","family":"Kawasaki-Takasuka","sequence":"additional","affiliation":[{"name":"Division of Applied Chemistry, Institute of Engineering, Tokyo University of Agriculture and Technology, 2-24-16 Nakamachi, Koganei 184-8588, Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Takashi","family":"Yamazaki","sequence":"additional","affiliation":[{"name":"Division of Applied Chemistry, Institute of Engineering, Tokyo University of Agriculture and Technology, 2-24-16 Nakamachi, Koganei 184-8588, Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2021,7,19]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"7981","DOI":"10.1002\/chem.202000178","article-title":"Polar Organofluorine Substituents: Multivicinal Fluorines on Alkyl Chains and Alicyclic Rings","volume":"26","year":"2020","journal-title":"Chem. Eur. J."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"109630","DOI":"10.1016\/j.jfluchem.2020.109630","article-title":"Synthesis of Complex Unnatural Fluorine-containing Amino Acids","volume":"239","author":"Brittain","year":"2020","journal-title":"J. Fluor. Chem."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"5574","DOI":"10.1002\/ejoc.201900981","article-title":"Synthesis of Fluorine-Containing Molecular Entities Through Fluoride Ring Opening of Oxiranes and Aziridines","volume":"2019","author":"Remete","year":"2019","journal-title":"Eur. J. Org. Chem."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"5822","DOI":"10.1021\/acs.jmedchem.7b01788","article-title":"Fluorine and Fluorinated Motifs in the Design and Application of Bioisosteres for Drug Design","volume":"61","author":"Meanwell","year":"2018","journal-title":"J. Med. Chem."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"7168","DOI":"10.1039\/C7CC02341C","article-title":"Exploiting the Unusual Effects of Fluorine in Methodology","volume":"53","author":"Orsi","year":"2017","journal-title":"Chem. Commun."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"5945","DOI":"10.1016\/j.tet.2009.05.087","article-title":"Facile Conversion of 4,4,4-Trifluorobut-2-yn-1-ols to 4,4,4-Trifluorobut-2-en-1-ones","volume":"65","author":"Yamazaki","year":"2009","journal-title":"Tetrahedron"},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"1507","DOI":"10.3762\/bjoc.13.149","article-title":"Base-promoted Isomerization of CF3-containing Allylic Alcohols to the Corresponding Saturated Ketones under Metal-free Conditions","volume":"13","author":"Hamada","year":"2017","journal-title":"Beilstein J. Org. Chem."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"13408","DOI":"10.1021\/jacs.6b08350","article-title":"Base-Catalyzed Stereospecific Isomerization of Electron-Deficient Allylic Alcohols and Ethers through Ion-Pairing","volume":"138","author":"Ahlquist","year":"2016","journal-title":"J. Am. Chem. Soc."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"8140","DOI":"10.1021\/jo00130a012","article-title":"Highly Diastereoselective Sequential Enolate-Michael Addition-Ireland Claisen Rearrangement","volume":"60","author":"Yamazaki","year":"1995","journal-title":"J. Org. Chem."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"5657","DOI":"10.1021\/acs.orglett.8b02369","article-title":"Palladium-Catalyzed Enantioselective Csp3\u2013Csp3 Cross-Coupling for the Synthesis of (Poly)fluorinated Chiral Building Blocks","volume":"20","author":"Lu","year":"2018","journal-title":"Org. Lett."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"10109","DOI":"10.1021\/jacs.8b05560","article-title":"Catalytic Enantioselective Synthesis of Acyclic Quaternary Centers: Palladium-Catalyzed Decarboxylative Allylic Alkylation of Fully Substituted Acyclic Enol Carbonates","volume":"140","author":"Alexy","year":"2018","journal-title":"J. Am. Chem. Soc."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"2383","DOI":"10.1055\/s-0033-1339755","article-title":"Stereoselective Synthesis of Fluoroalkylated Butanolides","volume":"24","author":"Czekelius","year":"2013","journal-title":"Synlett"},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"43","DOI":"10.1016\/S0968-0896(97)10006-2","article-title":"Structure-activity Studies of Fluoroalkyl-substituted \u03b3-Butyrolactone and \u03b3-Thiobutyrolactone Modulators of GABAA Receptor Function","volume":"6","author":"Canney","year":"1998","journal-title":"Bioorg. Med. Chem."