- Photogeneration of thiyl radicals using metal-halide perovskite for highly efficient synthesis of thioethers
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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.
- Liu, Xin,Bai, Rong,Guo, Zhifen,Che, Yan,Guo, Chunyi,Xing, Hongzhu
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- Transition-Metal-Free and Base-Promoted Carbon-Heteroatom Bond Formation via C-N Cleavage of Benzyl Ammonium Salts
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A facile and general method for constructing carbon-heteroatom (C-P, C-O, C-S, and C-N) bonds via C-N cleavage of benzyl ammonium salts under transition-metal-free conditions was reported. The combination of t-BuOK and 18-crown-6 enabled a wide range of substituted benzyl ammonium salts to couple readily with different kinds of heteroatom nucleophiles, i.e. hydrogen phosphoryl compounds, alcohols, thiols, and amines. Good functional group tolerance was demonstrated. The scale-up reaction and one-pot synthesis were also successfully performed.
- Liu, Long,Tang, Yuanyuan,Wang, Kunyu,Huang, Tianzeng,Chen, Tieqiao
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p. 4159 - 4170
(2021/03/09)
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- Efficient visible light initiated hydrothiolations of alkenes/alkynes over Ir2S3/ZnIn2S4: Role of Ir2S3
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The hydrothiolations of alkynes/alkenes with thiols is an atom-economic and thus attractive method for the constructions of C-S bonds. Here Ir2S3/ZnIn2S4 nanocomposites with varied Ir2S3 loadings were obtained by one-pot solvothermal method from ZnCl2, InCl3 and thioacetamide with IrCl3. The loading of Ir2S3 on the surface of ZnIn2S4 promoted the hydrothiolations of alkenes and alkynes, with an optimum performance observed over 0.5 molpercent Ir2S3/ZnIn2S4 nanocomposite. Based on the studies on the performance of several other cocatalysts (MoS2, NiS and Pd) loaded ZnIn2S4 and the EIS analyses, it was proposed that the superior performance over Ir2S3/ZnIn2S4 nanocomposite can be ascribed to an improved efficiency on the photogeneration of the thiyl radicals by loading Ir2S3 as well as its inactivity for photocatalytic hydrogen evolution, a side reaction in the light initiated hydrothiolation reaction over ZnIn2S4. This study not only demonstrates an efficient and green strategy to synthesize thiolated products under visible light based on semiconductor photocatalysis, but also provides some guidances for the design and development of photocatalytic systems for light induced organic syntheses.
- Li, Yuanyuan,Li, Zhaohui,Wang, Xinglin
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p. 409 - 416
(2020/07/30)
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- Zirconium-catalysed direct substitution of alcohols: enhancing the selectivity by kinetic analysis
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Kinetic analysis was used as a tool for rational optimization of a catalytic, direct substitution of alcohols to enable the selective formation of unsymmetrical ethers, thioethers, and Friedel-Crafts alkylation products using a moisture-tolerant and commercially available zirconium complex (2 to 8 mol%). Operating in air and in the absence of dehydration techniques, the protocol furnished a variety of products in high yields, including glycosylated alcohols and sterically hindered ethers. In addition, the kinetic studies provided mechanistic insight into the network of parallel transformations that take place in the reaction, and helped to elucidate the nature of the operating catalyst.
- Camaj, David,Carlsson, Robin,Dalla-Santa, Oscar,Lill, Malin,Lundberg, Helena,Margarita, Cristiana,Ramstr?m, Anja,Tu?on, Hernando,Villo, Piret
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p. 7420 - 7430
(2021/11/23)
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- Photoactive Metal-Organic Frameworks for the Selective Synthesis of Thioethers: Coupled with Phosphine to Modulate Thiyl Radical Generation
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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
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p. 8672 - 8681
(2021/06/28)
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- Nickel-Catalyzed Inter- and Intramolecular Aryl Thioether Metathesis by Reversible Arylation
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A nickel-catalyzed aryl thioether metathesis has been developed to access high-value thioethers. 1,2-Bis(dicyclohexylphosphino)ethane (dcype) is essential to promote this highly functional-group-tolerant reaction. Furthermore, synthetically challenging macrocycles could be obtained in good yield in an unusual example of ring-closing metathesis that does not involve alkene bonds. In-depth organometallic studies support a reversible Ni0/NiII pathway to product formation. Overall, this work not only provides a more sustainable alternative to previous catalytic systems based on Pd, but also presents new applications and mechanistic information that are highly relevant to the further development and application of unusual single-bond metathesis reactions.
