- NaI-Mediated Acetamidosulfenylation of Alkenes with Bunte Salts as Thiolating Reagent Leading to β-Acetamido Sulfides
-
A direct and efficient method for the acetamidosulfenylation reaction of alkenes was developed, in which NaI was used as a catalyst, DMSO as the oxidant, nitriles as both the solvent and nucleophiles and stable, readily available Bunte salts as thiolating reagents. The reactions were carried out under mild conditions generating β-acetamido sulfides in good yields. Moreover, the reaction can be performed when alcohols are used as nucleophiles providing the corresponding β-alkoxysulfides in moderate yields, respectively.
- Zhang, Rongxing,Yan, Zhaohua,Wang, Dingyi,Wang, Yuanxing,Lin, Sen
-
-
Read Online
- Synthesis and characterization of benzylidene bis-dithiobenzoate
-
Benzal chloride reacts with sodium sulfide in alcoholic solution to yield three main products: benzyl disulfide, benzyl dithiobenzoate, and a new interesting compound 5, C21H16S4, which was isolated and characterized as benzylidene bis-dithiobenzoate. The intermediates obtained from the autoxidation-reduction of the unisolable thiobenzaldehyde are implied in subsequent nucleophilic addition and substitution processes. NMR spectra and X-Ray structure analysis of 5 are discussed. Copyright Taylor & Francis Inc.
- Quintanilla, Ma. Gloria,Guerra, Eva,Dotor, Jessica,Maresova, Jirina,Barba, Fructuoso,Martin, Avelino
-
-
Read Online
- Direct preparation of anhydrous sodium oligosulfides from metal sodium and elemental sulfur in aprotic organic media directed toward synthesis of silane coupling agent
-
Anhydrous sodium oligosulfide was prepared by the heterogeneous reaction of metal sodium and elemental sulfur in aprotic solvents. The oligosulfide consisted of a mixture of several Na2Sn (n = 2 - 8). Organic oligosulfides (R2Sn, n ≥ 2) including moisture-sensitive one were synthesized by the reaction with organic halides in high yeilds under mild conditions.
- Yamada, Nobuo,Furukawa, Mutsuhisa,Nishi, Masayuki,Takata, Toshikazu
-
-
Read Online
- Reductive Dimerization of Organic Thiocyanates to Disulfides Mediated by Tetrathiomolybdate
-
An interesting reductive dimerization of organic thiocyanates assisted by benzyltriethylammonium tetrathiomolybdate, , 1, leads to the formation of the corresponding disulfides in high yields.
- Prabhu, Kandikere R.,Ramesha, A. R.,Chandrasekaran, Srinivasan
-
-
Read Online
- A convenient method for production of thionitrites and disulfides under mild and heterogeneous condition
-
Thiols can be readily converted to their corresponding thionitrite with a combination of inorganic acidic salts and sodium nitrite in dichloromethane at room temperature. Disulfides result from the homolytic cleavage of the sulfur-nitrogen bond of the unstable thionitrite and subsequent coupling of the resultant thiyl radicals.
- Zolfigol, Mohammad Ali
-
-
Read Online
- Sulfur transfer reactions of tetrathiomolybdate in water: Synthesis of alkyl disulfides from alkyl halides
-
Reaction of a number of alkyl halides with tetrathiomolybdate in water as the solvent affords the corresponding disulfides in good yields.
- Ilankumaran, Palanichamy,Prabhu, Kandikere R.,Chandrasekaran, Srinivasan
-
-
Read Online
- Convenient stereoselective synthesis of 3-hydroxy-2-iodo-2(E)-alkenyl sulfides via iodohydroxylation of 1,2-allenyl sulfoxides in the presence of BnSH
-
The iodohydroxylation of 1,2-allenyl sulfoxides with I2 in the presence of BnSH affords 3-hydroxy-2-iodo-2(E)-alkenyl sulfides in good yields and selectivities. The stereochemistry for the products of this transformation is opposite to what was obtained from the iodohydroxylation of 1,2-allenyl sulfides. Based on the results of some control experiment, a mechanism was proposed.
- Fu, Chunling,Huang, Xian,Ma, Shengming
-
-
Read Online
- Imidazole Promoted Highly Efficient Large-Scale Thiol-Free Synthesis of Symmetrical Disulfides in Aqueous Media
-
A highly efficient and environmentally friendly method for the imidazole promoted preparation of symmetrical organic disulfides from Bunte salts is described. This thiol-free procedure produces the desired disulfides even on a large scale by reaction of Bunte salts with imidazole in good to high yields in aqueous media.
- Mokhtari, Babak,Kiasat, Ali Reza,Monjezi, Javid
-
-
Read Online
- Copper(I)/S8 reversible reactions leading to an end-on bound dicopper(II) disulfide complex: Nucleophilic reactivity and analogies to copper-dioxygen chemistry
-
Elemental sulfur (S8) reacts reversibly with the copper(I) complex [(TMPA′)CuI]+ (1), where TMPA′ is a TMPA (tris(2-pyridylmethyl)amine) analogue with a 6-CH2OCH 3 substituent on one pyridyl ligand arm, affording a spectroscopically pure end-on bound disulfido-dicopper(II) complex [{(TMPA′)CuII}2(μ-1,2-S2 2-)]2+ (2) {ν(S-S) = 492 cm-1; ν(Cu-S)sym = 309 cm-1}; by contrast, [(TMPA)Cu I(CH3CN)]+ (3)/S8 chemistry produces an equilibrium mixture of at least three complexes. The reaction of excess PPh3 with 2 leads to formal "release" of zerovalent sulfur and reduction of copper ion to give the corresponding complex [(TMPA′)-CuI(PPh3)]+ (11) along with S=PPh3 as products. Dioxygen displaces the disulfur moiety from 2 to produce the end-on Cu2O2 complex, [{(TMPA′)Cu II}2(μ-1,2-O22-)]2+ (9). Addition of the tetradentate ligand TMPA to 2 generates the apparently more thermodynamically stable [{(TMPA)CuII}2(μ-1,2-S 22-)]2+ (4) and expected mixture of other species. Bubbling 2 with CO leads to the formation of the carbonyl adduct [(TMPA′)CuI-(CO)]+ (8). Carbonylation/sulfur- release/CO-removal cycles can be repeated several times. Sulfur atom transfer from 2 also occurs in a near quantitative manner when it is treated with 2,6-dimethylphenyl isocyanide (ArNC), leading to the corresponding isothiocyanate (ArNCS) and [(TMPA′)CuI(CNAr)]+ (12). Complex 2 readily reacts with PhCH2Br: [{(TMPA′)Cu II}2(μ-1,2-S22-)]2+ (2) + 2 PhCH2Br → [{(TMPA′)-CuII(Br)} 2]2+ (6) + PhCH2SSCH2Ph. The unprecedented substrate reactivity studies reveal that end-on bound μ-1,2-disulfide-dicopper(II) complex 2 provides a nucleophilic S 22- moiety, in striking contrast to the electrophilic behavior of a recently described side-on bound μ-η2: η2-disulfido-dicopper(II) complex, [{(N3)Cu II}2(μ-η2:η2-S 22-)]2+ (5) with tridentate N3 ligand. The investigation thus reveals striking analogies of copper/sulfur and copper/dioxygen chemistries, with regard to structure type formation and specific substrate reactivity patterns.
