The reaction of trifluoroacetyl amides with Grignard reagent for the substitution of CF group with various alkyl or aryl groups is described. A variety of aryl, quinolin-8-yl, and (hetero)alkyl functional groups as well as F, Cl, and Br atoms are well tolerated. These moisture-stable and easily available trifluoroacetyl amides can be conveniently obtained and used as new versatile precursors for isocyanates. The control experiments show that the reaction proceeds via an isocyanate intermediate and/or alkoxide/amide dual anionic intermediate.
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http://dx.doi.org/10.1021/acs.joc.9b00583 | DOI Listing |
Org Lett
December 2023
Laboratory for Chemistry and Life Science, Institute of Innovative Research, Tokyo Institute of Technology, 4259 Nagatsuta-cho Midori-ku, Yokohama 226-8501, Japan.
Chemoselective α-acylation of tertiary amides proceeded with highly electrophilic acid anhydrides and weak bases under mild conditions. β-Ketoamides containing trifluoroacetyl or perfluoroacyl groups were selectively obtained even in the presence of other functional groups such as ketone, ester, etc. Density functional theory calculations suggest that 1-acyloxyenamine is the key intermediate for the chemoselective α-acylation.
View Article and Find Full Text PDFJ Org Chem
September 2022
Department of Chemistry and Industrial Chemistry, University of Pisa, via Moruzzi 13, 56124 Pisa, Italy.
A C2-symmetrical bis-thiourea chiral solvating agent (CSA), , for NMR spectroscopy has been obtained by reacting (1,2)-1,2-bis(2-hydroxyphenyl)ethylenediamine and 3,5-bis(trifluoromethyl)phenyl isothiocyanate. shows remarkable propensity to enantiodiscriminate -trifluoroacetyl (-TFA) and -acetyl (-Ac) derivatives of amino acids with free carboxyl functions, with the co-presence of 1,4-diazabicyclo[2.2.
View Article and Find Full Text PDFOrg Biomol Chem
May 2022
Key Laboratory of Molecule Synthesis and Function Discovery, and Fujian Provincial Key Laboratory of Electrochemical Energy Storage Materials, College of Chemistry, Fuzhou University, Fuzhou 350108, China.
A base promoted annulation of pyridinium ylides with trifluoroacetyl diazoester has been reported. Highly functionalized 4-trifluoromethyl pyridazines were synthesized in good yields without the use of any heavy metal catalysts. The developed methodology was compatible with a variety of important functional groups.
View Article and Find Full Text PDFJ Org Chem
March 2022
Department of Organic Synthesis & Process Chemistry, CSIR-Indian Institute of Chemical Technology (CSIR-IICT), Hyderabad 500007, India.
Herein, we report tailored 3-trifluoroacetyl-quinolin-2(1)-ones () as carbonyl and acid surrogates in Passerini- and Ugi-type reactions for the synthesis of α-trifluoromethyl-α-hydroxy carboxamides () and α-trifluoromethyl α-amino acids () in high yields, respectively. The reaction proceeds under mild reaction conditions via an exocyclic carboximidate intermediate (). The amide group in compound acts as an acid component as well as a reversible oxygen nucleophile to facilitate the reaction.
View Article and Find Full Text PDFMolecules
December 2020
Department of Chemistry and Biotechnology, School of Science, Tallinn University of Technology, Akadeemia tee 15, 12618 Tallinn, Estonia.
Oxidative fragmentation of tertiary cyclopropanols with phenyliodine(III) dicarboxylates in aprotic solvents (dichloromethane, chloroform, toluene) produces mixed anhydrides. The fragmentation reaction is especially facile with phenyliodine(III) reagents bearing electron-withdrawing carboxylate ligands (trifluoroacetyl, 2,4,6-trichlorobenzoyl, 3-nitrobenzoyl), and affords 95-98% yields of the corresponding mixed anhydride products. The latter can be straightforwardly applied for the acylation of various nitrogen, oxygen and sulfur-centered nucleophiles (primary and secondary amines, hydroxylamines, primary alcohols, phenols, thiols).
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