- Rewiring Chemical Networks Based on Dynamic Dithioacetal and Disulfide Bonds
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The control of the connectivity between nodes of synthetic networks is still largely unexplored. To address this point we take advantage of a simple dynamic chemical system with two exchange levels that are mutually connected and can be activated simultan
- Orrillo, A. Gastón,La-Venia, Agustina,Escalante, Andrea M.,Furlan, Ricardo L. E.
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- Mapping mechanisms in glycosylation reactions with donor reactivity: Avoiding generation of side products
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The glycosylation reaction, which is key for the studies on glycoscience, is challenging due to its complexity and intrinsic side reactions. Thioglycoside is one of the most widely used glycosyl donors in the synthesis of complex oligosaccharides. However, one of the challenges is its side reactions, which lower its yield and limits its efficiency, thereby requiring considerable effort in the optimization process. Herein, we reported a multifaceted experimental approach that reveals the behaviors of side reactions, such as the intermolecular thioaglycon transformation and N-glycosyl succinimides, via the glycosyl intermediate. Our mechanistic proposal was supported by low temperature NMR studies that can further be mapped by utilizing relative reactivity values. Accordingly, we also presented our findings to suppress the generation of side products in solving this particular problem for achieving high-yield glycosylation reactions.
- Wang, Cheng-Chung,Chang, Chun-Wei,Lin, Mei-Huei,Wu, Chia-Hui,Chiang, Tsun-Yi
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p. 15945 - 15963
(2021/01/18)
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- Alternating Current Electrolysis for the Electrocatalytic Synthesis of Mixed Disulfide via Sulfur–Sulfur Bond Metathesis towards Dynamic Disulfide Libraries
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A novel approach of electrolysis using alternating current was applied in the sulfur–sulfur bond metathesis of symmetrical disulfides towards unsymmetrical disulfides. As initially expected, a statistical distribution in disulfides was obtained. Furthermore, the influence of electrode polarisation by alternating current was investigated on a two-disulfide matrix. The highly dynamic nature of this chemistry resulted in the creation of dynamic disulfide libraries by expansion of the matrices, consisting of up to six symmetrical disulfides. In addition, mixing of matrices and stepwise expanding of a matrix by using alternating current electrolysis were realised.
- Hilt, Gerhard,Otten, Chris Josef,Sattler, Lars Erik
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supporting information
(2020/02/27)
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- Phthalimide-Carried Disulfur Transfer to Synthesize Unsymmetrical Disulfanes via Copper Catalysis
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A versatile Cu-catalyzed cross-coupling reaction to various unsymmetrical disulfanes has been presented, from phthalimide-carried disulfur transfer reagents and commercially available boronic acids under mild and practical conditions. The method features the unprecedented use of phthalimide-carried disulfurating reagents (Harpp reagent) in cross-coupling chemistry and is highlighted by the broad substrate scopes, even applicable for the transfer of aryl-disulfur moieties (ArSS-). Notably, the robustness of this methodology is shown by the late-stage modification of bioactive scaffolds of coumarin, estrone, and captopril.
- Zou, Jiaoxia,Chen, Jinhong,Shi, Tao,Hou, Yongsheng,Cao, Fei,Wang, Yongqiang,Wang, Xiaodong,Jia, Zhong,Zhao, Quanyi,Wang, Zhen
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p. 11426 - 11430
(2019/11/21)
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- A Novel Method for the Direct Synthesis of Symmetrical and Unsymmetrical Sulfides and Disulfides from Aryl Halides and Ethyl Potassium Xanthogenate
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An efficient and new method for the synthesis of disulfides and sulfides via the reaction of aryl halides with ethyl potassium xanthogenate in the presence of MOF-199 is described. O -Ethyl- S -aryl carbonodithioate has a key role as an intermediate in this procedure; it was converted into symmetrical diaryl disulfides in DMF. Additionally, this could be applied to the synthesis of unsymmetrical aryl alkyl(aryl′) disulfides by the reaction with S -alkyl(aryl) sulfurothioates (Bunte salts) as well as unsymmetrical aryl alkyl(aryl′) sulfides in DMSO.
- Soleiman-Beigi,Arzehgar
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supporting information
p. 986 - 992
(2018/02/09)
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- Unsymmetrical disulfide and sulfenamide synthesis via reactions of thiosulfonates with thiols or amines
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The reactivity of thiosulfonates with nucleophilic reagents was investigated. When reactions of thiosulfonates with thiols were performed, unsymmetrical disulfides were obtained in excellent yields. This procedure could employ numerous aryl or alkyl thiols. On the other hand, reactions of thiosulfonates with amines proceeded in the presence of a copper catalyst. The procedure was performed efficiently in air, and afforded the corresponding sulfenamides.