- Maiti, Debabrata,Woertink, Julia S.,Vance, Michael A.,Milligan, Ashley E.,Narducci Sarjeant, Amy A.,Solomon, Edward I.,Karlin, Kenneth D.
-
-
Read Online
- Kinetic investigation on liquid-liquid-solid phase transfer catalyzed synthesis of dibenzyl disulfide with H2S-laden monoethanolamine
-
An investigation has been done on the utilization of H2S for the synthesis of dibenzyl disulfide (DBDS) using Amberlite IR-400 as a phase transfer catalyst. This involves absorption of H2S in aqueous monoethanolamine (MEA) followed by reaction of this H2S-laden MEA with organic reactant benzyl chloride (BC) to yield DBDS under liquid-liquid-solid (L-L-S) phase transfer catalysis condition. The effect of various parameters on the conversion of BC was studied and the selectivity of desired product was 100% at some level of process parameters. A suitable reaction mechanism has been proposed and a mathematical model has been developed to explain the kinetics of the reaction. Waste minimization was therefore affected with the utilization of H2S-laden gas for production of a value-added fine chemical.
- Singh, Gaurav,Nakade, Priya G.,Mishra, Pratik,Jha, Preeti,Sen, Sujit,Mondal, Ujjal
-
-
Read Online
- Phthalimidomethyl Group. A New Protecting Group of Thiols
-
Phthalimidomethyl group is employed as a protecting group of thiols.This group can be introduced to thiols under mild reaction conditions and be removed by treatment with hydrazine hydrate followed by mercuric acetate or cupric acetate.
- Gong, Young-Dae,Iwasawa, Nobuharu
-
-
Read Online
- A tetra-: N -butylammonium iodide mediated reaction of indoles with Bunte salts: Efficient 3-sulfenylation of indoles under metal-free and oxidant-free conditions
-
A highly efficient tetra-n-butylammonium iodide (TBAI) triggered procedure for 3-sulfenylation of indoles with Bunte salts is demonstrated. This protocol provides a simple strategy to prepare 3-alkylthioindoles and 3-arylthioindoles from the corresponding indoles under metal-free and oxidant-free conditions.
- Li, Jian,Cai, Zhong-Jian,Wang, Shun-Yi,Ji, Shun-Jun
-
-
Read Online
- Reactivities of organic isothiocyanates and thiocyanates toward dialkyl bis(phosphine) complexes of palladium(II) and platinum(II)
-
Room-temperature reactions of trans-[PdEt2L2] (L = PMe3, PEt3, PMe2Ph) with organic isothiocyanates [R-NCS; R = benzyl; CH(CH3)Ph, R-(-) and S-(+); indanyl, S-(+)] afforded the S,S-coordinated Pd(II) complexes [Pd(S2CN-R)L2] containing a dithiocarbonimidato (S2CN-R) group. Similar reactions involving allyl isothiocyanates produced the cationic η3-allyl Pd complex [Pd(η3-allyl)(PMe3)2]+(NCS)-. When [Pd(S2CN-R)(PMe3)2] was treated with 1 equiv of a chelating phosphine [L-L = depe (1,2-bis(diethylphosphino)ethane) and dmpe (1,2-bis(dimethylphosphino)ethane)], the corresponding complexes [Pd(S2CN-R)(L-L)] were produced. Reactions of trans-[PdEt2L2] (L = PMe3, PMe2Ph) with organic thiocyanates (R-SCN; R = benzyl, Et) resulted in the formation of [Pd(CN)2L2] and an organic disulfide by S-C bond cleavage of R-SCN. However, similar reactions of the dimethyl analogs, trans-[PdMe2L2] (L = PMe3, PEt3), with benzyl thiocyanate afforded different products, [Pd(NCS)2L2] or [PdMe(NCS)L2]. Treating [Pt(styrene)(PMe3)2] with benzyl isothiocyanate gave the S-coordinated dithiocarbonimidato Pt(II) complex, [Pt(S2CN-R)(Me3P)2] (R = benzyl). In contrast, cis-[PtEt2(PMe3)2] reacted with the isothiocyanate to afford the trialkyl Pt(IV) complex [PtEt2(SCN)(CH2Ph)(PMe3)2].
- Lee, Seon Gye,Choi, Keun-Young,Kim, Yong-Joo,Park, Sujin,Lee, Soon W.
-
-
Read Online
- Fluorogenic hydrogen sulfide (H2S) donors based on sulfenyl thiocarbonates enable H2S tracking and quantification
-
Hydrogen sulfide (H2S) is an important cellular signaling molecule that exhibits promising protective effects. Although a number of triggerable H2S donors have been developed, spatiotemporal feedback from H2S release in biological systems remains a key challenge in H2S donor development. Herein we report the synthesis, evaluation, and application of caged sulfenyl thiocarbonates as new fluorescent H2S donors. These molecules rely on thiol cleavage of sulfenyl thiocarbonates to release carbonyl sulfide (COS), which is quickly converted to H2S by carbonic anhydrase (CA). This approach is a new strategy in H2S release and does not release electrophilic byproducts common from COS-based H2S releasing motifs. Importantly, the release of COS/H2S is accompanied by the release of a fluorescent reporter, which enables the real-time tracking of H2S by fluorescence spectroscopy or microscopy. Dependent on the choice of fluorophore, either one or two equivalents of H2S can be released, thus allowing for the dynamic range of the fluorescent donors to be tuned. We demonstrate that the fluorescence response correlates directly with quantified H2S release and also demonstrate the live-cell compatibility of these donors. Furthermore, these fluorescent donors exhibit anti-inflammatory effects in RAW 264.7 cells, indicating their potential application as new H2S-releasing therapeutics. Taken together, sulfenyl thiocarbonates provide a new platform for H2S donation and readily enable fluorescent tracking of H2S delivery in complex environments.
- Zhao, Yu,Cerda, Matthew M.,Pluth, Michael D.
