- Exploring Regioselective Bond Cleavage and Cross-Coupling Reactions using a Low-Valent Nickel Complex
-
Recently, esters have received much attention as transmetalation partners for cross-coupling reactions. Herein, we report a systematic study of the reactivity of a series of esters and thioesters with [{(dtbpe)Ni}2(μ-η2:η2-C6H6)] (dtbpe=1,2-bis(di-tert-butyl)phosphinoethane), which is a source of (dtbpe)nickel(0). Trifluoromethylthioesters were found to form η2-carbonyl complexes. In contrast, acetylthioesters underwent rapid Cacyl-S bond cleavage followed by decarbonylation to generate methylnickel complexes. This decarbonylation could be pushed backwards by the addition of CO, allowing for regeneration of the thioester. Most of the thioester complexes were found to undergo stoichiometric cross-coupling with phenylboronic acid to yield sulfides. While ethyl trifluoroacetate was also found to form an η2-carbonyl complex, phenyl esters were found to predominantly undergo Caryl-O bond cleavage to yield arylnickel complexes. These could also undergo transmetalation to yield biaryls. Attempts to render the reactions catalytic were hindered by ligand scrambling to yield nickel bis(acetate) complexes, the formation of which was supported by independent syntheses. Finally, 2-naphthyl acetate was also found to undergo clean Caryl-O bond cleavage, and although stoichiometric cross-coupling with phenylboronic acid proceeded with good yield, catalytic turnover has so far proven elusive. The reactivity of a low-valent nickel complex with esters and thioesters is reported. Trifluoromethylthioesters were found to form η2-carbonyl complexes, while acetylthioesters were found to undergo further Cacyl-S oxidative addition and decarbonylation to generate methylnickel complexes. In contrast, the same nickel precursor was found to induce Caryl-O bond cleavage in aryl esters to generate arylnickel acetate complexes (see scheme).
- Desnoyer, Addison N.,Friese, Florian W.,Chiu, Weiling,Drover, Marcus W.,Patrick, Brian O.,Love, Jennifer A.
-
-
Read Online
- Synthesis, Electronic Structure, and Reactivities of Two-Sulfur-Stabilized Carbones Exhibiting Four-Electron Donor Ability
-
Bis(sulfane)carbon(0) (BSC; Ph2S→C←SPh2 (1)) is successfully synthesized by deprotonation of the corresponding protonated salt 1?HTfO. The diprotonated salt 1?(HTfO)2 as the starting material can be also easily accessed by
- Morosaki, Tomohito,Iijima, Ryo,Suzuki, Tsubasa,Wang, Wei-Wei,Nagase, Shigeru,Fujii, Takayoshi
-
-
Read Online
- The reaction of 4,5-dichloro-1,2,3-dithiazolium chloride with DMSO: an improved synthesis of 4-chloro-1,2,3-dithiazol-5H-one
-
4,5-Dichloro-1,2,3-dithiazolium chloride 2 (Appel salt) reacts with either DMSO, diphenylsulfoxide 11 or methylphenylsulfoxide 12 to give 4-chloro-5H-1,2,3-dithiazol-5-one 1 in excellent yields. The use of catalytic amounts of DMSO (1 mol %) in MeCN in th
- Kalogirou, Andreas S.,Koutentis, Panayiotis A.
-
-
Read Online
- Reaction of benzyne with formamides and acetylimidazole
-
The reaction of DMF with o-trimethylsilylphenyl triflate in the presence of CsF afforded dimethyldiphenylammonium triflate, xanthene, and xanthone in 62%, 16%, and 24% yields, respectively. On the other hand, the reaction of dimethylthioformamide with triflate and CsF resulted in diphenyl sulfide, xanthene, and xanthone in 62%, 10%, and 12% yields, respectively. The reaction of acetylimidazole with benzyne gave 9-N,N-diphenylaminoanthracene in 85% yield.
- Okuma, Kentaro,Nojima, Akiko,Nakamura, Yuki,Matsunaga, Nahoko,Nagahora, Noriyoshi,Shioji, Kosei
-
-
Read Online
- Concerted aryl-sulfur reductive elimination from PNP pincer-supported Co(iii) and subsequent Co(i)/Co(iii) comproportionation
-
This report discloses a combined experimental and computational study aimed at understanding C-S reductive elimination from Co(iii) supported by a diarylamido/bis(phosphine) PNP pincer ligand. Divalent (PNP)Co-aryl complexes could be easily oxidized to five-coordinate Co(iii) derivatives, and anion metathesis provided five-coordinate (PNP)Co(Ar)(SAr′) complexes of Co(iii). In contrast to their previously described (POCOP)Co(Ar)(SAr′) analogs, but similarly to the (PNP)Rh(Ar)(SAr′) and (POCOP)Rh(Ar)(SAr′) analogs, (PNP)Co(Ar)(SAr′) undergo C-S reductive elimination with the formation of the desired diarylsulfide product ArSAr′. DFT studies and experimental observations are consistent with a concerted process. However, in contrast to the Rh analogs, the immediate product of such reductive elimination, the unobserved Co(i) complex (PNP)Co, un-dergoes rapid comproportionation with the (PNP)Co(Ar)(SAr′) starting material to give Co(ii) compounds (PNP)Co-Ar and (PNP)Co-SAr′.
- Foley, Bryan J.,Palit, Chandra Mouli,Bhuvanesh, Nattamai,Zhou, Jia,Ozerov, Oleg V.
-
-
Read Online
- A stable amine functionalized montmorillonite supported Cu, Ni catalyst showing synergistic and co-operative effectiveness towards C-S coupling reactions
-
The objective of this work is to prepare a cheap and highly stable heterogeneous catalyst. This was done by a simple two step approach. The first step involved the preparation of an organic-inorganic hybrid material by covalent grafting of amines on K10 m
- Varadwaj, G. Bishwa Bidita,Rana, Surjyakanta,Parida
-
-
Read Online
- Cyclopropyl-containing photoacid generators for chemically amplified resists
-
Several cyclopropyl-containing photoacid generators (PAGs) were synthesized in order to reduce absorbance at 193 nm and induce the photobleaching effect. From the GC-mass experiment, cleavage of S-C(cyclopropyl) which is more preferential than that of S-C
- Kim, Jin-Baek,Jang, Ji-Hyun,Kim, Hyun-Woo,Woo, Sang-Gyun
-
-
Read Online
- A novel synthesis of diaryl sulfides
-
Reaction of diphenyl disulfide and aryl iodides or diiodides at high temperature affords phenyl aryl sulfides or bis(phenylthio)arenes in good yields. Thermolysis of dialkyl disulfide with aryl iodides yields only diaryl sulfides.
- Wang,Hay
-
-
Read Online
- High activity and stability in the cross-coupling of aryl halides with disulfides over Cu-doped hierarchically porous zeolite ZSM-5
-
A Cu-doped zeolite ZSM-5 (Cu-ZSM-5-M) with a micro-meso-macroporous structure was directly synthesized, and it exhibits excellent catalytic activity and good recyclability in the cross-coupling of aryl halides with diphenyl disulfides. This feature should be attributed to the structural characteristics of meso-macropores and homogeneous dispersion of active Cuδ+ (δ 2) species in Cu-ZSM-5-M.
- Fu, Wenqian,Liu, Taotao,Fang, Zhongxue,Ma, Yuli,Zheng, Xiang,Wang, Wenchang,Ni, Xiaojun,Hu, Maolin,Tang, Tiandi
-
-
Read Online
- Room-temperature carbon-sulfur bond formation from Ni(II) σ-aryl complex via cleavage of the S-S bond of disulfide moieties
-
The formation of ArSY (Y: C(= S)NMe2, Ph, P(= O)(OEt) 2) by reductive elimination from σ-aryl complexes (M(PPh 3)2PhBr, M = Ni, Pd), associated with disulfides (YS-SY, Y: C(=S)NMe2 (1), Ph (2), P(=O)(OEt)2 (3)), at ambient temperature, has been investigated. Various mechanistic features of disulfide bond (S-S) cleavage have been elucidated using disulfide 1 by 31P NMR spectroscopy and matrix-assisted laser desorption/ionization-time of flight mass spectrometric investigations. Based upon the results of nucleophilic cleavage of the S-S bond by PPh3, studies of the reductive elimination process show that when M(PPh3)2PhBr is mixed with disulfide 1, competitive reactions occur between the PPh3 ligand, disulfide 1 and a trace amount of water, leading to low C-S coupling yields; an oxidation reaction of PPh3 with disulfide and water occur prior to C-S cross-coupling, and phosphonium ion intermediates are likely involved. However, when the disulfide 1 is pretreated with PPh3, the Ni(II) σ-aryl complex affords the C-S coupling product nearly quantitatively at room temperature. The pretreatment method is also effective for the coupling reaction of disulfide 2 and Ni(II) σ-aryl complex. The difference between Ni(II) and Pd(II) σ-aryl complexes on C-S bond formation by reductive elimination can be explained by the affinity of metal for the thiolate ligands derived from the cleaved disulfide. Copyright 2013 John Wiley & Sons, Ltd. The formation of ArSY (Y: C(= S)NMe2, Ph, P(= O)(OEt)2) by reductive elimination from σ-aryl complexes (M(PPh3)2PhBr, M = Ni, Pd) at ambient temperature, has been investigated, a result that shows an effective C-S cross-coupling reaction. Copyright
- Okamoto, Ken,Housekeeper, Jeremy B.,Luscombe, Christine K.