- Taniguchi, Nobukazu
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p. 2030 - 2035
(2017/03/17)
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- Catalyst-Free S–S Bond Insertion Reaction of a Donor/Acceptor-Free Carbene by a Radical Process: A Combined Experimental and Computational Study
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Herein, a donor/acceptor-free carbene insertion reaction of an S–S bond through a radical process is presented. This catalyst-free reaction was thermally induced and provided the dithioketal products in moderate to high yields. A mechanism involving radical intermediates was proposed according to the computational study, and these intermediates were verified experimentally and intercepted for the first time by using a cross-coupling reaction.
- Zheng, Yang,Bian, Rongjian,Zhang, Xiaolu,Yao, Ruwei,Qiu, Lihua,Bao, Xiaoguang,Xu, Xinfang
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supporting information
p. 3872 - 3877
(2016/08/16)
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- Heterogeneously catalyzed direct C-H thiolation of heteroarenes
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The first general methodology for the direct thiolation of electron-rich heteroarenes was developed by employing Pd/Al2O3, a recoverable and commercially available heterogeneous catalyst, and CuCl2. This method represents an operationally simple approach for the synthesis of these valuable compounds. Preliminary mechanistic studies indicate a heterogeneous catalytic system, in which both metals play a complementary role in the formation of the thiolated products. (Hetero)genius: A general method for the direct thiolation of electron-rich heteroarenes was developed by employing Pd/Al2O3, a recoverable and commercially available heterogeneous catalyst, and CuCl2. Preliminary mechanistic studies indicate a heterogeneous active catalytic species, with the two metals playing complementary roles in the formation of the thiolated products.
- Vsquez-Cspedes, Suhelen,Ferry, Anglique,Candish, Lisa,Glorius, Frank
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p. 5772 - 5776
(2015/06/17)
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- Mechanistic insight into the photoredox catalysis of anti-markovnikov alkene hydrofunctionalization reactions
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We describe our efforts to understand the key mechanistic aspects of the previously reported alkene hydrofunctionalization reactions using 9-mesityl-10-methylacridinium (Mes-Acr+) as a photoredox catalyst. Importantly, we are able to detect alk
- Romero, Nathan A.,Nicewicz, David A.
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supporting information
p. 17024 - 17035
(2015/02/18)
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- Microwave-assisted synthesis of disulfides
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A new microwave-assisted synthesis methodology for the preparation of substituted disulfide derivatives is presented. 4-Substituted sulfenimides were reacted with 4-substituted thiols under neat (to right doughy consistency) conditions in chloroform, with both microwave heating and conventional methods. The resulting 4-substituted disulfide derivatives were obtained at higher yields and in shorter reaction times with microwave heating. Their chemistry was confirmed by 1H-NMR, 13C-NMR, infrared (IR), and elemental analysis.
- Kutuk, Halil,Turkoz, Nalan
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experimental part
p. 1515 - 1522
(2011/10/05)
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- A versatile and convenient preparation of unsymmetrical diaryl disulfides
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We have developed a convenient method for the synthesis of unsymmetrical diaryl disulfides under mild conditions in excellent yields. The described method is based on the straightforward preparation of 5,5-dimethyl-2-thioxo-1,3, 2-dioxaphosphorinane-2-sulfenyl bromide from readily available 5,5-dimethyl-2-sulfanyl-2-thioxo-l,3,2-dioxaphosphorinane or bis(5,5-dimethyl-2-thioxo-l,3,2-dioxaphosphorinan-2-yl) disulfide. The unsymmetrical diaryl disulfides can be obtained from aromatic thiol derivatives bearing electron-withdrawing or electron-donating groups. Thieme Stuttgart.
- Demkowicz, Sebastian,Rachon, Janusz,Witt, Dariusz
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body text
p. 2033 - 2038
(2009/04/03)
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- N-trifluoroacetyl arenesulfenamides, effective precursors for synthesis of unsymmetrical disulfides and sulfenamides
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N-Trifluoroacetyl arenesulfenamides (3) were effective precursors for the synthesis of unsymmetrical disulfides (4) and sulfenamides (5). Reactions of 3 with a variety of aromatic thiols at room temperature were generally complete within 5 min and gave unsymmetrical diaryl disulfides in high yields. Aralkyl disulfides were isolated in high yields from the reaction of 3 with aliphatic thiols. The nucleophilic substitution reactions of 3 with amines proceeded smoothly and provided N-substituted sulfenamides in good to excellent yields.
- Bao, Ming,Shimizu, Masao
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p. 9655 - 9659
(2007/10/03)
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- Biomimetic methane generation and disulfide formation by catalysis with a nickel complex
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The final metabolic process of methanogen, methane generation and simultaneous disulfide formation, is simulated by the reaction of thioanisole with a toluenethiyl radical in the presence of a nickel complex, which is generated by the photolysis of a toluenethiolato-nickel complex.