-
-
Read Online
- Silylating Disulfides and Thiols with Hydrosilicones Catalyzed by B(C6F5)3
-
Hydrosilanes and silicones, catalyzed with B(C6F5)3, may be used to silylate thiols or cleave disulfides giving silyl thio ethers. Alcohols were found to react faster than thiols or disulfides, while alkoxysilanes (the Piers-Rubinsztajn reaction) were slower such that the overall order of reactivity was found to be HO>HS>SS>SiOEt. The resulting silane and silicone-protected thio ethers produced from the sulfur-based functional groups could be cleaved to thiols using alcohols or mild acid with rates that depend on the steric bulk of the siloxane.
- Brook, Michael A.,Liao, Mengchen,Zheng, Sijia
-
supporting information
p. 2694 - 2700
(2021/06/25)
-
- Practical and efficient recyclable oxidative system for the preparation of symmetrical disulfides under aerobic conditions
-
An efficient and practical oxidative coupling of thiols to symmetrical disulfides is developed at room temperature under aerobic conditions. The commercially available sodium methoxide solution 30 wt. % in methanol together with the air was used as a retrievable promoter system and green oxidant, respectively, for the preparation of symmetrical disulfides. The desired products were obtained in good to high yields by an economical procedure. No overoxidation of the symmetrical disulfides was observed, and various functional groups were well tolerated in the current protocol. Moreover, the new reagent reduces the generation of hazardous waste due to its high reusability. The reaction proceeded in the absence of light, and it was not inhibited by TEMPO. Also, the low yield of TEMPO-benzyl thiol adduct was detected under these conditions. Based on our experiments, a possible mechanism was proposed in the absence and presence of TEMPO.
- Ling, Ong Chiu,Heidelberg, Thorsten,Ching, Juan Joon,Khaligh, Nader Ghaffari
-
p. 281 - 294
(2020/12/13)
-
- Oxygen-to-Oxygen Silyl Migration of α-Siloxy Sulfoxides and Oxidation-Triggered Allicin Formation
-
Oxidation of α-siloxy thioethers leads to the formation of the corresponding sulfoxides as unstable intermediates, which undergo an intramolecular oxygen-to-oxygen silyl migration to break the C-S linkage. This process produces silyl protected sulfenic acids and subsequently thiosulfinates. It was used to develop oxidation-triggered allicin donors.
- Kelly, Shane S.,Shen, Tun-Li,Xian, Ming
-
p. 3741 - 3745
(2021/05/10)
-
- Direct synthesis of sulfinic esters via ultrasound accelerated tandem reaction of thiols and alcohols with N-bromosuccinimide
-
The direct transformation of various thiols and simple alcohols with N-bromosuccinimide into sulfinic esters has been investigated by using different categories of base/acidic catalysts as well as co-solvents under varied reaction conditions. The reaction was found out to afford the sulfinic esters with high yields in the absence of catalysts, especially within the shorter time under the acceleration of ultrasonic irradiation than under the longer-lasting conventional stirring conditions.
- Nguyen, Lan-Anh Thi,Le, Tri-Nghia,Duong, Cong-Thang,Vo, Chi-Tam,Duus, Fritz,Luu, Thi Xuan Thi
-
p. 519 - 528
(2021/05/27)
-
- Photoactive Metal-Organic Frameworks for the Selective Synthesis of Thioethers: Coupled with Phosphine to Modulate Thiyl Radical Generation
-
Metal-organic framework (MOF) materials are intriguing photocatalysts to trigger radical-mediated chemical transformations. We report herein the synthesis and characterization of a series of isomorphic MOFs which show a novel structure, wide visible-light absorption, high chemical stability, and specific redox potential. The prepared MOFs were explored for the photoinduced single-electron oxidation of thiol compounds, generating reactive thiyl radicals to afford thioethers via a convenient thiol-olefin reaction. Importantly, we provide a widely applicable strategy by combing a photoactive MOF with phosphine to modulate the generation of thiyl radical in the reaction, thereby producing a single product of the thioether without the formation of a disulfide byproduct due to the dimerization of thiyl radicals. The photocatalytic reaction takes advantage of this strategy, showing great generality where tens of thiols and olefins have been examined as coupling partners. In addition, the strategy has also been demonstrated to be effective for the reactions catalyzed by other MOFs. Mechanism studies reveal that the selective synthesis of C-S products relies on a synergy between the photoinduced generation of a thiyl radical over the MOF and the in situ cleavage of S-S bond into a S-H bond by phosphine. It is notable that the synthesized MOFs show advanced performance in comparison with classical MOFs. The work not only provides a series of novel MOF photocatalysts that are capable of photoinduced thiol-olefin coupling but also indicates the great potential of MOFs for photochemical transformations mediated by reactive radicals.
- Guo, Zhifen,Liu, Xin,Bai, Rong,Che, Yan,Chi, Yanhong,Guo, Chunyi,Xing, Hongzhu
-
supporting information
p. 8672 - 8681
(2021/06/28)
-
- Photogeneration of thiyl radicals using metal-halide perovskite for highly efficient synthesis of thioethers
-
Recently, the use of metal-halide perovskite (MHP) for photoinduced organics transformation has attracted much attention. We report herein the development of photoinduced thiol-ene reaction using inorganic MHP of CsPbBr3 nanocrystal that is visible light-responsive, easy-to-prepare, and cost-effective. Under blue light-emitting diode (LED), a series of thiol substrates are demonstrated to be highly efficient reaction partners to couple with alkenes tolerated with various functional groups, affording diverse thioethers containing C–S bonds. The CsPbBr3-mediated thiol-ene reaction is characterized by high efficiency, broad substrate applicability, excellent yields, and mild conditions. Mechanism investigation shows that the visible light-excited CsPbBr3 induces the generation of thiyl radicals via hole oxidation to initiate the reaction, followed by redox neutral pathway and/or chain transfer pathway to accomplish thiol–olefin coupling. It is notable that CsPbBr3 exhibits advanced thiol-ene performance than that using MHP analogs and others. The work presents a new exploration of MHP-mediated transformation and shows great potential of MHPs for radical chemistry.