-
-
Read Online
- Superelectrophilic Activation of Crotonic/Methacrylic Acids: Direct Access to Thiochroman-4-ones from Benzenethiols by Microwave-Assisted One-Pot Alkylation/Cyclic Acylation
-
An efficient microwave-assisted protocol for the synthesis of 2-/3-methylthiochroman-4-ones by superacid-catalyzed alkylation followed by cyclic acylation (cyclization via intramolecular acylation) is described. Using easily accessible benzenethiols and crotonic acid/methacrylic acid with triflic acid (as catalyst of choice for needed optimal acidity), the reaction was tuned toward the formation of the cyclized products in good selectivity and yield. A mechanism involving the formation of carbenium-carboxonium superelectrophilic species is suggested.
- Vaghoo, Habiba,Prakash, G. K. Surya,Narayanan, Arjun,Choudhary, Rohit,Paknia, Farzaneh,Mathew, Thomas,Olah, George A.
-
-
Read Online
- Thermal fragmentation and rearrangement of β-ketosulfide and β-ketosulfone derivatives
-
Thermal fragmentation and rearrangement of neat phenacyl aryl sulfides I and II have been thoroughly investigated and found to involve cleavage of the C-S and C-C bonds followed by a series of H-abstraction, coupling, dimerization, rearrangement, and cyclization reactions. Also, in the presence of isoquinoline as a radical trap, I gave 1-phenyl- and 1-benzylisoquinoline in addition to the rearrangement products. Analogous results, beside SO2 arylsulfonic acid and biaryl, were also obtained on heating phenacyl aryl sulfones III and IV in tetraline. A suitable mechanism has been suggested to account for the isolated products.
- Gaber, Abd El-Aal M.
-
-
Read Online
- Cu-Catalyzed o-Amino Benzofuranthioether Formation from N-Tosylhydrazone-Bearing Thiocarbamates and Arylative Electrophiles
-
An important framework of o-amino benzofuranthioethers was constructed by Cu-catalyzed arylative cyclization of N-tosylhydrazone-bearing thiocarbamates with silylaryl triflates or ArI. This transformation provides a novel strategy for the synthesis of valuable arylative o-amino benzofuranthioethers in moderate yields which could not be obtained from known methods. The reaction features smart design, efficient construction, and mild reaction conditions.
- Li, Xue,Mai, Shaoyu,Li, Xin,Xu, Jian,Xu, Hetao,Song, Qiuling
-
-
Read Online
- Synthesis and catalytic properties of a heterocyclic-carbene complex of palladium
-
The palladium N-heterocyclic carbene complex trans-[PdCl 2{1,3-bis(2,6-diisopropylphenyl)-imidazol-2-ylidene}(NC 5H5)] has been prepared and its X-ray molecular structure is reported. The complex is highly catalytically active in the cross-coupling reaction of phenylhalides with phenylthiol to afford diphenyl sulfide and is efficient for the coupling of chlorobenzene.
- Shi, Yanhui,Cai, Zhengyuan,Peng, Yu,Shi, Zhan,Pang, Guangsheng
-
-
Read Online
- PHASE-TRANSFER CATALYSIS IN THE NICKEL- AND PALLADIUM-CATALYZED FORMATION OF ARYL AND ALKENYL SULFIDES
-
Aryl and alkenyl sulfides can be conveniently prepared from the corresponding halides and alkaline thiolates under phase transfer conditions in the presence of ?-Aryl-Ni2Cl or ?-Aryl-Pd2Br.
- Foa, M.,Santi, R.,Garavaglia, F.
-
-
Read Online
- Sulfuration of organoborates, an underexploited method
-
The combination of sulfurating agents with organoboranes is an underexploited synthetic transformation. The reactivity of borate complexes was investigated with several electrophilic sulfur species. Simple and practical methods for making carbon-sulfur bonds were created under almost neutral conditions. These enjoy a heavy metal-free environment and use not so toxic boron compounds. This is in contrast to the manipulation of poisonous H2S or the use of sulfur with Grignard reagents, under highly basic and moisture-sensitive conditions. (C) 2000 Elsevier Science Ltd.
- Kerverdo,Gingras
-
-
Read Online
- Microwave-assisted Ullmann C-S bond formation: Synthesis of the P38α MAPK clinical candidate VX-745
-
(Chemical Equation Presented) Microwave irradiation promotes the rapid and efficient reaction of a thiophenol and aryl or heteroaryl halide using a copper or palladium catalyst and a range of ligands, depending upon substrate. Of particular utility is the use of copper(I) iodide (5 mol %) and trans-cyclohexane-1,2-diol as ligand under basic conditions and microwave irradiation to give the corresponding sulfide in high yield. This method for C-S bond formation is applied in the four-step synthesis of the clinical candidate VX-745 in 38% overall yield. The inhibitory activity of VX-745 against p38α MAPK is confirmed in Werner syndrome dermal fibroblasts at 1.0 μM concentration by immunoblot assay. 2009 American Chemical Society.
- Bagley, Mark C.,Davis, Terence,Dix, Matthew C.,Fusillo, Vincenzo,Pigeaux, Morgane,Rokicki, Michal J.,Kipling, David
-
-
Read Online
- Molybdenum oxo-peroxo complex: A very fast catalyst for oxidation and reduction of sulfur-based compounds
-
We have evaluated the catalytic activity of a molybdenum(VI) oxo-peroxo complex through the oxidation and reduction of sulfur-based compounds. Arylalkyl, diaryl and dialkyl sulfides are selectively oxidized to corresponding sulfoxides, with tert-butyl hydroperoxide (TBHP), in the presence of MoO(O 2)(phox)2 complex as catalyst. This molybdenum complex was also found to be an efficient catalyst for the deoxygenation of sulfoxides to sulfides with PPh3 in excellent yields and chemoselectivity.
- Bagherzadeh, Mojtaba,Haghdoost, Mohammad Mehdi,Amini, Mojtaba,Derakhshandeh, Parviz Gohari
-
-
Read Online
- In situ synthesis of sub-nanometer metal particles on hierarchically porous metal-organic frameworks via interfacial control for highly efficient catalysis
-
In this work, we developed a strategy to in situ synthesize sub-nanometer metal particle/hierarchically mesoporous metal-organic framework (MOF) composites in emulsion. In this route, water droplets in the emulsion acted as both a solvent of the metal pre
- Zhang, Pei,Chen, Chunjun,Kang, Xinchen,Zhang, Lujun,Wu, Congyi,Zhang, Jianling,Han, Buxing
-
-
Read Online
- Preparation and Reactivities of S,S-Diaryl-S-aminothiazynes, Ar2S(NR2)(N)
-
Reaction of S,S-diaryl-S-fluorothiazynes with cyclic secondary amines gave novel thiazynes, the corresponding S-aminothiazynes in good yields.Spectroscopic studies, measurement of pKa values, pyrolysis and alkylation reactions of the aminothiazynes were carried out.
