Synthesis of new 3-(2,2,2-trifluoroethyl)-5-hydroxy-5-(phenylsulfanyl- or phenylsulfonyl-methyl)-1,5-dihydropyrrol-2-ones starting from α,β-unsaturated γ-lactones and primary amines

The paper presents an efficient and straightforward transformation of α,β-unsaturated γ-lactones into 2,2,2-trifluoroethyl substituted γ-lactams, starting from a variety of primary amines. The structures of all new compounds were ascribed using 1D NMR (¹⁹F, ¹H, ¹³C), IR, MS. Selected ¹⁹F, ¹³C NMR and IR data of γ-lactams were compared to those of one which was characterized by X-ray diffraction analysis. The possible mechanism for the formation of γ-lactams is also presented.     

Reaction of 1H,1H,ωH-Perfluoroalkyl Sulfones with α-Phenylglycine Methyl Ester

Russian Journal of Organic Chemistry -     

Diels–Alder reactions of perfluoroketene dithioacetals with electron-rich 1,3-dienes: a new access to polysubstituted aromatic sulfides

The present paper describes the Diels–Alder reactions of perfluoroketene dithioacetals with electron-rich 1,3-dienes (2,3-dimethylbuta-1,3-diene, isoprene, penta-1,3-diene) followed by spontaneous HF and thiol elimination, leading to polysubstituted aromatic sulfides in moderate to good yields. Reactions seem to be dependent on the substitution patterns of perfluoroketene dithioacetals; the best results were obtained from trifluoromethyl or pentafluoroethyl and ethylsulfanyl derivatives. Theoretical calculations performed at the DFT level are in good agreement with the experimental results and show that the overall process is controlled by the cycloaddition step.     

Nucleophilic Fluorination of α‐Aroylphosphinates with Morpholinosulfur Trifluoride

Nucleophilic fluorination of aroyl‐phenyl‐phosphinates is highly dependent on the nature of the alkoxy substituents attached to the phosphoryl group. A reaction of aroyl‐phenyl‐phosphinates with morpholinosulfur trifluoride was shown to be a convenient synthetic method for high‐yield synthesis of α,α‐difluorobenzyl‐phenyl‐phosphinates using steric protection of the phosphoryl group by a bulky isopropoxy substituent. The methyl esters of aroylphosphinic acids in the same reaction conditions yield (fluoro‐diaryl‐methyl)‐pentafluorophosphates as the main reaction products.     

Syntheses of fluorine‐containing enamines,ketenedithioacetals, and acetylene sulfoxides from 1‐alkythio‐3,3‐difluoropropynes‐1

Convenient methods of synthesis of fluorocontaining N,N‐dimethylenamines by the reactions of 1,1‐dihydrotetrafluoropropyl sulfides with KOH in dimethylformamide and of fluoro‐containing 1,4‐dienes by the cycloaddition reactions of 1‐(alkylsulfinyl)‐difluoropropynes with dimethylbutadiene or cyclopentadiene are described. © 2000 John Wiley & Sons, Inc. Heteroatom Chem 11:383–386, 2000     

2‐Benzothiazolyl‐N‐(arenesulfonyl)‐sulfinimidoyl fluorides

2‐Benzothiazolyl‐N‐(arenesulfonyl)‐sulfinimidoyl fluorides were synthesized by the treatment of benzothiazolyl‐2‐sulfur trifluoride with sulfonamides. The reaction of 2‐benzothiazolyl‐N‐ (p‐toluenesulfonyl)‐sulfinimidoyl fluoride with tert‐ butylamine and morpholine gave 2‐benzothiazolyl‐ N‐(arenesulfonyl)‐sulfinimidoyl amides. The reaction of 2‐benzothiazolyl‐N‐(p‐toluenesulfonyl)‐sulfinimi‐ doyl fluoride or 2‐benzothiazolyl‐¹⁵N‐(p‐tosyl)sul‐ finimidoyl fluoride with S‐trimethylsilylbenzenethiol gave di(benzothiazolyl‐2) disulfide, fluorotrimethylsi‐ lane and N,N′‐bis(p‐toluenesulfonyl)‐N,N′‐bis(phenyl‐ thio)‐hydrazine or ¹⁵N,¹⁵N′‐bis(p‐toluenesulfonyl)‐¹⁵N, ¹⁵N′‐bis(phenylthio)‐hydrazine, respectively. © 2005 Wiley Periodicals, Inc. Heteroatom Chem 16:352–356, 2005; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20102     

N-alkyl-C-polyfluoroalkyl-C-chlorosulfinimides RFC(Cl)SN?R

The N-alkyl-C-polyfluoroalkyl-C-chlorosulfinimides R_FC(Cl)SN R have been investigated. Some aspects of their thermal stability and their [3 + 2] and [3 + 1] cycloaddition reactions have been examined.     

Quantum chemistry investigation of electronic structure and NMR spectral characteristics for fluorides of dialkylamidosulfoxylic acids and related compounds

The parent (H₂N? S? F) and N,N‐dialkyl‐substituted fluorides of amidosulfoxylic acid (R₂N? S? F, R?Me or R₂N?Morph) as well as the related compounds X? S? F (X?CH₃, OH, F, SiH₃, PH₂, SH, Cl) have been investigated with quantum chemical calculations at the ab initio (MP2) level of approximation. The geometries, electronic structures, molecular orbital (MO) energies and NMR chemical shift values have been calculated to evaluate the role and extent of the polarization and delocalization effects in forming of the high‐field fluorine NMR resonances within the series of interest. The δF magnitudes for all investigated fluorides of amidosulfoxylic acid as well as the δN value calculated for Me₂N? S? F are in the good agreement with the ¹⁹F and ¹⁴N NMR chemical shift values measured experimentally. For the parent compounds, H₂N? S? F and H₂N? SO₂? F, the orientation of principal axes of the magnetic shielding tensors and the corresponding principal σ_ii values along these axes have been qualitatively interpreted basing on the analysis of the MO interactions in the presence of the rotating magnetic field. Copyright © 2009 John Wiley & Sons, Ltd.