Fluorinated NH-iminophosphonates and iminocarboxylates: novel synthons for the preparation of biorelevant α-aminophosphonates and carboxylates

Synthesis of 2-aryl-2-trifluoromethyl-1,3-thiazolidin-4-ones and 2-aryl-2-trifluoromethyltetrahydro-4H-1,3-thiazin-4-ones and their oxidation with hydrogen peroxide

“…The solvent was evaporated, and the residue was recrystallized from benzene-hexane. The physicochemical constants of compounds IIa, IIc, and IId coincided with those given in [12]. Yield 83 (IIa), 71 (IIc), 77% (IId).…”

“…The most convenient procedures for the synthesis of the majority of known trifluoromethyl-substituted 1,3thiazolidin-4-ones and tetrahydro-1,3-thiazin-4-ones were based on reactions of highly electrophilic hexa-(penta)fluoroacetone imines [9,10] or trifluoromethylpyruvic acid esters [11,12] with 2-sulfanylacetic and 3-sulfanylpropanoic acids, respectively. We previously developed a synthetic approach to 2-aryl-2-trifluoromethyl-1,3-thiazolidin-4-ones via condensation of 2sulfanylacetic acid or its alkyl esters with 1-aryl-1chloro-2,2,2-trifluoroethyl isocyanates [13,14].…”

α-(Imino)pyridyldifluoroethyl Phosphonates: Novel Promising Building Blocks in Synthesis of Biorelevant Aminophosphonic Acids Derivatives

“…At the same time, under basic conditions benzonitrile reacts with dialkyl or diphenyl phosphites to form phosphorylamino phosphonates II [16]. Recently we have shown that highly electrophilic polyfluoroalkylated nitriles in the reactions with dialkyl or diphenyl phosphite afford first representatives of NH-iminophosphonates III [17,18]. At the same time, mixed perfluoro(chloro) acetonitriles react with (RO) 2 POH (R = Et, Ph) by two competitive routes: addition to the C≡N bond affording the respective N-unprotected iminophosphonates III, or reductive dehalogenation leading to chloro(fluoro) acetonitriles IV and the respective halogenophosphates V [19].…”

Chemistry of 1,3-thiazin-4-ones and their derivatives, 1995 - mid-2018

“…Highly polarized imines 151 have been used to form the 2,2-disubstituted-2,3,5,6-tetrahydro-1,3-thiazin-4ones 197 at room temperature in benzene 96 or ether (Scheme 59). 97 Scheme 43 shows a similar reaction.…”