- Tada, Masaru,Masuzawa, Yoshihide
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p. 2161 - 2162
(2007/10/03)
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- The 'Thio-Arbuzov' reaction of sulfenate esters with sulfenyl chlorides: Fate of the thiosulfinate product
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The further reaction of thiosulfinate esters (putative products of the 'Thio-Arbuzov' reaction of sulfenate esters with sulfenyl chlorides) with sulfenyl chlorides and sulfenate esters has been studied. In the former case, sulfinyl chlorides and disulfides are formed. In the latter case sulfinate esters and disulfides are obtained. Copyright (C) 1996 Elsevier Science Ltd.
- Brown, Charles,Evans, Graham R.
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p. 9101 - 9104
(2007/10/03)
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- THIOSULFONATE PREPARATION BY THE THIOSULFINATE/SULFINIC ACID REACTION
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The reaction of thiosulfinates with amine salts of aryl sulfinic acids has been examined for the preparation of thiosulfonates, particularly unsymmetrical derivatives.Key words: Thiosulfinate; thiosulfonate; sulfinic acid amine salts.
- Clarke, Victor,Cole, Edward R.
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p. 171 - 174
(2007/10/02)
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- Novel Generation of Arylsulfenium Ion Intermediates and Efficient Aromatic Arylthiolation by the Intermediates
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Reactions of hydrazoic acid and alkyl azides with alkyl aryl sulfide in trifluoroacetic acid containing trifluoromethanesulfonic acid or H2SO4 proceeded through an S-arylaminosulfonium ion and a protonated S-arylsulfenamide, giving efficiently 4-alkylthiophenyl aryl sulfide via an arylsulfenium ion interacting with both the counter-anion and the unshared electron pair of the amine.The use of the S-arylsulfenamide instead of the azides also afforded the above product by aromatic arylthiolation in a good yield via the sulfenium ion along with its ortho-isomer, diaryl disulfide and diaryl sulfide.The formation of the sulfenium ion was demonstrated by the effect of the counter-anion, the amine, the aryl substituent of the sulfenamide and the solvent nucleophilicity.We ruled out the possibility that the arylthiolation occurs via an arylthiyl radical and an aminium radical from the sulfenamide and by direct reaction of the protonated sulfenamide with alkyl aryl sulfides.
- Takeuchi, Hiroshi,Oya, Hiromo,Yanase, Takehiro,Itou, Katsutaka,Adachi, Taki,et al.
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p. 827 - 834
(2007/10/02)
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- The Kinetics and Mechanism of the Reaction of Tricoordinate Phosphorus Compounds with Diaryl Trisulfides
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Kinetic data and activation parameters are reported for the reaction of a series of tricoordinate phosphorus compounds, , with diaryl trisulfides.The second-order rate coefficients for series of arylphosphines, phosphinites and phosphonites, correlate with the Hammett ? constants of the aryl substituents with ρ values of -1.1, -1.1 and -1.1 respectively and these results are discussed in terms of a biphilic mechanism analogous to that proposed for the reaction of tricoordinate phosphorus with S8.
- Hall, C. Dennis,Tweedy, Bruce R.,Kayhanian, Robert,Lloyd, John R.
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p. 775 - 779
(2007/10/02)
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- Photochemical Anion-Promoted Carbon-Sulfur Cleavage Reactions of Diaryl Sulfides, Alkyl Aryl Sulfides, and Related Sulfoxides and Sulfones
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Diaryl sulfides and the related sulfoxides and sulfones react with substances such as diethyl phosphite anion, pinacolone enolate, and diphenylphosphide anion under irradiation to cleave one carbon-sulfur bond and form diethyl arylphosphonates, arylmethyl tert-butyl ketones, and aryldiphenylphosphines.Alkyl aryl sulfides and the related sulfones also experience carbon-sulfur bond cleavage under these conditions to produce arenethiols.Generally, these reactions occur in synthetically useful yields.The reactions of the anions with these sulfides, sulfoxides, and sulfones all require irradiation, but is notable that the reactions of diphenylphosphide anion occur in the visible region of the spectrum.Several lines of evidence suggest that the reaction proceeds via the familiar SRN1 pathway and that the photochemically-induced electron transfer occurs in an arene-anion complex.Thermochemical considerations dictate the cleavage direction in the anion radicals of unsymmetrical sulfides.
- Cheng, Carlos,Stock, Leon M.
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p. 2436 - 2443
(2007/10/02)
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- Chemistry of Tetrathiotungstates: A Novel Synthesis of Disulfides from Sulfonyl Derivatives
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In an unusually novel reaction, piperidinium tetrathiotungstate has been found to induce reductive dimerization of a variety of sulfonyl derivatives to the corresponding disulfides under very mild conditions.
