5433-76-1Relevant academic research and scientific papers
Pyridine-catalyzed desulfonative borylation of benzyl sulfones
Maekawa, Yuuki,Ariki, Zachary T.,Nambo, Masakazu,Crudden, Cathleen M.
supporting information, p. 7300 - 7303 (2019/08/15)
Herein, we report the transition-metal free, pyridine-catalyzed desulfonative borylation of benzyl sulfones with bis(pinacolato)diboron (B2pin2). A variety of benzhydryl- and benzyl boronic esters could be synthesized from readily prepared sulfone derivatives. The borylation of cyclic sulfones accompanied by ring opening also proceeded to afford the corresponding sulfonate, which could be converted into functionalized sulfones and sulfonamides.
Arylative Desulfonation of Diarylmethyl Phenyl Sulfone with Arenes Catalyzed by Scandium Triflate
Nambo, Masakazu,Ariki, Zachary T.,Canseco-Gonzalez, Daniel,Beattie, D. Dawson,Crudden, Cathleen M.
supporting information, p. 2339 - 2342 (2016/06/09)
A scandium-triflate-catalyzed arylative desulfonation of diarylmethyl phenyl sulfones with arenes and heteroarenes was established. A variety of both sulfone and arene substrates were reacted to afford symmetric and nonsymmetric triarylmethanes in good yields. Further transformations of the resulting triarylmethanes and application to the concise synthesis of a bactericidal agent analogue were also demonstrated.
Modular synthesis of triarylmethanes through palladium-catalyzed sequential arylation of methyl phenyl sulfone
Nambo, Masakazu,Crudden, Cathleen M.
, p. 742 - 746 (2014/01/23)
Triarylmethanes, which are valuable structures in materials, sensing and pharmaceuticals, have been synthesized starting from methyl phenyl sulfone as an inexpensive and readily available template. The three aryl groups were installed through two sequential palladium-catalyzed C-H arylation reactions, followed by an arylative desulfonation. This method provides a new synthetic approach to multisubstituted triarylmethanes using readily available haloarenes and aryl boronic acids, and is also valuable for the preparation of unexplored triarylmethane-based materials and pharmaceuticals. Unsymmetric triarylmethanes have been synthesized starting from methyl phenyl sulfone as an inexpensive and readily available template. The three aryl groups were installed through two sequential palladium-catalyzed C-H arylation reactions, followed by an arylative desulfonation. Copyright
Nucleophilicity and nucleofugality of phenylsulfinate (PhSO 2-): A key to understanding its ambident reactivity
Baidya, Mahiuddin,Kobayashi, Shinjiro,Mayr, Herbert
supporting information; experimental part, p. 4796 - 4805 (2010/06/17)
Second-order rate constants for the reactions of the phenylsulfinate ion PhSO2- with benzhydrylium ions Ar2CH + have been determined in DMSO, acetonitrile, and aqueous acetonitrile solution using laser-flash and stopped-flow techniques. The rate constants follow the correlation equation log k (20 °C) = s(N + E), which allows the determination of the nucleophile-specific parameters N and s for PhSO2- in different solvents. With N = 19.60, PhSO 2- is a slightly weaker nucleophile than malonate and azide ions in DMSO. While PhSO2- reacts with highly stabilized benzhydrylium ions to give benzhydryl phenyl sulfones exclusively, highly reactive benzhydrylium ions give mixtures of sulfones Ar 2CH-SO2Ph and sulfinates Ar2CH-OS(O)Ph; the latter rearrange to the thermodynamically more stable sulfones through an ionization recombination sequence. Sulfones generated from PhSO2 - and stabilized amino-substituted benzhydrylium ions undergo heterolysis in aqueous acetonitrile and the rate of formation of the colored benzhydrylium ions was followed spectrophotometrically by stopped-flow techniques. The ranking of the electrofugalities of the benzhydrylium ions (i.e., the relative ionization rates of Ar2CH-SO2Ph) was not the inverse of the ranking of their electrophilicities (i.e., the relative reactivities of Ar2CH+ with nucleophiles), which was explained by differences in Marcus intrinsic barriers. While sulfones are thermodynamically more stable than the isomeric sulfinates, the intrinsic barriers for the attack of benzhydrylium ions at the oxygen of PhSO 2- are significantly lower than the intrinsic barriers for S-attack, and the activation energies for the attack of carbocations at sulfur are only slightly smaller than those for attack at oxygen. Because reactions of PhSO2- with carbocations of an electrophilicity E > -2 (i.e., carbocations which are more reactive than Ph3C+) are diffusion-controlled, the regioselectivities of the reactions of PhSO 2- with ordinary carbocations do not reflect relative activation energies.
Palladium-catalyzed Negishi α-arylation of alkylsulfones
Zhou, Gang,Ting, Pauline C.,Aslanian, Robert G.
experimental part, p. 939 - 941 (2010/05/18)
A general, mild catalytic system for α-monoarylation of various alkyl sulfones is described that utilizes palladium-catalyzed Negishi cross-coupling approach.