- Bai, Rong,Che, Yan,Guo, Chunyi,Guo, Zhifen,Liu, Xin,Xing, Hongzhu
-
-
- Synthesis and reactivity of α-sulfenyl-β-chloroenones, including oxidation and Stille cross-coupling to form chalcone derivatives
-
The synthesis of a range of novel α-sulfenyl-β-chloroenones from the corresponding α-sulfenylketones, via a NCS mediated chlorination cascade, is described. The scope of the reaction has been investigated and compounds bearing alkyl- and arylthio substituents have been synthesised. In most instances, the Z α-sulfenyl-β-chloroenones were formed as the major products, while variation of the substituent at the β-carbon position led to an alteration in stereoselectivity. Stille cross-coupling with the Z α-sulfenyl-β-chloroenones led to selective formation of Z sulfenyl chalcones, while the E α-sulfenyl-β-chloroenones did not react under the same conditions. Oxidation of the Z α-sulfenyl-β-chloroenones was followed by isomerisation, leading to the E α-sulfinyl-β-chloroenones. Stille cross-coupling with the E α-sulfinyl-β-chloroenones produced the E sulfinyl chalcones. Either the E or Z sulfinyl chalcones can be obtained by altering the sequence of oxidation and Stille cross-coupling.
- Kearney, Aoife M.,Murphy, Linda,Murphy, Chloe C.,Eccles, Kevin S.,Lawrence, Simon E.,Collins, Stuart G.,Maguire, Anita R.
-
supporting information
(2021/05/04)
-
- PROCESS FOR CLEAVING SULFUR-SULFUR AND SULFUR-HYDROGEN BONDS IN ORGANIC COMPOUNDS
-
The present application provides a low-temperature process to reduce S-S and/or S-H bonds in organic compounds, including sulfur-cured elastomers, which for example, permits the de-crosslinking of the elastomer and recovery of organic polymers from inorganic constituents.
- -
-
Paragraph 0094; 00105-00107
(2020/10/31)
-
- Phenylboronic acid-catalyzed tandem construction of S-S and C-S bonds: a new method for the synthesis of benzyl disulfanylsulfone derivatives fromS-benzyl thiosulfonates
-
A unique phenylboronic acid-catalyzed dimerization-sulfonylation ofS-benzyl thiosulfonates has been disclosed. A metal-free tandem construction of S-S and C-S bonds is an operationally simple method to access a wide range of benzyl disulfanylsulfone derivatives in high to excellent yields. Moreover, the robustness of this tandem transformation has been demonstrated by gram-scale reactions, and a plausible mechanism is also proposed.
- Jannapu Reddy, Raju,Rama Krishna, Gamidi,Waheed, Md.
-
supporting information
p. 3243 - 3248
(2020/05/14)
-
- Oxidative Formation of Disulfide Bonds by a Chemiluminescent 1,2-Dioxetane under Mild Conditions
-
The oxidation of alkyl thiols to disulfides has been achieved under mild conditions using a chemiluminescent 1,2-dioxetane as a stoichiometric oxidant. Besides the mild and biocompatible reaction conditions, this approach offers the possibility to monitor the presence of thiols through oxidation and chemiluminescence of the remaining dioxetane.
- Sauer, Caroline S.,K?ckenberger, Johannes,Heinrich, Markus R.
-
p. 9331 - 9338
(2020/08/14)
-
- Unsymmetrical Disulfides Synthesis via Cs2CO3-Catalyzed Three-Component Reaction in Water
-
An unsymmetrical disulfides synthesis by Cs2CO3-catalyzed three-component coupling reaction of thioacetate, sodium thiosulfate, and benzyl halide in water is described. The safe, stable, and non-toxic Na2S2O3 was invoked as the sulfur-source, successfully avoiding the odor generation in the process of S?S bond formation. A wide range of substrate suitability and appropriate functional group tolerance were observed for the transformation. Notably, the approach reported here was compatible with various biomolecules including glucose, coumarin, and quinolinone. (Figure presented.).
- Wang, Dungai,Gao, Yuanji,Tong, Yunli,Xiong, Mingteng,Liang, Xiao,Zhu, Heping,Pan, Yuanjiang
-
supporting information
p. 4991 - 4995
(2020/09/23)
-
- Trisulfides over disulfides: Highly selective synthetic strategies, anti-proliferative activities and sustained H2S release profiles
-
Temperature-and solvent-induced selective synthesis of trisulfides and disulfides is demonstrated. A remarkable selectivity was achieved using Na2S as a sulfur-Transfer agent under mild, greener, catalyst-free and additive-free conditions. This study reveals trisulfides as a better model than disulfides in general for a sustained release of H2S and potent anti-cancer activities.
- Bhattacherjee, Debojit,Sufian, Abu,Mahato, Sulendar K.,Begum, Samiyara,Banerjee, Kaustav,De, Sharmistha,Srivastava, Hemant Kumar,Bhabak, Krishna P.
-
supporting information
p. 13534 - 13537
(2019/11/14)
-
- PHOTOCATALYTIC SYSTEM AND APPLICATIONS THEREOF
-
The present invention relates to novel poly(heptazine imides), a photocatalytic system comprising such poly(heptazine imides) and a sulfur source as well as the application thereof in photocatalytic reactions.
- -
-
Page/Page column 27; 28; 29; 30
(2019/05/15)
-
- First use of an organobismuth reagent in C(sp3)–S bond formation: Access to aryl cyclopropyl sulfides via copper-catalyzed S–Cyclopropylation of thiophenols using tricyclopropylbismuth
-
The direct S-cyclopropylation of thiophenols using tricyclopropylbismuth is reported. The reaction is catalyzed by copper(II) acetate and operates under mild conditions to afford the corresponding aryl cyclopropyl sulfides in moderate to good yields. This reaction represents the first use of an organobismuth reagent in C(sp3)–S bond formation.
- Benoit, Emeline,Bueno, Bianca,Choinière, Catherine,Gagnon, Alexandre
-
supporting information
p. 72 - 77
(2019/05/15)
-
- Acyl Selenyl Sulfides as the Precursors for Reactive Sulfur Species (Hydrogen Sulfide, Polysulfide, and Selenyl Sulfide)
-
Persulfides are receiving increased attention due to their links to hydrogen sulfide (H2S) and hydrogen polysulfide (H2Sn). Their close analogues selenyl sulfides (RSeSHs), however, have limited literature precedent, and their reactivity and possible role in biology are largely unknown. Here, we devised an acyl selenyl sulfide template to study RSeSH chemistry. Their stability and reactivity toward amines/thiols were studied. These compounds can produce H2S or H2S2 under different conditions, suggesting that RSeSHs are possible intermediates.