- Yoshimura, Toshiaki,Takata, Eiichi,Miyake, Takahiro,Shimasaki, Choichiro,Hasegawa, Kiyoshi,Tsukurimichi, Eiichi
-
-
Read Online
- PHOSPHA-S-TRIAZINES. X. THIOPHENYL-SUBSTITUTED PHOSPHA-S-TRIAZINES
-
A series of thiophenyl-substituted mono- and diphospha-s-triazines was prepared.These materials exhibited physical characteristics similar to those of the corresponding phenyl analogues, but the mass spectral breckdown patterns were dominated by the loss of the thiophenyl group and differed significantly from that of the other phospha-s-triazines investigated to date.The thiophenyl-phospha-s-triazines exhibited anticorrosive and antioxidative action when used as additives in perfluoroalkylether fluids.At elevated temperatures, 316 deg C, these materials were less effective than the phenyl analogues.The monophospha-members of the series were thermally and oxidatively less stable the corresponding diphospha-s-triazines: 67 versus 96percent starting material recovery after exposure to air at 235 deg C for 24 hr.Both the mono- and diphospha-s-triazines were completely degraded in 24 hr at 316 deg C in nitrogen.
- Paciorek, K. J. L.,Harris, D. H.,Nakahara, J. H.,Smythe, M. E.,Kratzer, R. H.
-
-
Read Online
- The thermal charge-transfer reduction of uranyl UO22+(VI) to UO2+(V) by various functionalized organic compounds, and evidence for possible spin-spin interactions between UO2+(V) and hydroxymethyl ([rad]CH2OH) radical and between UO2+(V) and diphenyl sulfide radical cation (Ph2S[rad]+)
-
The linear uranyl UO22+(VI) cation (D∞h symmetry) exhibited strong and broad absorptions at 350–400 nm in anhydrous methanol and methanol-water mixtures in the UV-Vis spectra. The intensity of the absorptions (represented by absorbance at 375 nm) is directly proportional to molar concentrations of methanol and UO22+(VI), respectively. The linear relationships indicate formation of an electron-donor-acceptor (EDA) complex [UO22+, CH3OH]. The absorptions at 350–400 nm originate from the charge-transfer (single-electron transfer) from CH3OH (electron donor) to UO22+ (electron acceptor) within the [UO22+, CH3OH] complex. Electron paramagnetic resonance (EPR) studies of various mixtures of UO22+-CH3OH and UO22+-CH3OH-H2O have shown that the charge-transfer also took place slowly in the dark, resulting in thermal reduction of UO22+(VI) to UO2+(V) (singlet, g = 2.08) by CH3OH, and CH3OH was oxidized to the hydroxymethyl [rad]CH2OH radical (generating an axial signal). The charge-transfer oxidation-reduction reaction is believed to take place via the EDA [UO22+, CH3OH] complex. EPR studies suggested spin-spin coupling between UO2+(V) and [rad]CH2OH in anhydrous methanol, supporting the formation of a [UO2+, [rad]CH2OH] ion-radical pair. The EPR studies have also shown that UO22+(VI) was reduced to UO2+(V) thermally by other alcohols (ethanol, 2-propanol, and cyclohexanol), and by diphenyl sulfide (Ph2S), L-ascorbic acid (AA), and 2-methyl-5-(propan-2-yl)phenol (carvacrol, ArOH), respectively. Ph2S, AA, and ArOH were oxidized to the diphenyl sulfide Ph2S+[rad] radical cation (singlet, g = 2.00), ascorbic acid AA[rad] radical (singlet, g = 2.00), and carvacrol ArO[rad] radical (singlet, g = 1.98), respectively. Both EPR and UV-Vis studies indicate that the reactions followed the ground-state charge-transfer mechanisms similar to that of the UO22+/methanol reaction. EPR evidence supported formation of the [UO2+, Ph2S+[rad]] ion-radical pair in the charge-transfer reaction of UO22+ and Ph2S and spin-spin interactions within the ion-radical pair. The sulfuric-acid-catalyzed isomerization of [rad]CH2OH to CH3O[rad] was found by EPR studies.
- Sun, Xiaoping,Kolling, Derrick R.J.,Deskins, Seth,Adkins, Ethan
-
-
Read Online
- Cu attached functionalized mesoporous MCM-41: a novel heterogeneous nanocatalyst for eco-friendly one-step thioether formation reaction and synthesis of 5-substituted 1H-tetrazoles
-
In the current study, a mesoporous copper-attached functionalized MCM-41 with the DL-Pyroglutamic acid framework has been produced through a post-synthetic method. The MCM-41 functionalization technique has been used to synthesize this novel heterogeneous catalyst. The material has been identified fully using XRD, FT-IR, BET, EDX, elemental mapping, SEM, and TGA. This catalyst displays high catalytic performance in the one-step thioether formation (C–S) reaction and synthesis of 5-substituted 1H-tetrazoles. The main aspects of this economical copper-catalyzed procedure are green synthesis, slighter experimental conditions, and less reaction time with no additives. Further benefits comprise experimental comfort of handling, secure replacement to dangerous, damaging, and poisoning regular Lewis’s acid catalysts, and reusability with constant catalytic performance. Graphic abstract: [Figure not available: see fulltext.]
- Molaei, Somayeh,Ghadermazi, Mohammad
-
-
Read Online
- Anchimeric assistance of the sulfinyl group in the hydrolysis of cyano groups: A new mild method for the reduction of sulfoxides
-
Conditions to achieve reductive hydrolysis of β-cyanosulfoxides into their corresponding β-sulfenylamides are reported. The anchimeric assistance of the sulfinyl oxygen in the hydrolysis of the cyano group is proposed to explain the mild condition required to achieve it and several proofs supporting this assumption are indicated. From these results a new mild method to transform sulfoxides into sulfides has been developed.
- Garcia Ruano, Jose L.,Martin Castro, Ana M.,Rodriguez Ramos, Jesus H.
-
-
Read Online
- Domino Processes of Arynes Reacting with Three Classes of Nucleophiles for Organic Syntheses
-
Synthetic application of arynes is broadened by their reactions with neutral N-, S-, and O-containing nucleophiles to produce three types of compounds. Accordingly, 1,2-dihydroquinolines are synthesized from Schiff bases, alkynes, and arynes through a Diels-Alder reaction. Epoxides are prepared from thioethers and arynes along with aldehydes or ketones through a Johnson-Corey-Chaykovsky reaction. Phenolic ethers are produced from allyl ethers and arynes through a Claisen-type rearrangement. These target molecules, including natural products γ-asarone, asaricin, and a cholesteryl phenolic ether, are formed through reactions initiated by arynes. These new reactions share a prevailing feature of domino processes, which are carried out in a single flask and afford the desired products in good to high yields.
- Hwu, Jih Ru,Panja, Avijit,Gupta, Nitesh K.,Hu, Yu-Chen,Tan, Kui-Thong,Lin, Chun-Cheng,Hwang, Kuo-Chu,Hsu, Ming-Hua,Huang, Wen-Chieh,Tsay, Shwu-Chen
-
-
Read Online
- The syntheses of sulfides by deoxygenation of sulfoxides using Woollins' reagent
-
Woollins' reagent (WR) acts as a deoxygenation reagent for a wide range of sulfoxides affording the corresponding sulfides in good to excellent yields (up to 99% isolated yield) under mild conditions.
- Hua, Guoxiong,Woollins, J. Derek
-
-
Read Online
- Environmentally Friendly and Recyclable CuCl 2-Mediated C-S Bond Coupling Strategy Using DMEDA as Ligand, Base, and Solvent
-
Simple reaction conditions and recyclable reagents are crucial for environmentally friendly industrial applications. An environment-friendly, recyclable and economic strategy was developed to synthesize diaryl chalcogenides by the CuCl2-catalyzed C S bondformation reaction via iodobenzenes and benzenethiols/1,2-diphenyldisulfanes using N,N'-dimethylethane-1,2-diamine (DMEDA) as ligand, base, and solvent. For these reactions, especially the reactions of diiodobenzenes and aminobenzenethiols/disulfanediyldianilines, a range of substrates are compatible and give the corresponding products in good to excellent yields. Both of the reagents in the catalytic system (CuCl2/DMEDA) are inexpensive, conveniently separable, and recyclable for more than five cycles.