- Delcaillau, Tristan,Bismuto, Alessandro,Lian, Zhong,Morandi, Bill
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supporting information
p. 2110 - 2114
(2019/12/24)
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- Bis(alkyl) scandium and yttrium complexes coordinated by an amidopyridinate ligand: Synthesis, characterization and catalytic performance in isoprene polymerization, hydroelementation and carbon dioxide hydrosilylation
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New neutral bis(alkyl) Sc and Y complexes [N,Npy,N-]Ln(CH2SiMe3)2(THF)n [n = 0, Ln = Sc (1Sc), Y (1Y); n = 1, Ln = Y (1YTHF)] stabilized by a tridentate monoanionic amidopyridinate ligand were straightforwardly prepared by alkane elimination, upon mixing ligand [N,Npy,N-]H and metal precursor Ln(CH2SiMe3)3(THF)2 in toluene at 0 °C. Depending on the work-up conditions, yttrium bis(alkyl)s were isolated as either a pentacoordinate Lewis base free complex [N,Npy,N-]Y(CH2SiMe3)2 (1Y) or as a hexacoordinate THF adduct [N,Npy,N-]Y(CH2SiMe3)2THF (1YTHF). For the smaller Sc ion the only solvent-free complex [N,Npy,N-]Y(CH2SiMe3)2 (1Sc) was isolated as a pentacoordinate species irrespective of the reaction/work-up/crystallization conditions applied. Complexes 1Ln (Ln = Y, Sc) and 1YTHF were scrutinized as pre-catalysts in ternary catalytic systems Ln/borate/AliBu3 (borate = [HNMe2Ph][B(C6F5)4] or [Ph3C][B(C6F5)4]), applied to isoprene (IP) polymerization, providing moderate activity albeit high selectivity with predominant formation of 1,4-cis polyisoprene (up to 99%). The same complexes proved to be effcient catalysts also for the intermolecular hydrolelementation of styrene with various EH sustrates (pyrrolidine, morpholine, Ph2PH, PhPH2, PhSH) affording linear anti-Markovnikov addition products exclusively. After a preliminary activation by B(C6F5)3, selected bis(alkyl) complexes from this series have been finally used as valuable pre-catalysts for the CO2 hydrosylilation to CH4 in the presence of organosilanes as reducing agents (PhMe2SiH, PhSiH3, Et2MeSiH).
- Gurina,Kissel,Lyubov,Luconi,Rossin,Tuci,Cherkasov,Lyssenko,Shavyrin,Ob'Edkov,Giambastiani,Trifonov
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p. 638 - 650
(2020/01/30)
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- Nanolayered cobalt-molybdenum sulphides (Co-Mo-S) catalyse borrowing hydrogen C-S bond formation reactions of thiols or H2S with alcohols
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Nanolayered cobalt-molybdenum sulphide (Co-Mo-S) materials have been established as excellent catalysts for C-S bond construction. These catalysts allow for the preparation of a broad range of thioethers in good to excellent yields from structurally diverse thiols and readily available primary as well as secondary alcohols. Chemoselectivity in the presence of sensitive groups such as double bonds, nitriles, carboxylic esters and halogens has been demonstrated. It is also shown that the reaction takes place through a hydrogen-autotransfer (borrowing hydrogen) mechanism that involves Co-Mo-S-mediated dehydrogenation and hydrogenation reactions. A novel catalytic protocol based on the thioetherification of alcohols with hydrogen sulphide (H2S) to furnish symmetrical thioethers has also been developed using these earth-abundant metal-based sulphide catalysts.
