5427-11-2Relevant academic research and scientific papers
Functionalization of a Single C?F Bond of Trifluoromethylarenes Assisted by an ortho-Silyl Group Using a Trityl-Based All-in-One Reagent with Ytterbium Triflate Catalyst
Kim, Youngchan,Kanemoto, Kazuya,Shimomori, Ken,Hosoya, Takamitsu,Yoshida, Suguru
supporting information, p. 6136 - 6140 (2020/05/20)
Catalytic thiolation and azidation of a single C?F bond of trifluoromethylarenes were achieved assisted by an ortho-silyl group with all-in-one reagents to generate a trityl cation and nucleophiles. The reactions catalyzed by ytterbium triflate efficientl
A Self-Assembled Cage with Endohedral Acid Groups both Catalyzes Substitution Reactions and Controls Their Molecularity
Bogie, Paul M.,Holloway, Lauren R.,Ngai, Courtney,Miller, Tabitha F.,Grewal, Divine K.,Hooley, Richard J.
supporting information, p. 10232 - 10238 (2019/07/09)
A self-assembled Fe4L6 cage complex internally decorated with acid functions is capable of accelerating the thioetherification of activated alcohols, ethers and amines by up to 1000-fold. No product inhibition is seen, and effective
Structural and solvent effects on the C-S bond cleavage in aryl triphenylmethyl sulfide radical cations
Del Giacco, Tiziana,Lanzalunga, Osvaldo,Mazzonna, Marco,Mencarelli, Paolo
experimental part, p. 1843 - 1852 (2012/04/23)
Steady-state and laser flash photolysis (LFP) studies of a series of aryl triphenylmethyl sulfides [1, 3,4-(CH3O)2-C 6H3SC(C6H5)3; 2, 4-CH3O-C6H4SC(C6H5) 3; 3, 4-CH3-C6H4SC(C 6H5)3; 4, C6H5SC(C 6H5)3; and 5, 4-Br-C6H 4SC(C6H5)3] has been carried out in the presence of N-methoxyphenanthridinium hexafluorophosphate in CH 3CN, CH2Cl2, CH2Cl 2/CH3CN, and CH2Cl2/CH3OH mixtures. Products deriving from the C-S bond cleavage in the radical cations 1?+-5?+ have been observed in the steady-state photolysis experiments. Time-resolved LFP showed first-order decay of the radical cations accompanied by formation of the triphenylmethyl cation. A significant decrease of the C-S bond cleavage rate constants was observed by increasing the electron-donating power of the arylsulfenyl substituent, that is, by increasing the stability of the radical cations. DFT calculations showed that, in 2?+ and 3?+, charge and spin densities are mainly localized in the ArS group. In the TS of the C-S bond cleavage an increase of the positive charge in the trityl moiety and of the spin density on the ArS group is observed. The higher delocalization of the charge in the TS as compared to the initial state is probably at the origin of the observation that the C-S bond cleavage rates decrease by increasing the polarity of the solvent.
Synthetic Applications of N-N Linked Heterocycles. Part 12. The Preparation of 4-Alkylthio- and 4-Arylthio-pyridines by Regiospecific Attack of Thioalkoxide Ions on N-(4-Oxopyridin-1-yl)pyridinium Salts
Sammes, Michael P.,Leung, Christopher W. F.,Mak, Chi Keung,Katritzky, Alan R.
, p. 1585 - 1590 (2007/10/02)
Thiolate ions add regiospecifically to N-(4-oxopyridin-1-yl)pyridinium salts (2)-(7) to give in good to excellent yields only the 1,4-dihydropyridine adducts (8)-(13), regardless of whether or not the pyridone moiety carries substituents for sterically shielding the 2- and 6-positions of the pyridinium ring.The addition is believed to be thermodynamically controlled.Decomposition of the dihydro-adducts under free-radical conditions, or by pyrolysis, gives good yields of pyridin-4-yl thioethers (14) and (16) though the reaction failed with the 2-methyl adducts (9).An improved synthesis of 6-methyl-4-oxopyran-2-carboxylic acid is also described.