- Hamsath, Akil,Wang, Yingying,Yang, Chun-Tao,Xu, Shi,Ca?edo, Danica,Chen, Wei,Xian, Ming
-
p. 5685 - 5688
(2019/08/01)
-
- Cyclic Sulfenyl Thiocarbamates Release Carbonyl Sulfide and Hydrogen Sulfide Independently in Thiol-Promoted Pathways
-
Hydrogen sulfide (H2S) is an important signaling molecule that provides protective activities in a variety of physiological and pathological processes. Among the different types of H2S donor compounds, thioamides have attracted attention due to prior conjugation to nonsteroidal anti-inflammatory drugs (NSAIDs) to access H2S-NSAID hybrids with significantly reduced toxicity, but the mechanism of H2S release from thioamides remains unclear. Herein, we reported the synthesis and evaluation of a class of thioamide-derived sulfenyl thiocarbamates (SulfenylTCMs) that function as a new class of H2S donors. These compounds are efficiently activated by cellular thiols to release carbonyl sulfide (COS), which is quickly converted to H2S by carbonic anhydrase (CA). In addition, through mechanistic investigations, we establish that COS-independent H2S release pathways are also operative. In contrast to the parent thioamide-based donors, the SulfenylTCMs exhibit excellent H2S releasing efficiencies of up to 90percent and operate through mechanistically well-defined pathways. In addition, we demonstrate that the sulfenyl thiocarbamate group is readily attached to common NSAIDs, such as naproxen, to generate YZ-597 as an efficient H2S-NSAID hybrid, which we demonstrate releases H2S in cellular environments. Taken together, this new class of H2S donor motifs provides an important platform for new donor development.
- Pluth, Michael D.,Steiger, Andrea K.,Zhao, Yu
-
supporting information
(2019/09/06)
-
- Sodium Iodide Mediated Oxysulfenylation of Olefins with Thiosulfates: A Strategy for Constructing Sulfenylated 2,3-Dihydrobenzofurans and β-Acetoxy Sulfides
-
A strategy has been developed for constructing sulfenylated 2,3-dihydrobenzofurans and β-acetoxy sulfides through NaI/DMSO-mediated oxysulfenylation of alkenes with environmentally friendly thiosulfates. The reactions involve simple operations and give a series of sulfenylated 2,3-dihydrobenzofurans or β-acetoxy sulfides in moderate to good yields.
- Zhang, Rongxing,Yan, Zhaohua,Lin, Sen
-
supporting information
p. 336 - 339
(2017/10/30)
-
- HBr/H2O2-mediated formation of C–S bond with thiosulfates
-
A novel, efficient, and green protocol to construct C–S bond has been developed via HBr/H2O2-mediated sulfenylation of styrenes and 4-hydroxycoumarins leading to unsymmetrical sulfides. Various unsymmetrical sulfides were prepared in one step with moderate to good yields using environmentally-friendly H2O2 as oxidant and HBr as catalyst. Based on the preliminary experimental results, a plausible reaction mechanism was proposed for HBr/H2O2-mediated formation of C–S bond with thiosulfates.
- Zhang, Rongxing,Jin, Shengzhou,Wan, Yuanxing,Lin, Sen,Yan, Zhaohua
-
p. 841 - 847
(2018/02/06)
-
- A rapid, efficient and green procedure for transformation of alkyl halides/ tosylates to organochalcogens in water
-
A one-pot and efficient synthesis of dialkyl dichalcogenides (S, Se) in aqueous media under catalyst-free conditions using benzylic, allylic and primary halides with elemental sulfur and selenium has been developed. Also, this procedure was extended to preparation of trisulfides and triselenides from secondary and tertiary halides in same condition. In all cases, products can be obtained in good to excellent yield in short reactions time.
- Soleiman-Beigi, Mohammad,Yavari, Issa,Sadeghizadeh, Fatemeh
-
-
- A novel dual-nano assisted synthesis of symmetrical disulfides from aryl/alkyl halides
-
Here, we have reported a novel approach towards dual-nano assisted synthesis of disulfides from coupling of alkyl/aryl halides and sulfur nanoparticles. The indium oxide nanoparticles as catalyst expedite the conversion and sulfur nanoparticle notably enhances the miscibility, providing a faster, high yielding and cost-effective process in ethanol-water system. The method has synthetic advantages in terms of mild reaction framework, catalyst regeneration, and absence of any sulfide or polysulfide linkage as by-product leading to a column free synthesis. A variety of alkyl, aryl and heteroaryl symmetrical disulfides are obtained in good to excellent yields up to exceeding 98%.
- Devi, Namita,Hazarika, Sukanya,Gogoi, Prasanta,Barman, Pranjit
-
supporting information
p. 1927 - 1938
(2018/07/21)
-
- Thermal conversion of primary alcohols to disulfides: Via xanthate intermediates: An extension to the Chugaev elimination
-
Primary alcohols are converted into dialkyl disulfides via heating in situ generated O-alkyl S-difluoro(ethoxycarbonyl)methyl xanthates from ethyl bromodifluoroacetate and potassium xanthates, prepared from primary alcohols and carbon disulfide in the presence of KOH. The reaction mechanism is suggested as an alkyl C[1,3] shift followed by a radical mechanism. This extends to the Chugaev elimination which yields olefins. The current research provides easy access to dialkyl disulfides from commercially available primary alkanols.
- He, Wei,Ding, Yong,Tu, Jianzhuo,Que, Chuqiang,Yang, Zhanhui,Xu, Jiaxi
-
p. 1659 - 1666
(2018/03/21)
-
- Electrochemical synthesis of methyl sulfoxides from thiophenols/thiols and dimethyl sulfoxide
-
A new route for a one-pot synthesis of methyl sulfoxides from thiophenols/thiols and dimethyl sulfoxide using an electrochemical technique was developed. This protocol proceeded smoothly by employing electrons and hydrogen peroxide as clean oxidants, and a wide range of aromatic and aliphatic sulfoxides were synthesized in moderate to good yields.
- Du, Ke-Si,Huang, Jing-Mei
-
supporting information
p. 1405 - 1411
(2018/03/27)
-
- A waiting carbon nitride radical anion: A charge storage material and key intermediate in direct C-H thiolation of methylarenes using elemental sulfur as the s -source
-
Potassium poly(heptazine imide), a carbon nitride based semiconductor with high structural order and a valence band potential of +2.2 V vs. NHE, in the presence of hole scavengers and under visible light irradiation gives the corresponding polymeric radical anion, in which the specific density of unpaired electrons reaches 112 μmol g-1. The obtained polymeric radical anion is stable under anaerobic conditions for several hours. It was characterized using UV-vis absorption, time resolved and steady state photoluminescence spectra. The electronic structure of the polymeric radical anion was confirmed by DFT cluster modelling. The unique properties of potassium poly(heptazine imide) for storing charges were employed in visible light photocatalysis. A series of substituted dibenzyldisulfanes was synthesized in 41-67% yield from the corresponding methylarenes via cleavage of the methyl C-H bond under visible light irradiation and metal-free conditions.
