124910-41-4Relevant academic research and scientific papers
Reaction of trifl uoromethanesulfonamide with heterodienes under oxidation conditions
Moskalik,Astakhova,Shainyan
, p. 1567 - 1571 (2013)
Reactions of trifl uoromethanesulfonamide with divinyl sulfone, divinyl sulfoxide, divinyl sulfide, diphenyl sulfide, vinyl allyl and diallyl ethers was investigated in the presence of oxidation system t-BuOCl + NaI. The reaction with divinyl sulfone afforded a product of 1,5-heterocyclization, 2,6-diiodo-4-[(trifl uoromethyl) sulfonyl]thiomorpholine 1,1-dioxide. The same product was obtained in the reaction with divinyl sulfoxide apparently due to its preliminary oxidation to sulfone. In reactions with divinyl sulfide and unsaturated ethers only the oxidation of substrates was observed accompanied with strong tarring; the products of a reaction with trifl uoromethanesulfonamide were absent. With diphenyl sulfide a product was formed resulting from the oxidation at the sulfur atom [S(II) → S(IV)], N-(diphenyl-λ4-sulfanylidene)trifl uoromethanesulfonamide. Pleiades Publishing, Ltd., 2013.
Imination of sulfides and sulfoxides with sulfonylimino- λ3-bromane under mild, metal-free conditions
Ochiai, Masahito,Naito, Masao,Miyamoto, Kazunori,Hayashi, Satoko,Nakanishi, Waro
supporting information; experimental part, p. 8713 - 8718 (2010/10/19)
Exposure of sulfides and sulfoxides to trifluoromethanesulfonylimino(aryl)- λ3-bromane in dichloromethane at 0°C results in a facile transfer of the sulfonylimino group to sulfur atoms and affords N-triflylsulfilimines and -sulfoximines in high yields under transition-metal-free conditions. Imination of (R)-methyl p-tolyl sulfoxide proceeded with predominant retention of configuration at the stereogenic sulfur center. The Hammett plot afforded ρ values of -0.58 for para-substituted thioanisoles and -0.49 for their equivalent sulfoxides, which suggests a buildup of positive charge on the sulfur atoms of sulfides and sulfoxides in the transition state. Calculations suggest a bimolecular nucleophilic-substitution mechanism on the negatively charged nitrogen atom of the sulfonylimino- λ3-bromane, which involves the attack of a sulfide from the opposite side to bromine(III).