- Shen, Guodong,Lu, Qichao,Wang, Zeyou,Sun, Weiwei,Zhang, Yalin,Huang, Xianqiang,Sun, Manman,Wang, Zhiming
-
supporting information
p. 184 - 198
(2021/09/20)
-
- TFAA/DMSO-Promoted Fluorination of P(O)?H and P(O)?OH Compounds: Compatible Access to Fluorophosphonates and Phosphonofluoridates
-
A TFAA/DMSO/NaF-based system for the efficient fluorination of P(O)?H and P(O)?OH compounds has been developed. Without adding highly toxic and expensive fluorination reagents, this novel transformation provides direct and compatible access to a variety o
- Li, Qi-Wei,Zhang, Xin-Yue,Lu, Lu,Wu, Zi-Qian,Li, Ji,Li, Gui-Zhi,Sun, Kai,Yang, Shang-Dong,Yang, Bin
-
supporting information
p. 938 - 946
(2022/02/07)
-
- Copper based on diaminonaphthalene-coated magnetic nanoparticles as robust catalysts for catalytic oxidation reactions and C-S cross-coupling reactions
-
In this work, the immobilization of copper(ii) on the surface of 1,8-diaminonaphthalene (DAN)-coated magnetic nanoparticles provides a highly active catalyst for the oxidation reaction of sulfides to sulfoxides and the oxidative coupling of thiols to disulfides using hydrogen peroxide (H2O2). This catalyst was also applied for the one-pot synthesis of symmetrical sulfidesviathe reaction of aryl halides with thiourea as the sulfur source in the presence of NaOH instead of former strongly basic and harsh reaction conditions. Under optimum conditions, the synthesis yields of sulfoxides, symmetrical sulfides, and disulfides were about 99%, 95%, and 96% respectively with highest selectivity. The heterogeneous copper-based catalyst has advantages such as the easy recyclability of the catalyst, the easy separation of the product and the less wastage of products during the separation of the catalyst. This heterogeneous nanocatalyst was characterized by FESEM, FT-IR, VSM, XRD, EDX, ICP and TGA. Furthermore, the recycled catalyst can be reused for several runs and is economically effective.
- Yarmohammadi, Nasrin,Ghadermazi, Mohammad,Mozafari, Roya
-
p. 9366 - 9380
(2021/03/16)
-
- Palladium-catalysed thioetherification of aryl and alkenyl iodides using 1,3,5-trithiane as sulfur source
-
Thioetherification reaction of aryl iodides catalysed by palladium(II) complexes in the presence of 1,3,5-trithiane as sulphur source is reported. The paper presents the first homogeneous catalytic application of 1,3,5-trithiane in synthesis. Detailed optimization steps, the frames of the novel reaction are described, as well as the limitations and the substrate scope are also demonstrated. Moderate to good thioether yields were achieved in the presence of various substituted iodobenzenes and some alkenyl iodides, using palladium-xantphos catalyst system. Competitive reactions in the presence of mixed substrates were also performed and mechanistic considerations were assumed.
- Kollár, László,Pongrácz, Péter,Rajat Rao, Yalamarti Venkat,Zugó, Alexandra
-
-
- Copper-catalyzedortho-selective direct sulfenylation ofN-aryl-7-azaindoles with disulfides
-
A copper-catalyzed direct C-H chalcogenation ofN-aryl-azaindoles with disulfides is described. This transformation was performed using Earth abundant Cu(OAc)2as a catalyst, benzoic acid as an additive, air as a terminal oxidant, and readily available diaryl and dialkyldisulfides (or diselenide) as chalcogenation reagents. High functional group tolerance and excellent regioselectivity are demonstrated by the efficient preparation of a wide range ofortho-sulfenylation-7-azaindoles.
- Ru-Jian, Yu,Chun-Yan, Zhang,Xiang, Zhou,Xiong, Yan-Shi,Duan, Xue-Min
-
p. 2901 - 2906
(2021/04/14)
-
- Ni(II) Precatalysts Enable Thioetherification of (Hetero)Aryl Halides and Tosylates and Tandem C?S/C?N Couplings
-
Ni-catalyzed C?S cross-coupling reactions have received less attention compared with other C-heteroatom couplings. Most reported examples comprise the thioetherification of most reactive aryl iodides with aromatic thiols. The use of C?O electrophiles in this context is almost uncharted. Here, we describe that preformed Ni(II) precatalysts of the type NiCl(allyl)(PMe2Ar’) (Ar’=terphenyl group) efficiently couple a wide range of (hetero)aryl halides, including challenging aryl chlorides, with a variety of aromatic and aliphatic thiols. Aryl and alkenyl tosylates are also well tolerated, demonstrating, for the first time, to be competent electrophilic partners in Ni-catalyzed C?S bond formation. The chemoselective functionalization of the C?I bond in the presence of a C?Cl bond allows for designing site-selective tandem C?S/C?N couplings. The formation of the two C-heteroatom bonds takes place in a single operation and represents a rare example of dual electrophile/nucleophile chemoselective process.
- Martín, M. Trinidad,Marín, Mario,Maya, Celia,Prieto, Auxiliadora,Nicasio, M. Carmen
-
supporting information
p. 12320 - 12326
(2021/08/09)
-
- Heterogeneously Ni-Pd nanoparticle-catalyzed base-free formal C-S bond metathesis of thiols
-
This study rationally designed a heterogeneously catalyzed system (i.e., using Ni-Pd alloy nanoparticles supported on hydroxyapatite (Ni-Pd/HAP) under an H2atmosphere) achieving an efficient base-free formal C-S bond metathesis of various thiolsviasuppression of the Ni catalysis deactivation.
- Mitamura, Kanju,Yatabe, Takafumi,Yamamoto, Kidai,Yabe, Tomohiro,Suzuki, Kosuke,Yamaguchi, Kazuya
-
supporting information
p. 3749 - 3752
(2021/04/21)
-
- Rh(I)-Catalyzed Intramolecular Decarbonylation of Thioesters
-
Decarbonylative synthesis of thioethers from thioesters proceeds in the presence of a catalytic amount of [Rh(cod)Cl]2 (2 mol %). The protocol represents the first Rh-catalyzed decarbonylative thioetherification of thioesters to yield valuable thioethers. Notable features include the absence of phosphine ligands, inorganic bases, and other additives and excellent group tolerance to aryl chlorides and bromides that are problematic using other metals to promote decarbonylation. Gram scale synthesis, late-stage pharmaceutical derivatization, and orthogonal site-selective cross-couplings by C-S/C-Br cleavage are reported.
- Cao, Han,Liu, Xuejing,Bie, Fusheng,Shi, Yijun,Han, Ying,Yan, Peng,Szostak, Michal,Liu, Chengwei
-
p. 10829 - 10837
(2021/07/28)
-
- Pd-Catalyzed Double-Decarbonylative Aryl Sulfide Synthesis through Aryl Exchange between Amides and Thioesters
-
We report the palladium-catalyzed double-decarbonylative synthesis of aryl thioethers by an aryl exchange reaction between amides and thioesters. In this method, amides serve as aryl donors and thioesters are sulfide donors, enabling the synthesis of valuable aryl sulfides. The use of Pd/Xantphos without any additives has been identified as the catalytic system promoting the aryl exchange by C(O)-N/C(O)-S cleavages. The method is amenable to a wide variety of amides and sulfides.
- Bie, Fusheng,Cao, Han,Liu, Chengwei,Liu, Xuejing,Shi, Yijun,Szostak, Michal,Zhou, Tongliang
-
p. 8098 - 8103
(2021/10/25)
-
- N-bromosuccinimide/HCl mediated reduction of sulfoxides to sulfides
-
An efficient reduction of sulfoxides to sulfides mediated by N-bromosuccinimide (NBS)/HCl system has been developed. This protocol shows good functional group compatibility as well as broad substrates scope with operational simplicity.
- Wang, Jianqiang,Shi, Fangmin,Dai, Dongyan,Xiong, Liping,Yang, Yongpo
-
supporting information
p. 439 - 443
(2021/02/03)
-
- Scalable electrochemical reduction of sulfoxides to sulfides
-
A scalable reduction of sulfoxides to sulfides in a sustainable way remains an unmet challenge. This report discloses an electrochemical reduction of sulfoxides on a large scale (>10 g) under mild reaction conditions. Sulfoxides are activated using a substoichiometric amount of the Lewis acid AlCl3, which could be regeneratedviaa combination of inexpensive aluminum anode with chloride anion. This deoxygenation process features a broad substrate scope, including acid-labile substrates and drug molecules.