- Savateev, Aleksandr,Kurpil, Bogdan,Mishchenko, Artem,Zhang, Guigang,Antonietti, Markus
-
p. 3584 - 3591
(2018/04/12)
-
- Visible-Light-Triggered C-C and C-N Bond Formation by C-S Bond Cleavage of Benzylic Thioethers
-
The cleavage of sulfidic C-S bonds under visible-light irradiation was harnessed to generate carbocations under neutral conditions and synthesize valuable di- and triarylalkanes as well as benzyl amines. To this end, photoredox catalysis and direct photoinduced C-S bond cleavage are used as complementary approaches and participate in the versatility of the general strategy. Extensive mechanistic studies have demonstrated the diversity of the reaction mechanism at work in these different reactions.
- Lanzi, Matteo,Merad, Jérémy,Boyarskaya, Dina V.,Maestri, Giovanni,Allain, Clémence,Masson, Géraldine
-
supporting information
p. 5247 - 5250
(2018/09/13)
-
- Simple and green method for synthesis of symmetrical dialkyl disulfides and trisulfides from alkyl halides in water; PMOxT as a sulfur donor
-
An environmentally new, mild and efficient method has been developed for the synthesis of dialkyl disulfides and dialkyl trisulfides in aqueous conditions by a reaction between alkyl halides (and tosylate) and potassium-5-methyl-1,3,4-oxadiazole-2-thiolate (PMOxT) as a sulfur transfer reagent. The advantages of this method are that it occurs under mild reaction conditions, it is base free, it uses water as the solvent and it occurs in high yields. A variety of dialkyl disulfides and dialkyl trisulfides can be obtained in good to excellent yields up to 98%.
- Soleiman-Beigi, Mohammad,Mohammadi, Fariba
-
p. 134 - 141
(2017/03/07)
-
- Europhtal (8020) efficiently catalyzes the aerobic oxidation of in situ generated thiols to symmetric disulfides (disulfanes)
-
Efficient, odorless and scalable synthetic protocols have been introduced for the preparation of symmetric alkyl disulfides by treatment of the corresponding organic halides with thiourea and NaHCO3in the presence of commercially available Europhtal catalyst (8020) in both H2O and poly ethylene glycol (PEG-200) media at 80–90 °C. Structurally diverse primary, secondary, allylic and benzylic halides were examined successfully whereas, the result with tert-butyl bromide was not satisfactory. Also, another procedure has been introduced for achieving symmetric aryl disulfides in high yields by reacting aryl halides, thiourea and NaHCO3in PEG-200 at 115–120 °C using CuI along with Europhtal catalysts. The results showed that the aerobic oxidation of in situ generated thiols proceeded efficiently in the presence of Europhtal catalyst giving the symmetric disulfide without contamination by symmetric sulfide side-product.
- Abbasi, Mohammad,Sabet, Askar,Sabet, Askar
-
-
- Conversion of organic halides to disulfanes using KCN and CS2
-
A sulfur transfer reagent was produced in situ upon stirring a mixture of KCN and CS2 in DMF at r.t. for 15 min, which after heating with an alkyl halide or aryl halide and CuI gave the corresponding symmetric dialkyl or diaryl disulfide, respectively, in high to excellent yields.
- Abbasi, Mohammad,Nowrouzi, Najmeh,Borazjani, Saeedeh Ghassab
-
p. 4251 - 4254
(2017/10/11)
-
- Method for producing thionocarbamate and dibenzyl disulfide
-
The invention discloses a method for producing thionocarbamate and dibenzyl disulfide. The method comprises the following steps: carrying out an esterification reaction on alkyl xanthate and benzyl halide to obtain alkyl benzyl xanthate; carrying out an aminolysis reaction on the alkyl benzyl xanthate and fatty amine to obtain a thionocarbamate and benzyl mercaptan mixture; and carrying out an oxidation reaction on the thionocarbamate and benzyl mercaptan mixture and hydrogen peroxide, and carrying out liquid-solid separation to obtain a solid which is the dibenzyl disulfide product and a liquid, and allowing the liquid to stand for oil and water layering in order to obtain an oil phase which is the thionocarbamate product. The dibenzyl disulfide product and thionocarbamate product obtained through the method have high yield and high purity, and the method has the advantages of easiness in separation of the products in the preparation process, environmental protection, high atom economy property, low production cost, and easiness in realization of industrial production.
- -
-
-
- Diarylmethylene disulfide compound as well as preparation method and application thereof
-
The invention relates to the technical field of medicines and in particular relates to a diarylmethylene disulfide compound as well as a preparation method and application thereof. An experiment result shows that on a cell model, the diarylmethylene disulfide compound provided by the invention has an effect of inhibiting neurotoxicity caused by excessive glutamic acid and an effect of inhibiting neurotoxicity caused by hydrogen peroxide; the diarylmethylene disulfide compound also has a platelet aggregation resisting effect and can be used for reducing a cerebral infarct area in a mouse MCAO (Middle Cerebral Artery Occlusion) model. The results show that the diarylmethylene disulfide compound provided by the invention can have prevention and/or treatment effects on cerebral stroke.
- -
-
Paragraph 0055; 0056; 0057; 0058; 0059; 0060; 0061; 0062; 00
(2018/01/03)
-
- Thiol Reactivity toward Atomic Oxygen Generated during the Photodeoxygenation of Dibenzothiophene S-Oxide
-
Aromatic heterocyclic oxides, such as dibenzothiophene S-oxide (DBTO), have been suggested to release ground state atomic oxygen [O(3P)] upon irradiation, and as such, they have been used to create a condensed phase reactivity profile for O(3P). However, thiols, which are highly reactive with O(3P) in the gas phase, were not previously investigated. An earlier study of O(3P) with proteins in solution indicated a preference for thiols. A further investigation of the apparent thiophilicity provided the subject for this study. DBTO was employed as a putative O(3P)-precursor. However, the effective rate of O(3P) formation was found to be dependent on reactant concentrations in certain cases. All reactants were found to increase the rate of deoxygenation to some extent, but in the presence of reactants containing an alcohol linked to a reactive functional group, deoxygenation occurred substantially more rapidly. The rate enhancement was quantified and attributed to the reaction of activated O atom within the solvent cage prior to escape into the bulk solution. Through competition experiments, the relative rate constants of O(3P) with thiols and other functional groups were found. A small preference for primary thiols was observed over other thiols, sulfides, and alkenes. A much larger preference was observed for thiols, sulfides, and alkenes over aromatic groups. In summary, DBTO was successfully used as an O(3P)-precursor, and the thiophilicity of O(3P) was confirmed and quantified.
- Omlid, Sara M.,Zhang, Miao,Isor, Ankita,McCulla, Ryan D.