- Corma, Avelino,Sorribes, Iván
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p. 3130 - 3142
(2019/03/13)
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- Metal-free photocatalytic thiol-ene/thiol-yne reactions
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The organic photocatalyst (9-mesityl-10-methylacridinum tetrafluoroborate) in the presence of visible light is used to initiate thiol-ene and thiol-yne reactions. Thiyl radicals are generated upon quenching the photoexcited catalyst with a range of thiols
- Kaur, Sarbjeet,Zhao, Gaoyuan,Busch, Evan,Wang, Ting
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supporting information
p. 1955 - 1961
(2019/02/20)
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- Visible light initiated hydrothiolation of alkenes and alkynes over ZnIn2S4
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The construction of C-S bonds is very important. The hydrothiolation of alkenes or alkynes with thiols represents an attractive and atom economical approach for the formation of C-S bonds. In this manuscript, flowerlike microspheres of ZnIn2S4 consisting of interweaving nanoflakes were prepared by a solvothermal method and were applied for the first time in the visible light initiated hydrothiolation of alkenes and alkynes. The reactions between a broad range of thiols and alkynes or alkenes over irradiated ZnIn2S4 afford the corresponding hydrothiolated products in moderate to excellent yields. The mechanism proposed based on the ESR results suggests that the holes generated over irradiated ZnIn2S4 are reductively quenched by the thiols to generate thiyl radicals, which are added to the alkynes/alkenes to generate alkene/alkyl radicals for the propagation of thiol-ene/thiol-yne coupling reactions. The use of solar light and a semiconductor-based photocatalyst to realize the thiol-ene and thiol-yne coupling reactions in a green solvent (methanol), with only stoichiometric thiols required and applicable to a broad substrate scope, makes this reaction protocol a green, sustainable and cost-effective strategy for the synthesis of thiolated products. This study also highlights the great potential of semiconductor-based photocatalysis for advanced organic syntheses.
- Li, Yuanyuan,Cai, Jingyu,Hao, Mingming,Li, Zhaohui
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p. 2345 - 2351
(2019/05/21)
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- Efficient dehydrative alkylation of thiols with alcohols catalyzed by alkyl halides
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Alcohols can be efficiently converted into the useful thioethers by a transition metal- and base-free dehydrative S-alkylation reaction with thiols or disulfides by employing alkyl halides as the effective catalyst. This simple and efficient method is a green and practical way for the preparation of thioethers, as it tolerates a wide range of substrates such as aryl and alkyl thiols, as well as benzylic, allylic, secondary, tertiary, and even the less reactive aliphatic alcohols.
- Yang, Yaqi,Ye, Zihang,Zhang, Xu,Zhou, Yipeng,Ma, Xiantao,Cao, Hongen,Li, Huan,Yu, Lei,Xu, Qing
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supporting information
p. 9638 - 9642
(2017/11/30)
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- Photoinitiated Thiol-Ene “Click” Reaction: An Organocatalytic Alternative
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The thiol-ene coupling (TEC) reaction has attracted a lot of scientific attention during the last years, particularly in the fields of polymers, materials and more recently in drug design. The combination of organocatalysis and photocatalysis has enabled the development of an efficient synergistic protocol for the addition of various thiols to a plethora of olefins. Utilizing phenylglyoxylic acid as the catalyst-initiator and common household bulbs as the light source, we report an organocatalytic photoinitiated TEC reaction showing exceptional tolerance in the presence of various functionalities, untangling previously unsolved problems. (Figure presented.).
- Limnios, Dimitris,Kokotos, Christoforos G.
