Recent Advances of α‐Isothiocyanato Compounds in the Catalytic Asymmetric Reaction

Reaction of 4-fluoro-N-sulfinylaniline with norbornene and norbornadiene has afforded the Diels–Alder adducts of benzothiazine structure that have been oxidized into the corresponding benzothiazine sulfonamides. Structure of the obtained compounds and stereochemistry of the diene addition and epoxidation of norbornene olefin bonds have established by means of X-ray diffraction method.

Synthesis of benzothiazine sulfonamides via heteroatomic Diels–Alder reaction of para-fluoro-N-sulfinylaniline with bicyclo[2.2.1]heptenes

N-Sulfinyl-3-(trifluoromethyl)aniline reacted with bicyclo[2.2.1]hept-2-ene and bicyclo[2.2.1]-hepta-2,5-diene to give the corresponding Diels‒Alder adducts which were oxidized to 8-trifluoromethyl-2,3,4,4a,6,10b-hexahydro-5λ6-1,4-methanodibenzo[c,e][1,2]thiazine-5,5(1H)-diones. The cycloaddition occurred predominantly with participation of the S=N–C1=C6 fragment of N-sulfinyl-3-(trifluoromethyl)aniline and exclusively at the endo side of bicyclo[2.2.1]heptenes.

Synthesis of cyclic sulfonamides by reaction of N-Sulfinyl-3-(trifluoromethyl)aniline with Norbornenes

From classical to supramolecular dynamic stereochemistry: Double crystallization-induced diastereomerization of thiazine sulfonamide.

Assessment of the molecular structure and spectroscopic properties of CF3-substituted sulfinylaniline derivatives

Reactions of N-sulfinylanilines with norbornene and norbornadiene result in the Diels-Alder adducts of benzo-ortho-thiazine structure, which was confirmed by the NMR, IR spectroscopy and XRD analysis. In all cases the diene added to the norbornenes bicyclic system at the side of the endo-methylene bridge. The methyl group of meta-N-sulfinyl toluidine directs the norbornene entry into the para-position.

N-Sulfinylanilines as Dienes in the Diels-Alder Reaction. Structural Aspects

From substituted N-sulfinylanilines acting as dienes in the Diels-Alder reaction with norbornadiene S-oxides of benzo-ortho-thiazines were obtained, which were oxidized into the corresponding S,S-dioxides belonging to the class of hybrid thiazinesulfonamide compounds.

P. V. Merabov

Papers

N-Sulfinylanilines as Dienes in the Diels-Alder Reaction. Structural Aspects

Synthesis of benzo- ortho -thiazines S -oxides by Diels-Alder reaction of N -sulfinylanilines with norbornadiene

Synthesis of Benzo-ortho-thiazines S-Oxides by Diels—Alder Reaction of N-Sulfinylanilines with Norbornadiene.