Reaction of 2,2,3,3-tetrafluoropropyl dichloro-phosphite with 1,1,2-trichloro-1-nitrosoethane

Conclusions Depending on the reaction conditions, 2,2,3,3-tetrafluoropropyi dichlorophosphate and 1,1,2-trichloro-1-nitrosoethane give either O-chloromethylchloroformiminodichlorophosphate or O-chloromethylchloroformimino-O-2,2,3,3-tetrafluoropropylchlorophosphate.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1422–1423, June, 1987.     

Reaction of perfluoroalkylethylens with nucleophiles

Perfluoroalkylethylenes react with some carbon-, oxygen-, sulfur-, selenium-, nitrogen-, and phosphorus-based nucleophiles by formal S_N2′ displacement of fluoride ion.     

Reaction of enyne triflates with nucleophiles

Reaction of nucleophiles with enyne triflates R₁R₂CC(OTf)CCR₃1, via an S_N-2′ process, results in functionalized enynes by way a 1,3-hydride shift from the initially formed butatrienes.     

Reaction of octafluorocyclopentene with various carbon nucleophiles

The treatment of octafluorocyclopentene with organolithium reagents gave the corresponding symmetrical disubstituted perfluorocyclopentenes in good to high yields. The reaction with Grignard reagents led to the monosubstituted perfluorocyclopentenes, which were subjected to the further nucleophilic substitution reaction using another Grignard or aryllithium reagents, unsymmetrical disubstituted perfluorocyclopentenes being obtained in high yields.     

Reactions of tetrachloropyridazine with aliphatic nitrogen nucleophiles

Nucleophilic aromatic substitution reactions of tetrachloropyridazine with a series of aliphatic primary and secondary amines led selectively to products arising from replacement of chlorine at the 4‐position in all cases. The structures of the products were unambiguously confirmed by X‐ray crystallography. Substitution occurs at the most activated site para to ring nitrogen, despite the possible steric hindrance to substitution by adjacent chlorine atoms, reflecting the activating influence of ring nitrogen meta to the site of attack. N,N′‐Dimethylethylene diamine gave a mixture of [6,6] ring fused products following initial substitution at the 4‐position.     

Reaction of difluoromethyl pentafluorophenyl sulfoxide with nucleophiles

Reactions of 1-(difluoromethanesulfinyl)pentafluorobenzene with sodium methoxide, sodium phenoxide, potassium hydrosulfide, and methylamine resulted in substitution of fluorine atom in the 4-position (in the reaction with methylamine, also in the 2-position). Treatment of the title compound with sodium hydroxide afforded pentafluorobenzene due to cleavage of the C_arom?S bond.     

A general phosphoric acid-catalyzed desymmetrization of meso-aziridines with silylated selenium nucleophiles

The first example of meso-aziridine desymmetrization with selenium nucleophiles is reported. The reaction, promoted by VAPOL-hydrogen phosphate using (phenylseleno)trimethylsilane as the nucleophile, proves to be very general and highly enantioselective (84-99% ee).     

Reaction of 4-methyl-3,4-epoxytetrahydropyran with nucleophiles

Reaction of 4-methyl-3,4-epoxytetrahydropyran with phenols, thiols, thiocyanic acid and benzoic acid, thiourea, and with sodium sulfite and thiosulfate occurs with opening of the epoxide ring. Using IR spectroscopy it was shown that the products occur via trans-diaxial opening of the oxide ring at the least-substituted carbon atom.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1465–1468, November, 1990.     

Reaction of sulfolenes and their derivatives with some sulfur-containing nucleophiles

Reaction of 2-sulfolene, 4-hydroxy-2-sulfolene, 4-bromo- and 3-chloro-2-sulfolenes, 3-chloro-4-hydroxysulfolane, and 3,4-dibromo(dichloro)sulfolanes with sodium methane-, hexane-, allene-, benzene-, and p-toluenesulfinates and magnesium gave 3-methyl-, 3-hexyl-, 3-allyl-, 3-phenyl-, and 3-(p-tolylsulfonyl)sulfolanes, 3-methyl-, 3-phenyl-, and 3-(p-tolylsulfonyl)-4-hydroxysulfolanes, and 3-phenyl- and 4-phenylsulfonyl-2-sulfolenes.     

Reaction of 5-Allyl-2,3,5-trichloro-4,4-dimethoxycyclopent-2-en-1-one with amino acids

5-Allyl-2,3,5-trichloro-4,4-dimethoxycyclopent-2-en-1-one reacts with L-proline and L-methionine methyl esters to give diastereoisomeric mixtures of the corresponding chlorine replacement products at C³.     

Chemoselective opening of Vince lactam epoxide with nitrogen nucleophiles

Here is reported the chemoselective opening of the amide bond on a Vince lactam derivative with amines, without the cleavage of the epoxide-moiety, getting five new epoxides. Also reported is the rearrangement of the epoxides into the respective five new oxazolidinones with the use of BF₃·Et₂O. Crystal structures of some molecules and hydrogen bonding interactions are discussed.