- Kong, Zhenshuo,Pan, Chao,Li, Ming,Wen, Lirong,Guo, Weisi
-
supporting information
p. 2773 - 2777
(2021/04/21)
-
- Modulation of photochemical oxidation of thioethers to sulfoxides or sulfones using an aromatic ketone as the photocatalyst
-
We have developed an eco-friendly and chemo-selective photocatalytic synthesis of sulfoxides or sulfones via oxidation of sulfides (thioethers) at ambient temperature using air or O2 as the oxidant. An inexpensive thioxanthone was used as the photocatalyst. Our method offers excellent chemical yields and good functional group tolerance. The hydrogen bonding between hexafluoro-2-propanol (HFIP) and sulfoxides may play an important role in minimizing the over-oxidization of sulfoxides.
- Zhao, Bin,Hammond, Gerald B.,Xu, Bo
-
supporting information
(2021/09/13)
-
- Catalytic dehydrogenation of amines to imines and the in-situ reduction of sulfoxides into sulfides
-
The catalytic acceptorless dehydrogenation of primary amines into imines and H2 represents one of the most important organic transformations, and the in-situ utilization of the generated H2 for chemical reduction reactions has never
- Li, Bo,Liu, Bing,Liu, Xixi,Wang, Wei,Wang, Yanxin,Xiang, Nian,Zhang, Zehui
-
-
- Chan-Lam-Type C-S Coupling Reaction by Sodium Aryl Sulfinates and Organoboron Compounds
-
A Chan-Lam-Type C-S coupling reaction using sodium aryl sulfinates has been developed to provide diaryl thioethers in up to 92% yields in the presence of a copper catalyst and potassium sulfite. Both electron-rich and electron-poor sodium aryl sulfinates and diverse organoboron compounds were tolerated for the synthesis of aryl and heteroaryl thioethers and dithioethers. The mechanistic study suggested that potassium sulfite was involved in the deoxygenation of sulfinate through a radical process.
- Lam, Long Yin,Ma, Cong
-
supporting information
p. 6164 - 6168
(2021/08/16)
-
- Catalytic Reductive Cleavage of Poly(phenylene sulfide) Using a Hydrosilane
-
The solvent-insoluble poly(phenylene sulfide) main chain was reductively cleaved by using triethylsilane as a hydrogen source under palladium/I c Hex catalytic conditions. After the reaction, benzene and bis(triethylsilyl) sulfide as a sulfide source were formed efficiently. This method could be operated on a gram scale.
- Minami, Yasunori,Matsuyama, Nao,Matsuo, Yasuaki,Tamura, Masanori,Sato, Kazuhiko,Nakajima, Yumiko
-
supporting information
p. 3351 - 3354
(2021/07/17)
-
- Novel reaction course of thiiranes to vinyloxiranes: Reaction of benzyne with thiiranes and aldehydes
-
Reaction of 2 molar amount of 2-(trimethylsilyl)phenyl triflate with thiiranes and aldehydes in the presence of CsF afforded vinyloxiranes in one-pot operation. Reaction of benzyne with thiiranes gave the corresponding alkenyl phenyl sulfides, which furth
- Okuma, Kentaro,Qu, Yuxuan,Nagahora, Noriyoshi
-
p. 1294 - 1300
(2021/07/19)
-
- Aryl thioether compound and preparation method thereof
-
The invention discloses an aryl thioether compound and a synthesis method thereof, wherein an aryl carboxylic acid and a mercaptan (phenol) are used as main raw materials, and a nickel catalyst is prepared. Under the action of the phosphine ligand and the additive, the aryl carboxylic acid and the thiol (phenol) react in an organic solvent, and after the reaction is finished, the corresponding aryl thioether is obtained. The method has the advantages of low cost, high yield, simple and convenient operation, no pollution and the like, and has potential industrial application prospects. The method provides a cheap and green way for preparation of aryl thioether compounds.
- -
-
Paragraph 0010
(2021/11/27)
-
- Trisaminomethane–cobalt complex supported on Fe3O4 magnetic nanoparticles as an efficient recoverable nanocatalyst for oxidation of sulfides and C–S coupling reactions
-
In this work, trisaminomethane–cobalt complex immobilized onto the surface of Fe3O4 magnetic nanoparticles was successfully prepared via a simple and inexpensive procedure. The prepared nanocatalyst was considered a robust and clean nanoreactor catalyst for the oxidation and synthesis of sulfides under green conditions. This ecofriendly heterogeneous catalyst was characterized by Fourier transform infrared spectroscopy, X-ray diffractometry, energy-dispersive X-ray spectroscopy, inductively coupled plasma-atomic emission spectroscopy, thermogravimetric analysis, vibrating sample magnetometry, X-ray mapping, scanning electron microscopy, and transmission electron microscopy techniques. Use of green medium, easy separation and workup, excellent reusability of the nanocatalyst, and short reaction time are some outstanding advantages of this method.
- Ashraf, Muhammad Aqeel,Liu, Zhenling,Peng, Wan-Xi
-
-
- Magnetically recoverable ferromagnetic 3D hierarchical core-shell Fe3O4@NiO/Co3O4 microspheres as an efficient and ligand-free catalyst for C–S bond formation in poly (ethylene glycol)
-
A simple and efficient protocol for the synthesis of diaryl thioethers from the reaction of thiourea with a wide variety of aryl halides, including aryl iodides, aryl bromides and aryl chlorides in the presence of 3D hierarchical core-shell Fe3O4@NiO/Co3O4 microspheres has been described. This reaction enables the one-pot synthesis of diaryl thioethers in good to high yields using a non-toxic and magnetically separable catalyst in PEG-400 as an eco-friendly, safe, inexpensive and thermally stable solvent. Magnetic separation and reusability of catalyst for eight times without any significant loss of activity, the use of a commercially available, eco-friendly, cheap and chemically stable sulfur transfer agent and solvent, operational simplicity, environmentally benign, easier work-up procedure and cost efficiency make this method a promising candidate for potential applications in some organic reactions. The catalytic activity of Fe3O4@NiO/Co3O4 as a novel and inexpensive catalyst was investigated in the C-S cross coupling reaction.
- Vatandoust Namanloo, Ahad,Akhlaghinia, Batool,Mohammadinezhad, Arezou
-
p. 446 - 461
(2020/05/13)
-
- A Unified Strategy for Arylsulfur(VI) Fluorides from Aryl Halides: Access to Ar-SOF3 Compounds
-
A convenient protocol to selectively access various arylsulfur(VI) fluorides from commercially available aryl halides in a divergent fashion is presented. Firstly, a novel sulfenylation reaction with the electrophilic N-(chlorothio)phthalimide (Cl-S-Phth) and arylzinc reagents afforded the corresponding Ar-S-Phth compounds. Subsequently, the S(II) atom was selectively oxidized to distinct fluorinated sulfur(VI) compounds under mild conditions. Slight modifications on the oxidation protocol permit the chemoselective installation of 1, 3, or 4 fluorine atoms at the S(VI) center, affording the corresponding Ar-SO2F, Ar-SOF3, and Ar-SF4Cl. Of notice, this strategy enables the effective introduction of the rare and underexplored -SOF3 moiety into various (hetero)aryl groups. Reactivity studies demonstrate that such elusive Ar-SOF3 can be utilized as a linchpin for the synthesis of highly coveted aryl sulfonimidoyl fluorides (Ar-SO(NR)F).
- Cornella, Josep,Wang, Lin
-
supporting information
p. 23510 - 23515
(2020/10/29)
-
- Preventing Pd-NHC bond cleavage and switching from nano-scale to molecular catalytic systems: Amines and temperature as catalyst activators
-
Many reactions catalyzed by Pd complexes with N-heterocyclic carbene (NHC) ligands are performed in the presence of amines which usually act as coupling reagents or mild bases. However, amines can react with Pd/NHC complexes in a number of ways: enhancing molecular catalysis, causing the catalyst deactivation or triggering the ligandless modes of catalysis by producing NHC-free active palladium species. This study gains insight into conditions required for the efficient use of amines as activators of molecular Pd/NHC catalysis and preventing the undesirable reductive cleavage of the Pd-NHC bond in catalytic systems. Reactions of Pd/NHC complexes with various amines within a temperature range of 25-140 °C and thermal stability of the resulting amino-complexes are examined. The results indicate the major influence of the amine structure and reaction temperature on the catalyst transformation. In particular, thermal decomposition of Pd/NHC complexes with aliphatic amine ligands predominantly leads to reductive Pd-NHC bond cleavage, while deprotonation of the complexes with primary and secondary aliphatic amine ligands in the presence of strong bases at 25-60 °C promotes the activation of molecular Pd/NHC catalysis. Efficient Pd-PEPPSI complex-amine systems suitable for strong-base-promoted C-S cross-coupling reactions between aryl halides and thiols are suggested on the basis of these findings.
