Rudenko T. Synthesis of functional substituted thiolanes by [3+2]-cycloaddition reactions of thiocarbonylylide

The dissertation is devoted to a synthetic approach to obtaining functionalized thiolanes, including their bicyclic and spirocyclic derivatives, by the reaction of 1,3-dipolar cycloaddition of thiocarbonylylide to a compound with activated multiple bonds, including (hetero)cyclic aliphatic alkenes with an endo- and exo-cyclic double bond. A preparative convenient method of obtaining chloromethyltrimethylsilylmethyl sulfide - the precursor of unsubstituted thiocarbonylylide (thioformaldehyde S-methylide) has been developed. The reaction conditions of fluoride ion-activated desilylation of chloromethyltrimethylsilylmethyl sulfide for in situ generation of thiocarbonyl ylide and its subsequent cycloaddition to a model dipolarophile, methyl cyclohex-1-enoate, were optimized. The synthetic approach to thiolanes (hydrogenated thiophenes) with ester, nitrile, aromatic, trifluoromethyl substituents in the 3 or 3 and 4 positions has been extended through the [3+2]-cycloaddition reaction of thiocarbonyl ylide to a number of acyclic compounds with an activated or conjugated multiple bond. As part of the post-functionalization of cycloaddition products, a number of thiolane and sulfolane derivatives - carboxylic acids, amines, aldehydes, amidines - were obtained with good yields in multigram quantities [1]. An approach to 4-(trifluoromethyl)tetrahydrothiophene derivatives containing ester, sulfone, sulfoximine, sulfamide, and phosphonate in position 3 was developed, It consists in [3+2]-cycloaddition reactions of 1-functionalized 3,3,3-trifluoropropenes to thiocarbonyl ylide. Several examples of 4-(trifluoromethyl)tetrahydrothiophenyl-S-oxides, S-imino-S-oxides and S,S-dioxides were obtained [2].