-
p. 13333 - 13341
(2017/12/15)
-
- Microwave-assisted direct thioesterification of carboxylic acids
-
A one-pot synthesis of thioesters directly from carboxylic acids, N,N′-diphenylthiourea, triethylamine, and primary alkyl halides is described. Microwave-assisted heating and a catalytic amount of 4- (dimethylamino)pyridine (DMAP) further improved the yields. Both aromatic and aliphatic carboxylic acids were converted to the corresponding thioesters, and many functional groups were compatible with this reaction. Several possible reaction intermediates were investigated, and the quaternary ammonium salts, derived from alkyl halides and tertiary amines, were the intermediates to yield thioesters. A new reaction mechanism for this thioesterification is proposed.
- Chou, Yen-Lin,Jhong, Yi,Swain, Sharada Prasanna,Hou, Duen-Ren
-
p. 10201 - 10208
(2018/05/31)
-
- Electrochemical synthesis of organochalcogenides in aqueous medium
-
The electrochemical preparation of telluride, selenide and sulfide ions was carried out in NaOH aqueous solution, using a two compartment cell. Organochalcogenides were prepared from halogenated compounds in a two-step procedure. The monochalcogenides were obtained as the major products in good yields.
- Ribeiro Neto, Pedro B.,Santana, Sonydelane O.,Levitre, Guillaume,Galdino, Danilo,Oliveira, Jadson L.,Ribeiro, Rogério T.,Barros, Maria E. S. B.,Bieber, Lothar W.,Menezes, Paulo H.,Navarro, Marcelo
-
supporting information
p. 657 - 661
(2016/02/12)
-
- The synthesis of symmetrical disulfides by reacting organic halides with Na2S2O3·5H2O in DMSO
-
A one-pot, and scalable method to prepare symmetric disulfides from their corresponding primary, secondary, allylic, and benzylic halides has been developed. In this method, a disulfide is synthesized by reacting an alkyl halide with Na2S2O3·5H2O at 60-70 °C in DMSO.
- Abbasi, Mohammad,Mohammadizadeh, Mohammad Reza,Saeedi, Narges
-
supporting information
p. 89 - 92
(2016/01/12)
-
- One-pot conversion of alkyl halides to organic disulfides (disulfanes) using thiourea and hexamethyldisilazane (HMDS) in DMSO
-
A practical method to synthesize symmetric disulfides from alkyl halides has been developed. Using this procedure primary, secondary, benzylic and allylic disulfides were prepared by treating the corresponding alkyl halides with thiourea and HMDS in DMSO at 50 °C within 10-24 h in high yields.
- Abbasi, Mohammad,Jabbari, Arida
-
-
- Symmetrical disulfide synthesis via nickel-catalysis using potassium sulfide as sulfur source
-
Abstract: An efficient one-pot method for the synthesis of organic disulfides from aryl and alkyl halides and potassium sulfide has been described. K2S acts as an inexpensive and readily available sulfur source. A variety of symmetric diaryl and dialkyl disulfides was prepared in good to excellent yields using NiCl2·6H2O and acetylacetone as the catalytic system. Graphical abstract: [Figure not available: see fulltext.]
- Soleiman-Beigi, Mohammad,Arzehgar, Zeinab
-
p. 1759 - 1763
(2016/09/28)
-
- An efficient domino Cu-mediated access to organic disulfides from aryl/alkyl halides: Sodium thiosulfate used as a sulfurating reagent
-
Background: We have developed a one-pot, simple and efficient protocol for the direct synthesis of symmetrical organic disulfides in high yields via domino reaction between aryl/alkyl halides and Sodium thiosulfate as the sulfur source, in the presence of copper/imidazole and K2CO3. Methods: Owing to the importance seen in the synthesis disulfides, as is evident from the number of publications in the recent past, and our continuing interest in the synthesis of organosulfur compounds using direct synthesis and domino reaction. Herein we designed the synthesis of various disulfide using reaction of aryl/alkyl halides with sodium thiosulfate in presence CuI catalyst, K2CO3 and imidazol as ligand in solvent DMSO. The reaction of iodobenzene with sodium thiosulfate was studied under normal atmospheric conditions in order to optimize the reaction conditions in terms of temperature, amount of reagent and catalyst, and the type of ligand. Results: Effect of solvent and ligand was perceptible, The reaction proceeded not well in the absence of a ligand. The best ligand for these reaction was imidazole. The various solvents tested in this investigation. It was observed that excellent yield of the product was obtained when the reaction was carried out by using DMSO as solvent. The reaction no proceeded in the absence of a base. K2CO3 was a good choice. We examined various amount of the copper salt. It was found to be the best choice in presence 0.7 mmol from copper salt. Also it was significantly found that the reaction yield and rate increased with temperature. The reaction favoured at 130°C temperature. The 3 mmol Na2S2O3·5H2O concentration was sufficient to give maximum yield of the required product in comparison with other amounts. Diaryl/alkyl disulfides were synthesized in terms of the connecting and type position of the substituents on the aryl/alkyl groups, so that products with different substituents, both electron withdrawing and electron-donating substituent, were synthesized in the ortho, meta and para positions. The results show that iodobenzene and bromobenzene were effective for the reaction. Although it was seen that the reaction cannot progress with compound of aryl chloride. Symmetrical diheteroaryl disulfides were well synthesized from the corresponding heteroaryl iodides, bromides and chlorides. Conclusion: In summary, we have developed a new and effective method for the direct synthesis of diaryl/alkyl disulfides from various aryl/alkyl halides by domino reaction. In this work reports an effective and cheap metal catalyzed sulfur transfer reaction, which is more economic, and more environmentally friendly and more comprehensive than previous methods. As a novel sulfur source, Na2S2O3 shows notable advantage in this system. This reaction functions under mild conditions, and various functional groups are well tolerated.
- Soleiman-Beigi, Mohammad,Basereh, Ali,Mohammadi, Fariba
-
p. 706 - 710
(2017/02/05)
-
- Phase-vanishing method with gas evolution and its application to organic synthesis
-
Using a phase-vanishing (PV) system, hydrogen, oxygen, and hydrogen sulfide generated in situ from CaH2, KO2, and P2S5, respectively, were directly reacted with substances in the organic phase to afford the desired products. The selective synthesis of sulfides and disulfides was achieved with the evolution of H2S gas via tuning the bases used in the PV method. Using this PV system, reactions with hazardous gaseous reagents can be carried out easily and safely in a common test tube.