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supporting information
p. 323 - 328
(2017/02/05)
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- Luminescent Iridium(III) Pyridinium-Derived N-Heterocyclic Carbene Complexes as Versatile Photoredox Catalysts
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The development of novel luminescent iridium(III) complexes with highly tunable emission energy and versatile applications is of particular importance. In this Communication, a series of luminescent iridium(III) complexes supported by chromophoric pyridinium-derived N-heterocyclic carbene (NHC) ligands that display tunable emission from 516 to 682 nm were prepared. These complexes can be used as photocatalysts in photooxidation and photoreduction reactions and could have potential applications in pH sensing.
- Lam, Tsz Lung,Lai, Jing,Annapureddy, Rajasekar Reddy,Xue, Minying,Yang, Chen,Guan, Yunzhi,Zhou, Pingjian,Chan, Sharon Lai-Fung
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supporting information
p. 10835 - 10839
(2017/09/26)
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- Visible-Light-Mediated Thiol-Ene Reactions through Organic Photoredox Catalysis
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Synthetically useful radical thiol-ene reactions can be initiated by visible-light irradiation in the presence of an organic photocatalyst, 9-mesityl-10-methylacridinum tetrafluoroborate. The key thiyl radical intermediates are generated upon quenching of
- Zhao, Gaoyuan,Kaur, Sarbjeet,Wang, Ting
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supporting information
p. 3291 - 3294
(2017/06/23)
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- Visible light photocatalysis with benzophenone for radical thiol-ene reactions
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We report herein a simple, metal- and oxidant-free visible light promoted strategy for an anti-Markovnikov hydrothiolation of unactivated olefins using benzophenone as an inexpensive photocatalyst at room temperature. Anti-Markovnikov adducts of a wide va
- Singh, Manjula,Yadav, Arvind K.,Yadav, Lal Dhar S.,Singh
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supporting information
p. 2206 - 2208
(2017/05/16)
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- Benign and efficient preparation of thioethers by solvent-free S-alkylation of thiols with alkyl halides catalyzed by potassium fluoride on alumina
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The preparation of thioethers by S-alkylation of various thiols with alkyl halides under solvent-free reaction conditions using potassium fluoride on alumina (KF/Al2O3) as a solid catalyst has been investigated in detail with respect to three different modes of reaction activation (ultrasound irradiation, microwave irradiation, and conventional heating) for obtaining maximum yield of the thioether. The importance of KF/Al2O3 as a particularly efficient catalyst was corroborated for all three modes of reaction activation, although the reaction time was found to be strongly dependent on the mode of activation. The yield of the thioethers was also found to depend on the amount of the solid catalyst relative to the equimolar amounts of the two reactants.
- Nguyen, Kha Ngoc,Duus, Fritz,Luu, Thi Xuan Thi
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p. 349 - 360
(2016/06/01)
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- One-pot Metal-free Synthesis of Benzyl Alkyl Sulfides
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The synthesis of sulfides is important in various fields. This paper reports an efficient, odorless, and viable protocol for the base-mediated synthesis of benzyl alkyl sulfides using thiourea. The reactions were carried out under transition-metal-free co
- Lu, Xiaogang,Wang, Hongmei,Gao, Runli,Pei, Chengxin
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- Visible light promoted thiol-ene reactions using titanium dioxide
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The radical addition of thiols to alkenes is reported under photoredox conditions, using visible light and TiO2 as a cheap and readily available photocatalyst.
- Bhat, Venugopal T.,Duspara, Petar A.,Seo, Sangwon,Abu Bakar, Nor Syazwani Binti,Greaney, Michael F.
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supporting information
p. 4383 - 4385
(2015/03/18)
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- Ionic-liquid-assisted metal-free oxidative coupling of amines to give imines
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An oxidative coupling of amines to give imines in ionic liquids (ILs) under metal-free aerobic conditions has been developed. The high efficiency achievable in ILs is mechanistically explained in terms of activation of the starting materials (benzylamine and molecular oxygen) by an initial electron transfer, promoted by the ionic nature of the solvent. Reactivity data of variously p-substituted benzylamines show a general deactivating effect, which would imply a change in the rate-determining step in the reaction mechanism.
