- Photoredox Generation of Carbon-Centered Radicals Enables the Construction of 1,1-Difluoroalkene Carbonyl Mimics
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Described is a facile, scalable route to access functional-group-rich gem-difluoroalkenes. Using visible-light-activated catalysts in conjunction with an arsenal of carbon-radical precursors, an array of trifluoromethyl-substituted alkenes undergoes radical defluorinative alkylation. Nonstabilized primary, secondary, and tertiary radicals can be used to install functional groups in a convergent manner, which would otherwise be challenging by two-electron pathways. The process readily extends to other perfluoroalkyl-substituted alkenes. In addition, we report the development of an organotrifluoroborate reagent to expedite the synthesis of the requisite trifluoromethyl-substituted alkene starting materials.
- Lang, Simon B.,Wiles, Rebecca J.,Kelly, Christopher B.,Molander, Gary A.
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supporting information
p. 15073 - 15077
(2017/11/20)
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- Well-defined CuC2F5 complexes and pentafluoroethylation of acid chlorides
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Four new well-defined CuI complexes bearing a C2F5 ligand have been prepared and fully characterized: [(Ph3P)2CuC2F5] (2), [(bpy)CuC2F5] (3), [(Ph3P)Cu(phen)C2F5] (4), and [(IPr)CuC2F5] (5). X-ray structures of all four have been determined, showing that the C2F5-ligated Cu atom can be di- (5), tri- (2 and 3), and tetracoordinate (4). The mixed phen-PPh3 complex 4 is a highly efficient fluoroalkylating agent for a broad variety of acid chlorides. This high-yielding transformation represents the first general method for the synthesis of RCOC2F5 from the corresponding RCOCl. Four well-defined CuC2F5 complexes have been prepared and fully characterized, with [(phen)Cu(PPh3)C2F5] (phen=1,10-phenanthroline) proving to be a remarkably efficient fluoroalkylating agent for a broad variety of acid chlorides (see scheme). The procedure represents the first general method for the one-step conversion of RCOCl into valuable pentafluoroethyl ketones.
- Panferova, Liubov I.,Miloserdov, Fedor M.,Lishchynskyi, Anton,Martínez Belmonte, Marta,Benet-Buchholz, Jordi,Grushin, Vladimir V.
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supporting information
p. 5218 - 5222
(2015/04/27)
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- Synthesis of Perfluoroalkyl-Substituted Vinylcyclopropanes by Way of Enhanced Neighboring Group Participation
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A simple, high yielding, two-step, one-pot protocol for the preparation of trifluoromethyl-substituted vinylcyclopropanes from α-CF3 homoallyl alcohols is disclosed. Destabilization of the cationic intermediate by the electron-withdrawing CF3 group greatly enhances neighboring group participation of the alkene, allowing ring closure to predominate. The reaction can be extended to the difluoromethyl and pentafluoroethyl group, enabling the preparation of a diverse array of fluoroalkyl-substituted vinylcyclopropanes. A diverse array of fluoroalkyl-substituted vinylcyclopropanes are prepared in a simple, high-yielding, two-step, one-pot protocol by means of cationic ring-closure.
- Kelly, Christopher B.,Mercadante, Michael A.,Carnaghan, Emma R.,Doherty, Matthew J.,Fager, Diana C.,Hauck, John J.,Macinnis, Allyson E.,Tilley, Leon J.,Leadbeater, Nicholas E.
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supporting information
p. 4071 - 4076
(2015/06/30)
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- Pentafluoroethylating compositions
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The present invention relates to pentafluoroethylating compositions, processes for obtaining them, and their use in pentafluoroethylation reactions.
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Paragraph 0213
(2015/02/25)
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- PENTAFLUOROETHYLATING COMPOSITIONS
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The present invention relates to pentafluoroethylating compositions, processes for obtaining them, and their use in pentafluoroethylation reactions.
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Page/Page column 43
(2015/02/25)
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- FLUORIDE ION CATALYZED ISOMERIZATION OF 2-ARYL-F-BUTENES
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A kinetic study of the fluoride ion catalyzed isomerization of a series of 2-aryl-F-1-butenes shows the reactions to be pseudo first order in olefin at constant fluoride ion concentration.The resultant Hammett plot is non-linear with a concave downward br
- Burton, Donald J.,Headley, James A.
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p. 323 - 356
(2007/10/02)
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