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Herein, we would like to present deoxyfluorinating reagents such as DAST and PyFluor and their successful use as tools for selective modification of γ-amino-α-hydroxyphosphonates. Depending on the deoxyfluorinating reagent applied, an intramolecular cyclization leading to phosphonates containing the 1,3-oxazinan-2-one moiety or direct nucleophilic deoxyfluorination yielding the α-fluorinated derivatives of γ-aminophosphonates was observed. The obtained compounds may be used as precursors in the preparation of medicinally important compounds , dipeptide analogues or scaffolds containing the 1,3-oxazinan-2-one group.
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http://dx.doi.org/10.1039/d2ob00915c | DOI Listing |
Beilstein J Org Chem
April 2024
Institute of Chemistry and Biochemistry, Freie Universität Berlin, Fabeckstrasse 34-36, 14195 Berlin, Germany.
2-(Trifluoromethylthio)benzothiazolium triflate (BT-SCF) was used as deoxyfluorinating reagent for the synthesis of versatile acyl fluorides directly from the corresponding carboxylic acids. These acyl fluorides were reacted with amines in a one-pot protocol to form different amides, including dipeptides, under mild and operationally simple conditions in high yields. Mechanistic studies suggest that BT-SCF can generate acyl fluorides from carboxylic acids via two distinct pathways, which allows the deoxyfluorinating reagent to be employed in sub-stoichiometric amounts.
View Article and Find Full Text PDFOrg Biomol Chem
July 2022
Faculty of Chemistry, Adam Mickiewicz University in Poznań, Uniwersytetu Poznańskiego 8, 61-614 Poznań, Poland.
Herein, we would like to present deoxyfluorinating reagents such as DAST and PyFluor and their successful use as tools for selective modification of γ-amino-α-hydroxyphosphonates. Depending on the deoxyfluorinating reagent applied, an intramolecular cyclization leading to phosphonates containing the 1,3-oxazinan-2-one moiety or direct nucleophilic deoxyfluorination yielding the α-fluorinated derivatives of γ-aminophosphonates was observed. The obtained compounds may be used as precursors in the preparation of medicinally important compounds , dipeptide analogues or scaffolds containing the 1,3-oxazinan-2-one group.
View Article and Find Full Text PDFChem Commun (Camb)
August 2021
Key Laboratory of Organofluorine Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Ling-Ling Road, Shanghai 200032, China.
Aryl fluorosulfonates are developed as a deoxyfluorinating reagent in the transformation of primary and secondary alcohols into the corresponding alkyl fluorides. These reagents feature easy availability, low-cost, high stability and high efficiency. Diverse functionalities including aldehyde, ketone, ester, halogen, nitro, alkene, and alkyne are well tolerated under mild reaction conditions.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2019
Institute of Chemistry and Biochemistry (ICBMS-UMR CNRS 5246), Univ. Lyon, Université Lyon 1, CNRS, CPE-Lyon, INSA, 43 Bd du 11 Novembre 1918, 69622, Villeurbanne, France.
Herein, a new concept for the direct synthesis of carbamoyl fluoride derivatives is disclosed. The developed method makes use of CO as an inexpensive and abundant C source; a variety of amines were successfully converted in the presence of a deoxyfluorinating reagent. The corresponding products were often obtained in excellent yields under mild reaction conditions (1 atm and room temperature).
View Article and Find Full Text PDFChem Commun (Camb)
September 2018
Department of Chemistry, Humboldt-Universität zu Berlin, Brook-Taylor-Str. 2, 12489 Berlin, Germany.
The activation of the greenhouse gas SF using electron-rich N-heterocyclic carbenes gave 2,2-difluoroimidazolines or 2,2-difluoroimidazolidines as well as 2-thio derivatives of the carbene precursors. The N-heterocyclic carbenes can also convert SF to give similar products. The difluoroimidazolidine derivatives were applied in deoxyfluorination reactions.
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