- Matake, Ryosuke,Niwa, Yuki,Matsubara, Hiroshi
-
p. 672 - 675
(2016/01/26)
-
- Synthesis of Disulfanes from Organic Thiocyanates Mediated by Sodium in Silica Gel
-
We report an efficient procedure for the synthesis of symmetrical disulfanes from organic thiocyanates in the presence of sodium in silica gel at room temperature. By avoiding the use of foul-smelling thiols, the present protocol provides an attractive alternative to existing methods for the preparation of symmetrical disulfanes.
- Maurya, Chandra Kant,Mazumder, Avik,Kumar, Ajeet,Gupta, Pradeep Kumar
-
p. 409 - 411
(2016/02/09)
-
- Alternative Protocol for the Synthesis of Symmetrical Dibenzyl Diselenides and Disulfides
-
A one-pot protocol for the preparation of symmetrical dibenzyl diselenides and disulfides from the corresponding benzyl alcohols employing NaBH2Se3 and NaBH2S3 as selenium-transfer and sulfur-transfer reagent, respectively, is described. Structurally diverse substituted benzyl alcohols afforded the corresponding diselenides and disulfides in good to excellent yields. The protocol is simple and mild, and the products were obtained within a short reaction time.
- Panduranga, Veladi,Prabhu, Girish,Panguluri, Nageswara Rao,Sureshbabu, Vommina V.
-
p. 1711 - 1718
(2016/06/01)
-
- DCDMH-promoted synthesis of thiophosphates by coupling of H-phosphonates with thiols
-
DCDMH-mediated phosphorylation of versatile thiols with H-phosphonates for the preparation of synthetically and biologically important thiophosphates was demonstrated. Without metal catalysts and other additives, phosphorylation occurred to give the desired products with good to excellent yields within 10 min at ambient temperature in the air.
- Bi, Xiaojing,Li, Junchen,Meng, Fanhua,Wang, Hongmei,Xiao, Junhua
-
supporting information
p. 706 - 711
(2016/01/15)
-
- Electrochemical synthesis of aromatic sulfur compounds in ionic liquids
-
Electrochemical properties of ionic liquids (pyridinium and imidazolium salts) and the effect of additives of organic solvents on the electrochemical determination of organic compounds in ionic liquids have been studied. Transformations of aromatic and aliphatic sulfur compounds in ionic liquids in the presence of aromatic substrates are discussed. A new method has been proposed for identification of organic sulfur compounds-gas chromatography on columns with ionic liquid as the active phase.
- Okhlobystina,Okhlobystin,Letichevskaya,Abdulaeva,Movchan,Berberova
-
p. 291 - 295
(2016/04/20)
-
- Hemithioketal formation of vicinal tricarbonyl compound with thiols and their recovery
-
In this paper, we report hemithioketal formation of diphenylpropanetrione (DPPT) with thiols and their recovery. Addition of thiols to the central carbonyl group occurred readily at ambient temperature to provide the thiol adducts of DPPT (DPPT–thiols), which has a hemithioketal structure. On the other hand, oxidizing DPPT–thiols with an oxidation reagent enabled successful recovery of DPPT, which indicated the reversible nature of this system.
- Yuki, Tatsuya,Yonekawa, Morio,Matsumoto, Kozo,Sei, Yoshihisa,Tomita, Ikuyoshi,Endo, Takeshi
-
p. 4783 - 4788
(2016/07/18)
-
- Visible light mediated reductions of ethers, amines and sulfides
-
Visible light-mediated photoredox catalysis enables the chemoselective reduction of activated carbon–heteroatom bonds as a function of reduction potential. The expansion of the scope of C–X bond reductions towards less activated motifs, such as ethers, amines and sulfides, is important to both organic synthesis and macromolecular degradation method development. In the present report, exploration of photoredox catalysis in alcoholic solvents mediated a decrease in the super-stoichiometric use of iPr2NEt and HCO2H in the reduction of α-keto ethers, amines and sulfides. Additionally, in the absence of fragmentation, [Formula presented] bond formation was afforded, suggesting an intermediate ketyl radicals are present in these transformations.
- Monos, Timothy M.,Magallanes, Gabriel,Sebren, Leanne J.,Stephenson, Corey R.J.
-
p. 240 - 248
(2016/07/21)
-
- Activation of heteroallenes by coordinatively unsaturated nickel(II) alkyl complexes supported by the hydrotris(3-phenyl-5-methyl)pyrazolyl borate (TpPh,Me) ligand
-
Activation of sulfur containing heteroallenes by nickel(ii) alkyl complexes supported by the bulky hydrotris(3-phenyl-5-methylpyrazolyl)borate (TpPh,Me) ligand is described. Exposure of TpPh,MeNiCH2Ph (1a) and TpPh,MeNiCH2Si(CH3)3 (1b) to CS2 resulted in formation of the insertion products TpPh,MeNi(η2-CS2)CH2Ph (2a) and TpPh,MeNi(η2-CS2)CH2Si(CH3)3 (2b) in moderate yields. Reaction of 1a and MeNCS produced two species in a 1:1 ratio, identified as TpPh,MeNi(η2-MeNC)CH2Ph (3) and TpPh,MeNi(η2-MeNCS)SCH2Ph (4). Isolation of the unexpected insertion product (3) prompted an investigation into the activity of 1a-b in the presence of isocyanides (i.e.tBuNC), which resulted in isolation of TpPh,MeNi(η2-tBuNC)CH2Ph (5a) and TpPh,MeNi(η2-tBuNC)CH2Si(CH3)3 (5b). Similarly, reaction of 1a with OCS led to the isolation of a rare example of a Ni(i) carbonyl species TpPh,MeNiCO (6). Alternatively, complex 6 was also formed by exposure of 1a-b to an atmosphere of CO. Isolation of the intermediate species (TpPh,MeNi(η2-CO)CH2TMS (7b) and TpPh,MeNi(CO)(C(O)R, (8a-b) with R = Ph, TMS)) shed light on the formation of such species.
- Abubekerov, Mark,Eymann, Léonard Y. M.,Gianetti, Thomas L.,Arnold, John
-
p. 14581 - 14590
(2016/10/03)
-
- Selective synthesis of thioethers in the presence of a transition-metal-free solid Lewis acid
-
The synthesis of thioethers starting from alcohols and thiols in the presence of amorphous solid acid catalysts is reported. A silica alumina catalyst with a very low content in alumina gave excellent results in terms of both activity and selectivity also under solvent-free conditions. The reaction rate follows the electron density of the carbinol atom in the substrate alcohol and yields up to 99% and can be obtained for a wide range of substrates under mild reaction conditions.
- Santoro, Federica,Mariani, Matteo,Zaccheria, Federica,Psaro, Rinaldo,Ravasio, Nicoletta
-
supporting information
p. 2627 - 2635
(2017/01/09)
-