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"870","DOI":"10.1016\/j.tetlet.2008.11.112","article-title":"A Practical Preparation of Aryl \u03b2-Ketophosphonates","volume":"50","author":"Milburn","year":"2009","journal-title":"Tetrahedron Lett."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"8059","DOI":"10.1016\/j.tet.2015.08.048","article-title":"Convenient Stereoselective Synthesis of \u03b2-Perfluoroalkyl \u03b1,\u03b2-Unsaturated Esters via Horner\u2013Wadsworth\u2013Emmons Reactions","volume":"71","author":"Yamazaki","year":"2015","journal-title":"Tetrahedron"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1002\/9780470147221.ch1","article-title":"Stereoselective Aldol Condensations","volume":"13","author":"Allinger","year":"1982","journal-title":"Topic in Stereochemistry"},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"1121","DOI":"10.1055\/s-0032-1316869","article-title":"Claisen Rearrangement of Aliphatic Allyl Vinyl Ethers from 1912 to 2012: 100 Years of Electrophilic Catalysis","volume":"45","author":"Hiersemann","year":"2013","journal-title":"Synthesis"},{"key":"ref_18","first-page":"18","article-title":"Fluorinated Alcohols: A New Medium for Selective and Clean Reaction","volume":"2004","author":"Crousse","year":"2003","journal-title":"Synlett"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"1423","DOI":"10.1021\/cr00090a001","article-title":"The Thermal, Aliphatic Claisen Rearrangement","volume":"88","author":"Ziegler","year":"1988","journal-title":"Chem. Rev."},{"key":"ref_20","doi-asserted-by":"crossref","unstructured":"Hiersemann, M., and Abraham, L. (2002). Catalysis of the Claisen Rearrangement of Aliphatic Allyl Vinyl Ethers. Eur. J. Org. Chem., 1461\u20131471.","DOI":"10.1002\/1099-0690(200205)2002:9<1461::AID-EJOC1461>3.0.CO;2-1"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"6267","DOI":"10.1016\/S0040-4039(00)85449-0","article-title":"Palladium(II)-catalyzed Claisen Rearrangement of Allyl Vinyl Ethers","volume":"27","author":"Bickelhaupt","year":"1986","journal-title":"Tetrahedron Lett."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"2175","DOI":"10.1246\/cl.1991.2175","article-title":"Stereoselective Michael Addition Reactions of Acylated Oxazolidinones to Ethyl 3-Trifluoromethylacrylate","volume":"20","author":"Yamazaki","year":"1991","journal-title":"Chem. Lett."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"2171","DOI":"10.1246\/cl.1991.2171","article-title":"Highly Diastereoselective Michael Addition Reactions of Lithium Enolates to Ethyl 3-Trifluoromethylacrylate","volume":"20","author":"Yamazaki","year":"1991","journal-title":"Chem. Lett."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"2915","DOI":"10.1021\/ol016401g","article-title":"Effect of Allylic CH3-nFnGroups (n= 1\u22123) on \u03c0-Facial Diastereoselection","volume":"3","author":"Yamazaki","year":"2001","journal-title":"Org. Lett."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"1265","DOI":"10.1021\/cr980381n","article-title":"Inductive and Resonance Effects of Substituents on \u03c0-Face Selection","volume":"99","author":"Cieplak","year":"1999","journal-title":"Chem. Rev."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"3553","DOI":"10.1016\/0040-4020(78)88431-2","article-title":"Steric Effects\u2014I. A Critical Examination of the Taft Steric Parameters\u2013Es. Definition of a Revised, Broader and Homogeneous Scale. Extension to Highly Congested Alkyl Groups","volume":"34","author":"MacPhee","year":"1978","journal-title":"Tetrahedron"}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/26\/14\/4365\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T06:31:58Z","timestamp":1760164318000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/26\/14\/4365"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2021,7,19]]},"references-count":26,"journal-issue":{"issue":"14","published-online":{"date-parts":[[2021,7]]}},"alternative-id":["molecules26144365"],"URL":"https:\/\/doi.org\/10.3390\/molecules26144365","relation":{"has-preprint":[{"id-type":"doi","id":"10.20944\/preprints202106.0572.v1","asserted-by":"object"}]},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2021,7,19]]}}}