- Ananikov, Valentine P.,Astakhov, Alexander V.,Chernenko, Andrey Yu.,Chernyshev, Victor M.,Khazipov, Oleg V.,Pasyukov, Dmitry V.,Shevchenko, Maxim A.,Tafeenko, Victor A.
-
p. 1228 - 1247
(2020/03/26)
-
- Palladium complex containing meta-position carborane triazole ligand and preparation method and application of palladium complex
-
The invention relates to a palladium complex containing a meta-position carborane triazole ligand and a preparation method and application of the palladium complex. The palladium complex is prepared by the following steps: (1) dropwise adding an n-BuLi solution into a meta-position carborane m-C2B10H12 solution, carrying out stirring and reacting, then adding 3-propargyl bromide for a reaction again, and after the reaction is finished, carrying out separating to obtain 1,3-dipropargyl meta-carborane; and (2) under the catalytic condition of a catalyst CuI, carrying out a reaction on 1,3-dipropargyl meta-carborane and aryl azide, then adding PdCl2 into a reaction system, continuing the reaction, and after the reaction is finished, carrying out separation to obtain the palladium complex containing the meta-carborane triazole ligand. Compared with the prior art, the preparation method provided by the invention is simple and green; the complex can efficiently catalyze a coupling reaction of mercaptan and halogenated hydrocarbon to synthesize thioether compounds; reaction conditions are mild, substrate universality is good, catalytic efficiency is high, and few byproducts are produced;and the catalyst has high stability and is not sensitive to air and water.
- -
-
Paragraph 0041-0043; 0072-0076
(2020/08/07)
-
- A Robust Pd-Catalyzed C-S Cross-Coupling Process Enabled by Ball-Milling
-
An operationally simple mechanochemical C-S coupling of aryl halides with thiols has been developed. The reaction process operates under benchtop conditions without the requirement for a (dry) solvent, an inert atmosphere, or catalyst preactivation. The reaction is finished within 3 h. The reaction is demonstrated across a broad range of substrates; the inclusion of zinc metal has been found to be critical in some instances, especially for coupling of alkyl thiols.
- Browne, Duncan L.,Jones, Andrew C.,Nicholson, William I.,Smallman, Harry R.
-
supporting information
p. 7433 - 7438
(2020/10/09)
-
- Bimetallic BaMoO4 nanoparticles for the C-S cross-coupling of thiols with haloarenes
-
We disclosed new bimetallic BaMoO4 nanoparticles for the C-S cross-coupling reaction. The C-S cross-coupling reaction of alkyl/aryl thiols with haloarenes was accomplished with high yields. The reaction has good functional group tolerance and selectivity. This is an efficient protocol for synthesizing the building blocks of pharmaceuticals containing C-S bonds. The catalyst is recyclable. The unactivated bromo- and 4-acetyl fluoro-arenes can well couple to afford thioethers in high yields. The reaction is believed to proceed by oxidative addition and reductive elimination.
- Panda, Subhalaxmi,Sahu, Santosh Kumar,Behera, Pradyota Kumar,Panigrahi, Reba,Garnaik, Bamakanta,Rout, Laxmidhar
-
supporting information
p. 2500 - 2504
(2020/02/20)
-
- X-ray structurally characterized Mo (VI), Fe (III) and Cu (II) complexes of amide-imine conjugate: (bio)catalytic and histidine recognition studies
-
An amide-imine conjugate, (E)-N′-((2-hydroxybenzen-1-yl) methylene)-4-methylbenzohydrazide (H2LPTASAL), derived from 4-methyl-benzoic acid hydrazide (PTA) and 2-hydroxybenzaldehyde is used to prepare Mo (VI), Cu (II) and Fe (III) complexes. The X-ray structurally characterized complexes have been explored as catalyst for amine assisted asymmetric ring opening (ARO) of epoxide, carbon-heteroatom cross-coupling and ethyl benzene oxidation. In addition, their catecholase like activities have thoroughly been investigated. Moreover, the Cu (II) complex selectively recognizes histidine by fluorescence spectroscopy.
- Ta, Sabyasachi,Ghosh, Milan,Salam, Noor,Das, Jayanta,Islam, Manirul,Brand?o, Paula,Félix, Vítor,Sanmartin, Jesus,Das, Debasis
-
-
- CuMoO4 Bimetallic Nanoparticles, An Efficient Catalyst for Room Temperature C?S Cross-Coupling of Thiols and Haloarenes
-
CuII catalyst is less efficient at room temperature for C?S cross-coupling. C?S cross-coupling by CuII catalyst at room temperature is not reported; however, doping of copper with molybdenum metal has been realized here to be more efficient for C?S cross-coupling in comparison to general CuII catalyst. The doped catalyst CuMoO4 nanoparticle is found to be more efficient than copper. The catalyst works under mild conditions without any ligand at room temperature and is recyclable and effective for a wide range of thiols and haloarenes (ArI, ArBr, ArF) from milligram to gram scale. The copper-based bimetallic catalyst is developed and recognized for C?S cross-coupling of haloarenes with alkyl and aryl thiols.
- Panigrahi, Reba,Sahu, Santosh Kumar,Behera, Pradyota Kumar,Panda, Subhalaxmi,Rout, Laxmidhar
-
supporting information
p. 620 - 624
(2019/12/27)
-
- Dechalcogenization of Aryl Dichalcogenides to Synthesize Aryl Chalcogenides via Copper Catalysis
-
An application for dechalcogenization of aryl dichalcogenides via copper catalysis to synthesize aryl chalcogenides is disclosed. This approach is highlighted by the practical conditions, broad substrate scope, and good functional group tolerance with several sensitive groups such as aldehyde, ketone, ester, amide, cyanide, alkene, nitro, and methylsulfonyl. Furthermore, the robustness of this methodology is depicted by the late-stage modification of estrone and synthesis of vortioxetine. Remarkably, synthesis of more challenging organic materials with large ring tension under milder conditions and synthesis of some halogen contained diaryl sulfides which could not be synthesized using metal-catalyzed coupling reactions of aryl halogen are successfully accomplished with this protocol.
- Cao, Fei,Chen, Jinhong,Deng, Jiedan,Deng, Xuemei,Hou, Yongsheng,Shao, Xiangfeng,Shi, Tao,Wang, Yongqiang,Wang, Zhen,Wu, Lingxi,Yang, Jinru,Yang, Yuhang
-
p. 2707 - 2712
(2020/03/11)
-
- B2cat2-Mediated Reduction of Sulfoxides to Sulfides
-
An efficient and operationally simple method for the reduction of sulfoxides to sulfides has been developed using bis(catecholato)diboron (B2cat2) as a reducing agent. The present method accommodates various functional groups which are generally prone to reduction: halides, alkynes, carbonyls, nitriles, and heterocycles are totally intact, and only sulfoxide moieties undergo reduction chemoselectively. Moreover, the remaining diboron and the resulting boron-containing wastes are readily removable, the practicality of this protocol being thus demonstrated.
- Takahashi, Fumiya,Nogi, Keisuke,Yorimitsu, Hideki
-
supporting information
p. 3009 - 3012
(2020/03/25)
-
- Microwave-Assisted Copper Slag-Catalyzed Green S-Arylation of Arenethiols with Arylboronic Acids
-
Abstract: Diaryl sulfides have been synthesized in moderate to excellent yield by S-arylation of arenethiols with arylboronic acids using copper slag as a catalyst. Copper slag is a by-product obtained from smelting and refining of copper. Conventional heating method has been compared with the microwave-assisted technique. The proposed microwave-assisted synthesis provides excellent yields of diaryl sulfides in a short time (10 min) and is ligand-free, green, and cost-effective.
- Gavane, D. S.,Jambhorkar, V. S.,Kale, B. D.,Karnik, K. S.,Khandare, A. L.,Narula, I. S.,Rajhans, A. P.,Sarkate, A. P.