- Monopoli, Antonio,Cotugno, Pietro,Iannone, Francesco,Ciminale, Francesco,Dell'Anna, Maria Michela,Mastrorilli, Piero,Nacci, Angelo
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p. 5925 - 5931
(2015/03/30)
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- Selective approach to thioesters and thioethers via sp3 C-H activation of methylarenes
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Novel C-S cross-dehydrogenative coupling (CDC) approaches for the selective synthesis of thioesters and thioethers have been developed via sp3 C-H activation of methylarenes and subsequent functionalization. The reaction of methylarenes with thiols resulted in thioesters in the presence of a FeBr2/TBHP system, while treatment of methylarenes with thiols in the Pd(OAc)2/O2/TBHP system led to the formation of thioethers. Both the green protocols demonstrate good functional group tolerance and satisfactory yields. This journal is
- Feng,Lu,Cai
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p. 54409 - 54415
(2015/01/16)
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- Redox mediators in visible light photocatalysis: Photocatalytic radical thiol-ene additions
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Synthetically useful radical thiol-ene reactions can be initiated by visible light irradiation in the presence of transition metal polypyridyl photocatalysts. The success of this method relies upon the use of p-toluidine as an essential additive. Using th
- Tyson, Elizabeth L.,Niemeyer, Zachary L.,Yoon, Tehshik P.
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p. 1427 - 1436
(2014/03/21)
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- Transition metal photoredox catalysis of radical thiol-ene reactions
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We describe the anti-Markovnikov hydrothiolation of olefins using visible-light-absorbing transition metal photocatalysts. The key thiyl radical intermediates are generated upon quenching of photoexcited Ru*(bpz) 32 with a variety of thiols. The adducts of a wide variety of olefins and thiols are formed in excellent yield (73-99%).
- Tyson, Elizabeth L.,Ament, Michael S.,Yoon, Tehshik P.
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p. 2046 - 2050
(2013/03/29)
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- Iodine-mediated thioetherification of alcohols with disulfides or NaSh under microwave irradiation
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An efficient and novel method for the thioetherification of an alcohol with disulfides or NaSH under microwave irradiation is presented. In the presence of iodine, a variety of alcohols were smoothly S-alkylated with disulfides or NaSH to give the corresponding thioethers in moderate to excellent yields. Copyright
- Hu, Bolun,Sun, Leilei,Tang, Riyuan,Hu, Huanan
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p. 2556 - 2562,7
(2020/09/16)
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- TAPC-catalyzed synthesis of thioethers from thiols and alcohols
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A new synthesis of thioethers is described. The reaction of aryl alcohols with aryl, heteroaryl, and alkyl thiols in the presence of TAPC as an efficient catalyst affords good to excellent yields of thioethers. Furthermore, the reaction proceeds under metal-free and solvent-free conditions thus represents an interesting complement to known methods for thioether synthesis. A plausible mechanism for this reaction is delineated. Georg Thieme Verlag Stuttgart · New York.
- Bahrami, Kiumars,Khodaei, Mohammad Mehdi,Khodadoustan, Nayere
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experimental part
p. 2206 - 2210
(2011/10/09)
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- ZrCl4 dispersed on dry silica gel provides a useful reagent for S-alkylation of thiols with alcohols under solvent-free conditions
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ZrCl4 which is commercially available and not a costly compound, is a relatively safe chemical [LD50 [ZrCl4, oral rat] = 1688 mg Kg]. In this report we describe the use of ZrCl4 dispersed on dry silica gel as an efficient reagent for the efficient preparation of thioethers from thiols with alcohols under solvent-free conditions.
- Firouzabadi, Habib,Iranpoor, Nasser,Jafarpour, Maasoumeh
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- Synthesis of organic sulfides using Ce-exchanged NaY catalyst
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Synthesis of organic sulfides from thiols and alkyl halides is achieved using Ce-exchanged zeolite catalyst, Ce(72percent)NaY.
- Reddy, T. Indrasena,Varma, Rajender S.
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p. 621 - 622
(2007/10/03)
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