- Dhar, Preeti,Ranjan, Rajeev,Chandrasekaran, Srinivasan
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p. 3728 - 3729
(2007/10/02)
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- SYNTHESIS OF DISULPHIDES AND TRISULPHIDES via ORGANOSILICON COMPOUNDS
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Silyl sulphides 2a-b smoothly react with thiolsulphinates 1a-c and thiolsulphonates 6a-c to give unsymmetrical disulphides under mild conditions and in very good yields.The "neutral" conditions used allow one to avoid any side reactions and subsequent randomization of the products.When bis(trimethylsilyl)sulphide, 8, is used, symmetrical trisulphides may be obtained under the same experimental conditions.
- Capozzi, Giuseppe,Capperucci, Antonella,Degl'Innocenti, Alessandro,Duce, Rosa Del,Menichetti, Stefano
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p. 421 - 426
(2007/10/02)
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- 4'-NITROARENESULPHENANILIDES: THEIR USE IN THE SYNTHESIS OF UNSYMMETRICAL DISULPHIDES
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The reaction of 4'-nitroarenesulphenanilides with thiols in the presence of boron trifluoride etherate can provide an effective route to unsymmetrical disulphides.
- Benati, L.,Montevecchi, P. C.,Spagnolo, P.
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p. 1739 - 1742
(2007/10/02)
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- Sulfur-Sulfur Bond Cleavage Processes. Selective Desulfurization of Trisulfides
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The selectivity of sulfur removal in the desulfurization of trisulfides by tertiary phosphorus compounds has been investigated in detail.A mechanistic rationalization is proposed to account for central/terminal sulfur extrusion variation as a function of substrate structure and solvent polarity.
- Harpp, David N.,Smith, Roger A.
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p. 6045 - 6053
(2007/10/02)
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- REDUCTION OF SULFONIC ACIDS WITH PHOSPHORUS PENTASULFIDE
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Arene, and alkanesulfonic acids are easily reduced to the corresponding polysulfides R-(S)n-R (n= 2.9 3.3) by treatment with phosphorus pentasulfide.In this reaction, the formation of both P-O-S and P-S-H linkages is considered to be involved in the key step of the reduction.
- Oae, Shigeru,Togo, Hideo
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p. 4701 - 4704
(2007/10/02)
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- Facile Conversion of Thiosulfinic S-Ester to Sulfinic Ester
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Thiosulfinic S-esters are readily converted to the corresponding sulfinic esters in good yields by treating in alcohols with a catalytic amount of I2, Br2, or HCl in the presence of H2O2, replacing sulfenyl groups by alcohols.The mechanism of this reaction is also discussed.
- Takata, Toshikazu,Oae, Shigeru
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p. 3937 - 3938
(2007/10/02)
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- ANODIC OXIDATION OF DIALKYL AND DIARYL DITHIOACETALS
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The mechanism of the anodic oxidation of dithioacetals is discussed, taking into account new results concerning both mixed electrolyses and oxidations in super-dried solvents.In the case of the oxidation of aryldithioacetals, the formation of the -S-S- linkage is involved with a bond cleavage followed by a dimerisation.On the other hand, in the case of aliphatic starting materials the mechanism looks more consistent with the existence of a dicationic intermediate which is scavenged by nucleophiles.
- Gourcy, Jean,Martigny, Patrick,Simonet, Jacques,Jeminet, Georges
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p. 1495 - 1502
(2007/10/02)
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- FACILE REDUCTION OF SULFINIC ACID TO DISULFIDE WITH THIOL AND CHLOROTRIMETHYLSILANE
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Sulfinic acids were found to be readily reduced to the corresponding disulfide quantitatively at room temperature upon treatment with a mixture of thiols and chlorotrimethylsilane.
- Oae, Shigeru,Togo, Hideo,Numata, Tatsuo,Fujimori, Ken
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p. 1193 - 1196
(2007/10/02)
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- Physical Properties and Various Reactions of Thionitrites and Related Substances
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Several new sulfenyl or sulfonyl derivatives, thionitrates (RSNO2), sulfonyl nitrites (RSO2NO), were successfully isolated by treating corresponding thiols and sulfinic acids with dinitrogen tetraoxide (N2O4).Spectroscopic data of both stable and many rather unstable compounds were determined and compared with those of corresponding alkyl nitrites (RONO) or alkyl nitrates (RONO2).Chemical reactivities of these uncommon, novel S-nitroso and S-nitro compounds were investigated.
- Oae, Shigeru,Shinhama, Koichi,Fujimori, Ken,Kim, Yong Hae
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p. 775 - 784
(2007/10/02)
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