-
p. 1300 - 1303
(2020/10/02)
-
- Room temperature nickel-catalyzed cross-coupling of aryl-boronic acids with thiophenols: Synthesis of diarylsulfides
-
A NiCl2/2,2′-bipyridine-catalyzed cross-coupling of thiophenols with arylboronic acids has been developed for the synthesis of symmetric and unsymmetric diarylsulfides at room temperature and in air. This methodology is reliable and offers a mild and easy to operate process for the synthesis of arylthioethers, which are essential compounds with applications in the pharmaceutical and agricultural industries. This method avoids the use of expensive transition metals, such as Pd, Ir or Rh, sophisticated ligands and elevated temperatures. It also has a wide substrate scope (55 examples) and provides products in good to excellent yields (72-93%).
- Bhowmik, Amit,Fernandes, Rodney A.,Yadav, Mahesh
-
p. 2447 - 2458
(2020/04/15)
-
- Novel and facile procedure for the synthesis of Ni(II) and Pd(II) PSCOP pincer complexes. Evaluation of their catalytic activity on C-S, C-Se and C-C cross coupling reactions
-
A new and facile procedure for the synthesis of non-symmetric phosphinito-thiophosphinito PSCOP pincer complexes based on Ni(II) and Pd(II) was developed. The synthesis of the complexes was carried out in a single step, starting from 3,3-dihydroxydiphenyldisulfide. The Ni(II) complexes were tested as catalysts in C-S and C-Se coupling reactions, being the tBu derivative 3-Ni the one exhibiting the best performance in both transformations. In this case, the sterics of the substrates was studied, showing that higher steric hindrance leads to lower yields. Analogously, the Pd(II) complexes were used as catalyst in Suzuki-Miyaura couplings of para-substituted bromobenzenes and phenyl boronic acid, being the analogous tBu derivative complex 3-Pd the best catalysts for this process, exhibiting tolerance to a wide range of functional groups.
- Valderrama-García, Bianca X.,Rufino-Felipe, Ernesto,Valdés, Hugo,Hernandez-Ortega, Simón,Aguilar-Castillo, Bethsy Adriana,Morales-Morales, David
-
-
- Nickel-Catalyzed Thiocarbonylation of Arylboronic Acids with Sulfonyl Chlorides for the Synthesis of Thioesters
-
An interesting procedure for thioester synthesis via nickel-catalyzed thiocarbonylation of arylboronic acid with sulfonyl chlorides as the sulfur source has been explored. Using Mo(CO)6 as a solid CO surrogate and reductant, a broad range of thioesters were obtained in moderate to good yields with good functional group tolerance.
- Qi, Xinxin,Bao, Zhi-Peng,Yao, Xin-Tong,Wu, Xiao-Feng
-
supporting information
p. 6671 - 6676
(2020/09/02)
-
- Molecular iodine/DMSO mediated oxidation of internal alkynes and primary alcohols using a one-pot, two step approach towards 2,4,5-trisubstituted imidazoles: Substrate scope and mechanistic studies
-
An efficient, eco-friendly and practical oxidation of internal alkynes and primary alcohols as key steps towards the synthesis of 2,4,5-trisubstituted imidazoles is reported. This green synthetic methodology employed an acid and metal-free molecular iodine/DMSO system, to afford a variety of substituted imidazoles in moderate to good yields, with a range of functionalities tolerated. Mechanistic studies revealed two distinct oxidation pathways, which ultimately form the diketone and aldehyde that serve as key intermediates in the multicomponent domino synthesis.
- Jeena, Vineet,Naidoo, Shivani
-
supporting information
(2020/02/15)
-
- Dimethyl Sulfoxide as an Oxygen Atom Source Enabled Tandem Conversion of 2-Alkynyl Carbonyls to 1,2-Dicarbonyls
-
A tandem transformation of 2-alkynyl carbonyl compounds by means of a CuBr2/I2/DMSO/water system is developed, enabling the fromation of various functionalized 1,2-dicarbonyl compounds, including 1,2-diketones, α-keto amides and α-keto ester. This Cu-promoted iodine-mediated tandem procedure employs DMSO as the oxygen atom source of the formed carbonyl group through iodonium ion formation, nucleophilic DMSO addition and C?C bond cleavage cascades. (Figure presented.).
- Hu, Ming,Li, Jin-Heng,Li, Yang,Lu, Yuan,Luo, Mu-Jia
-
supporting information
(2020/05/01)
-
- DABCO-promoted Diaryl Thioether Formation by Metal-catalyzed Coupling of Sodium Sulfinates and Aryl Iodides
-
A scalable catalytic synthesis method using commodity chemicals for constructing diaryl thioethers directly from sodium arylsulfinates and iodoarenes is reported in this study. In the presence of CuO or other copper salts such as Cu(OAc)2 as well as palladium catalysts, DABCO demonstrated to be essential to promote this transformation. Various iodoarenes and aryl sulfinates were examined and demonstrated the viability of this method. The mechanistic study showed that radical reactions occurred, while DABCO N-oxide radical can be observed by mass spectrometry. A plausible catalytic mechanism involving DABCO is also discussed, suggesting synergistic reduction of sulfinate by Cu(II) and DABCO is the key step of this coupling reaction. (Figure presented.).
- Liu, Yanpeng,Lam, Long Yin,Ye, Jiqing,Blanchard, Nicolas,Ma, Cong
-
supporting information
p. 2326 - 2331
(2020/05/05)
-
- A template free protocol for fabrication of a Ni(ii)-loaded magnetically separable nanoreactor scaffold for confined synthesis of unsymmetrical diaryl sulfides in water
-
In the present report, an environmentally benign magnetically recoverable nickel(ii)-based nanoreactor as a heterogeneous catalyst has been developedviaa template free approach. The catalytic performance of the synthesized catalyst is assessed in the confined oxidative coupling of arenethiols with arylhydrazines to form unsymmetrical diaryl sulfides under aerobic conditions. The salient features of our protocol include oxidant- and ligand-free conditions, use of water as a green solvent, room temperature and formation of nitrogen and water as the only by-products. Moreover, a broad range of functional groups are tolerated well and provide the corresponding diaryl sulfides in moderate to good yields. Moreover, the heterogeneous nature of the catalyst permits facile magnetic recovery and reusability for up to seven runs, making the present protocol highly desirable from industrial and environmental standpoints.
- Arora, Gunjan,Gaur, Rashmi,Gupta, Radhika,Rana, Pooja,Sharma, Rakesh Kumar,Yadav, Manavi,Yadav, Priya
-
p. 19390 - 19396
(2020/06/04)
-
- Copper/Iodine-Cocatalyzed C-C Cleavage of 1,3-Dicarbonyl Compounds Toward 1,2-Dicarbonyl Compounds
-
A new, general oxidative route to transformations of 1,3-dicarbonyl compounds to 1,2-dicarbonyl compounds by merging copper and I2 catalysis is described. This method is applicable to broad 1,3-dicarbonyl compounds, including 1,3-diketones, 1,3-keto esters and 1,3-keto amides. Mechanistical studies show that the reaction is achieved via the C–C bond cleavage and CO release cascades.
- Chen, Li-Sha,Zhang, Lu-Bing,Tian, Yue,Li, Jin-Heng,Liu, Yong-Quan
-
supporting information
p. 5523 - 5526
(2020/09/02)
-
- Solid-State C-S Coupling in Nickel Organochalcogenide Frameworks as a Route to Hierarchical Structure Transfer to Binary Nanomaterials
-
In this work, the transfer of the flexible and easily tunable hierarchical structure of nickel organochalcogenides to different binary Ni-based nanomaterials via selective coupling of organic units was developed. We suggested the use of substituted aryl groups in organosulfur ligands (SAr) as traceless structure-inducing units to prepare nanostructured materials. At the first step, it was shown that the slight variation of the type of SAr units and synthetic procedures allowed us to obtain nickel thiolates [Ni(SAr)2]n with diverse morphologies after a self-assembly process in solution. This feature opened the way for the synthesis of different nanomaterials from a single type of precursor using the phenomenon of direct transfer of morphology. This study revealed that various nickel thiolates undergo selective C-S coupling under high-temperature conditions with the formation of highly demanding nanostructured NiS particles and corresponding diaryl sulfides. The in situ oxidation of the formed nickel sulfide in the case of reaction in an air atmosphere provided another type of valuable nanomaterial, nickel oxide. The high selectivity of the transformation allowed the preservation of the initial organochalcogenide morphologies in the resulting products.
- Ananikov, Valentine P.,Degtyareva, Evgeniya S.,Galushko, Alexey S.,Kashin, Alexey S.