Copper-catalyzed nitrogen loss of sulfonylhydrazones: A reductive strategy for the synthesis of sulfones from carbonyl compounds
Feng, Xing-Wen,Wang, Jian,Zhang, Ji,Yang, Jing,Wang, Na,Yu, Xiao-Qi
supporting information; experimental part, p. 4408 - 4411 (2010/12/19)
Figure Presented. An efficient method for the synthesis of sulfones via nitrogen loss of sulfonyl hydrazones is described. The reaction was performed in the presence of simple copper salt and base by utilization of sulfonyl hydrazones, which were easily p
Iron (III) chloride-catalyzed direct sulfonylation of alcohols with sodium arenesulfinates
Reddy, M. Amarnath,Reddy, P. Surendra,Sreedhar
supporting information; experimental part, p. 1861 - 1869 (2010/10/21)
A new protocol for the direct sulfonylation of benzylic, allylic and homoallylic alcohols with sodium arenesulfinates is described by using iron (III) chloride as a catalyst and chlorotrimethylsilane as an additive. This method requires no preactivation o
Catalyst-free alkylation of sulfinic acids with sulfonamides via sp 3 C-N bond cleavage at room temperature
Liu, Cong-Rong,Li, Man-Bo,Cheng, Dao-Juan,Yang, Cui-Feng,Tian, Shi-Kai
supporting information; scheme or table, p. 2543 - 2545 (2009/10/10)
An unprecedented catalyst-free alkylation of sulfinic acids with sulfonamides has been developed via sp3 C-N bond cleavage at room temperature. In the absence of external catalysts and additives, a wide variety of N-benzylic and N-allylic sulfonamides couple with sulfinic acids to give structurally diversified sulfones in moderate to excellent yields. Furthermore, the reaction of N-(2-acyl)allylic sulfonamides with sulfinic acids provides a convenient access to trisubstituted allyl sulfones with exclusive Z selectivity.
Novel model sulfur compounds as mechanistic probes for enzymatic and biomimetic oxidations
Penenory, Alicia B.,Argueello, Juan E.,Puiatti, Marcelo
, p. 114 - 122 (2007/10/03)
To test for the intermediacy of sulfide radical cations in biomimetic and enzymatic oxidations, the sulfides PhSCH3 (1a), PhSCH2Ph (1b), PhSCHPh2 (1c), PhSCPh3 (1d), CH 3SCHPh2 (2), PhSCH2CH=CH2 (3), PhSCH2CH=CHPh (4) and CH3SCH2CH=CHPh (5) were studied, and their results were compared to those obtained for the corresponding chemical electron transfer (CET) and photoinduced electron transfer (PET) oxidations. The radical cations generated from 3-5 by CET in the presence of cerium(IV) ammonium nitrate (CAN) yielded only fragmentation products from the alkyl cations and the thiyl radicals (RS.), whereas 2.+ afforded both fragmentation and mainly α-deprotonation products. Photochemical treatment of the sulfides 1a and 1b with C(NO2) 4 gave only the corresponding sulfoxides, while fragmentation was the main pathway for the photoreactions of 1c, 2 and 5, and for 1d only this latter process was observed. These results support our selection of the sulfides RSCHPh2, RSCH2CH=CHPh (R = Me, Ph) and PhSCPh3 as models for the biomimetic and enzymatic studies. As evidenced by the sulfoxides and sulfones detected as unique products both in protic and in aprotic solvents, it is proposed that the mechanism of the biomimetic sulfoxidations of sulfides 1c and 2-5 by TPPFeIIICI is direct oxygen transfer. Three enzymes - Coprinus cinereus peroxidase (CiP), horseradish peroxidase (HRP) and chloroperoxidase (CPO) - were studied in the oxidation of sulfides 1a, 2, 4 and 5. The use of a racemic alkyl hydroperoxide in the CiP enzymatic oxidation of sulfides 5 and 2 yielded the corresponding sulfoxides (23 and 29%) and the aldehyde or benzophenone (5%), respectively. These results suggest the involvement of an ET process for the CiP-catalysed oxidation. Fragmentation products were observed in the enzymatic oxidation of sulfide 4 with HRP, which confirms the previously proposed ET mechanism. On the other hand, the CPO-enzymatic oxidation of sulfide 5 yielded only the corresponding sulfoxide, as would be expected for a direct oxygen-transfer or oxene mechanism. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005.
Chemistry of trichlorofluromethane: Synthesis of chlorofluromethyl phenyl sulfone and fluoromethyl phenyl sulfone and some of their reactions
Saikia,Tsuboi
, p. 643 - 647 (2007/10/03)
It was observed that the reaction of CFCl3 with thiophenoxide gave only 10% of the corresponding thioether. On the other hand, these thioethers could be prepared in excellent yield from diaryl disulfides and CFCl3 in the presence of sodium hydroxymethanesulfinate in aqueous DMF at 4 atm pressure of nitrogen. Dechlorination of the thioether (PhSCFCl2) with different reducing agents were studied. Most of the reducing agents eliminated both fluorine and chlorine functionalities or gave the hydrolyzed products. But its sulfone on treatment with Zinc in methanol gave monochlorofluoromethyl and fluoromethyl phenyl sulfone in good yields. Darzens reaction of these compounds was also studied.
