6442-87-1Relevant articles and documents
Gas-phase dynamic NMR study of the internal rotation in N-trifluoroacetylpyrrolidine
Suarez, Cristina,Nicholas, Elisabeth J.,Bowman, Molly R.
, p. 3024 - 3029 (2003)
The barrier to the internal rotation around the C-N bond in N-trifluoroacetylpyrrolidine (TFAPYR) was characterized using dynamic NMR spectroscopy. Kinetic parameters, ΔG?298 = 71.4(1.2) kJ mol-1, ΔH? = 67.9(1.4) kJ mol-1, and ΔS? = -11.8(4.0) J mol-1), were found to be lower in the gas phase than in solution. The pyrrolidine ring substituent in TFAPYR reduces the bulkiness around the C-N amide bond, stabilizing the ground state and increasing the value of the internal rotation barrier, ΔG?298, compared to N,N-dimethyland N,N-diethyltrifluoroacetamide. The magnitude of ΔG?298 in TFAPYR is also comparable to that found in primary amide bonds in peptides, emphasizing the importance of having a relatively small energy difference between cis and trans conformations in proline's role as a switch in protein signaling.
Oxidative Amide Coupling from Functionally Diverse Alcohols and Amines Using Aerobic Copper/Nitroxyl Catalysis
Piszel, Paige E.,Vasilopoulos, Aristidis,Stahl, Shannon S.
supporting information, p. 12211 - 12215 (2019/07/31)
The aerobic Cu/ABNO catalyzed oxidative coupling of alcohols and amines is highlighted in the synthesis of amide bonds in diverse drug-like molecules (ABNO=9-azabicyclo[3.3.1]nonane N-oxyl). The robust method leverages the privileged reactivity of alcohol
Synthesis and reactivity of trifluorodithioacetates derived from trifluorothioacetamides
Laduron, Frederic,Nyns, Claire,Janousek, Zdenek,Viehe, Heinz G.
, p. 697 - 707 (2007/10/03)
A general synthesis of trifluorodithioacetates is described by thiolysis of trifluorothioamidium salts, derived from trifluorothioacetamides. The reactivity of these CF3 bearing C2 building blocks has been investigated towards nucleophiles and in cycloaddition reactions. Trifluorodithioacetates react with dienes to give thiopyrans and with diazo compounds to give trifluoromethyl vinyl sulphides via thiirane intermediates. With amines, trifluorodithioacetates give rise to trifluorothioacetamides while thiols add by thiophilic attack leading to new trifluoroethane dithioacetal disulphide. Two equivalents of phosphite furnish one equivalent of thiophosphate and one of phosphorylated trifluoroethane.