-
-
- Arylation of aryllithiums with: S-arylphenothiazinium ions for biaryl synthesis
-
Aryllithiums are one of the most common and important aryl nucleophiles; nevertheless, methods for arylation of aryllithums to produce biaryls have been limited. Herein, we report arylation of aryllithiums with S-arylphenothiazinium ions through selective
- Morofuji, Tatsuya,Yoshida, Tatsuki,Tsutsumi, Ryosuke,Yamanaka, Masahiro,Kano, Naokazu
-
supporting information
p. 13995 - 13998
(2020/11/21)
-
- C2-Selective C-H methylation of heterocyclic N-oxides with sulfonium ylides
-
A redox-neutral C2-selective methylation of heterocyclic N-oxides with sulfonium ylides is described herein. This report presents unprecedented findings for the utility of sulfonium ylides as the methylation source of N-heterocycles beyond the Corey-Chaykovsky reaction. Intriguingly, pyrrolidine plays a significant role in minimizing the reductive C2-methylation process. This method is characterized by its mild conditions, simplicity, and excellent site selectivity. The applicability of the developed protocol is showcased by the late-stage methylation and sequential transformations of complex drug molecules.
- An, Won,Choi, Su Bin,Kim, Namhoon,Kwon, Na Yeon,Ghosh, Prithwish,Han, Sang Hoon,Mishra, Neeraj Kumar,Han, Sangil,Hong, Sungwoo,Kim, In Su
-
supporting information
p. 9004 - 9009
(2020/11/30)
-
- Grignard-Reagent-Promoted Desulfonylation/Intramolecular Coupling for the Synthesis of 2-(1-Fluorovinyl)pyridines
-
A novel process involving Grignard-reagent-promoted desulfonylation/intramolecular coupling of readily available α-fluoro-α,β-unsaturated-(2-pyridyl)sulfones was realized that provided a series of polysubstituted 2-(1-fluorovinyl)pyridines in good yields. The intrinsic coordination between pyridine and Mg(II) along with the "negative fluorine effect"of the substrates should play the key role for the smooth transformation in the absence of transition-metal catalysts.
- Jiang, Gaoxi,Kang, Lei,Qian, Jinlong,Yang, Huameng,Zhang, Jinlong
-
supporting information
p. 9118 - 9122
(2020/12/02)
-
- CuI anchored onto mesoporous SBA-16 functionalized by aminated 3-glycidyloxypropyltrimethoxysilane with thiosemicarbazide (SBA-16/GPTMS-TSC-CuI): A heterogeneous mesostructured catalyst for: S -arylation reaction under solvent-free conditions
-
Herein, we report the novel synthesis of CuI anchored onto a cage-like mesoporous material (SBA-16), which was successfully functionalized by aminated 3-glycidyloxypropyltrimethoxysilane with thiosemicarbazide (SBA-16/GPTMS-TSC-CuI) into an efficient and highly recyclable heterogeneous catalyst. The as-synthesized mesostructured catalyst (SBA-16/GPTMS-TSC-CuI) was comprehensively characterized by different techniques, namely, FT-IR, FIR, SAXRD, XRD, XPS, BET, TEM, FE-SEM, EDX, EDX mapping, TGA, ICP-OES, and CHNS analyses. SBA-16 with a unique "super-cage" structure efficiently controlled the formation of dispersed organic and metal species in the mesoporous channels. These confined nanoparticles with a narrow particle size distribution (3-7 nm) exhibited excellent catalytic activity in the S-arylation reaction without necessitating the use of toxic solvents and/or expensive metal catalysts. Interestingly, the mesoporous catalyst was extremely stable under the reaction conditions and could be easily separated by a simple filtration process and reused for at least seven recycle runs (without any appreciable loss in catalytic activity). Due to the inimitable structure of the abovementioned mesostructured catalyst, the C-S coupling products of aryl halides with S8/thiourea under solvent-free conditions were obtained in good to excellent yields in remarkably reduced reaction times in comparison to those reported in earlier studies.
- Ghodsinia, Sara S.E.,Akhlaghinia, Batool
-
supporting information
p. 3029 - 3049
(2019/06/17)
-
- Ni-guanidine@MCM-41 NPs: a new catalyst for the synthesis of 4,4?-(arylmethylene)-bis-(3-methyl-1-phenyl-1H-pyrazol-5-ols) and symmetric di-aryl sulfides
-
In this work, the surface of mesoporous MCM-41 was modified with guanidine, and then, Nickel particles have become immobilized on its surface (Ni-guanidine@MCM-41NPs). This heterogeneous catalyst has been identified by various techniques including: low-angle X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, inductively coupled plasma, thermal gravimetric analysis and N2 adsorption–desorption measurement isotherms, and its catalytic application was studied in the synthesis of 4,4?-(arylmethylene)-bis-(3-methyl-1-phenyl-1H-pyrazol-5-ol) derivatives and symmetric di-aryl sulfides. The prepared organometallic complex could be isolated, post-reaction, by simple filtration for several consecutive cycles without a notable change in its catalytic activity.
- Filian, Hossein,Ghorbani-Choghamarani, Arash,Tahanpesar, Elham
-
p. 2673 - 2681
(2019/07/17)
-
- Immobilization of Pd(0) complex on the surface of SBA-15: A reusable catalyst for the synthesis of 5-substituted tetrazoles, sulfides and sulfoxides
-
A simple and efficient method for the synthesis of 5-substituted tetrazoles, sulfides and sulfoxides in the presence of Pd(0) complex immobilized on mesoporous SBA-15 as an efficient, recoverable and thermally stable mesostructure has been reported. Also, the prepared mesostructure was characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, X-ray mapping, energy-dispersive X-ray spectroscopy, N2 adsorption and desorption, inductively coupled plasma optical emission spectroscopy and thermal gravimetric analysis. Then, this mesostructured catalyst was applied in the synthesis of 5-substituted tetrazoles, sulfides and sulfoxides. The approach described here offers advantages such as short reaction times, high yield, purity yields, simple and eco- friendly, easy work-up. More importantly, this nanohybrid robust catalyst did not undergo metal leaching and applied several times without any decrease in catalytic activity.
- Tamoradi, Taiebeh,Ghorbani-Choghamarani, Arash,Ghadermazi, Mohammad
-
p. 374 - 380
(2018/11/01)
-
- Core–shell nanostructure (Fe3O4?MCM-41?Cu-P2C) as a highly efficient and recoverable nanocatalyst for the synthesis of polyhydroquinoline, 5-substituted 1H-tetrazoles and sulfides
-
Fe3O4 magnetic nanoparticles were used as a core for Cu(II) Schiff base complex functionalized mesoporous MCM-41 shell to provide a core–shell nanostructure (Fe3O4?MCM-41?Cu-P2C). A simple, environmentally friendly, inexpensive, green reaction conditions and efficient procedure for the synthesis of polyhydroquinoline, 5-substituted 1H-tetrazoles and sulfides derivatives using this core–shell nanostructure as an efficient, novel and recoverable nanocatalyst has been described. Fe3O4?MCM-41?Cu-P2C is stable, cost-effective, heterogeneous, easy to handle and recoverable nanocatalyst and can be reused for several consecutive runs without a significant loss of catalytic activity. The catalyst was characterized by fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), powder X-ray diffractometer (XRD), scanning electron microscopy (SEM), atomic absorption spectroscopy (AAS), Brunauer–Emmett–Teller (BET) and vibrating sample magnetometer (VSM) techniques.
- Nikoorazm, Mohsen,Erfani, Zahra
-
-
- An efficient clean methodology for the C-S coupling to aryl thioethers and S-S homocoupling to aromatic disulfides catalyzed over a Ce(IV)-leucine complex immobilized on mesoporous MCM-41
-
A novel Ce(iv)-anchored l-leucine covalently bonded to mesoporous MCM-41 has been synthesized by a non-hydrothermal post-functionalization approach. It has been thoroughly characterized by sophisticated physicochemical techniques. The material was applied in the efficient green synthesis of aromatic sulfides by C-S coupling using molecular sulfur and haloarenes. Another catalytic application was in the synthesis of symmetric disulfides by the homocoupling of aromatic thiols in the presence of H2O2 as an oxidant. The ligand-free protocol is simple, clean and free from hazardous chemicals. Moreover, the catalyst is reusable for several times, thus making the methodology sustainably viable.
- Veisi, Hojat,Tamoradi, Taibeh,Karmakar, Bikash
-
p. 10343 - 10351
(2019/07/09)
-
