27846-23-7Relevant academic research and scientific papers
Photogeneration of thiyl radicals using metal-halide perovskite for highly efficient synthesis of thioethers
Liu, Xin,Bai, Rong,Guo, Zhifen,Che, Yan,Guo, Chunyi,Xing, Hongzhu
, (2021/11/01)
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.
Photoactive Metal-Organic Frameworks for the Selective Synthesis of Thioethers: Coupled with Phosphine to Modulate Thiyl Radical Generation
Guo, Zhifen,Liu, Xin,Bai, Rong,Che, Yan,Chi, Yanhong,Guo, Chunyi,Xing, Hongzhu
supporting information, p. 8672 - 8681 (2021/06/28)
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.
Efficient visible light initiated hydrothiolations of alkenes/alkynes over Ir2S3/ZnIn2S4: Role of Ir2S3
Li, Yuanyuan,Li, Zhaohui,Wang, Xinglin
, p. 409 - 416 (2020/07/30)
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.
Nickel-Catalyzed Reductive Thiolation of Unactivated Alkyl Bromides and Arenesulfonyl Cyanides
Rao, Weidong,Wang, Fei,Wang, Shun-Yi
, p. 8970 - 8979 (2021/07/19)
The cross-electrophile coupling between unactivated alkyl bromides with arenesulfonyl cyanides catalyzed by Ni(acac)2under reductive conditions to form unsymmetrical sulfides is developed. This approach for sulfide synthesis is practical, relies on available, unfunctionalized materials such as alkyl (pseudo)halides, and is scalable. This catalytic strategy provides a complementary method for the preparation of unsymmetrical alkyl-aryl sulfides under mild conditions with good functional group tolerance.
Method for preparing thioether from unsaturated olefin without catalysis of transition metal
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Paragraph 0009-0018, (2020/05/11)
The invention relates to a synthetic method for preparing thioether by a reaction of unsaturated olefin and thiophenol without catalysis of transition metal. The synthetic method comprises the following steps: adding an unsaturated olefin substrate and a thiophenol substrate into a reaction tube, then adding a catalytic amount of tripentafluorophenyl boron, and carrying out a reaction at 30-80 DEGC for 1-24 hours so as to obtain a thioether compound. Main innovation points of the invention are as follows: the thioether compound can be efficiently prepared without using of a transition metal catalyst, so heavy metal pollution is avoided. The method provided by the invention has the advantages of greenness, no solvent, simple and convenient operation, mild conditions, rapid reaction, good substrate universality, high reaction yield and selectivity and the like.
Radical-Mediated Strategies for the Functionalization of Alkenes with Diazo Compounds
Su, Yong-Liang,Liu, Geng-Xin,Liu, Jun-Wen,Tram, Linh,Qiu, Huang,Doyle, Michael P.
supporting information, p. 13846 - 13855 (2020/09/21)
One of the most common reactions of diazo compounds with alkenes is cyclopropanation, which occurs through metal carbene or free carbene intermediates. Alternative functionalization of alkenes with diazo compounds is limited, and a methodology for the addition of the elements of Z-CHR2 (with Z = H or heteroatom, and CHR2 originates from N2 CR2) across a carbon-carbon double bond has not been reported. Here we report a novel reaction of diazo compounds utilizing a radical-mediated addition strategy to achieve difunctionalization of diverse alkenes. Diazo compounds are transformed to carbon radicals with a photocatalyst or an iron catalyst through PCET processes. The carbon radical selectively adds to diverse alkenes, delivering new carbon radical species, and then forms products through hydroalkylation by thiol-assisted hydrogen atom transfer (HAT), or forms azidoalkylation products through an iron catalytic cycle. These two processes are highly complementary, proceed under mild reaction conditions, and show high functional group tolerance. Furthermore, both transformations are successfully performed on a gram-scale, and diverse γ-amino esters, γ-amino alcohols, and complex spirolactams are easily prepared with commercially available reagents. Mechanistic studies reveal the plausible pathways that link the two processes and explain the unique advantages of each.
Br?nsted Acid-Assisted Zinc-Catalyzed Markovnikov-Type Hydrothiolation of Alkenes Using Thiols
Taniguchi, Nobukazu
, p. 6528 - 6534 (2020/07/14)
The zinc-catalyzed regioselective hydrothiolation of alkenes with thiols was achieved in the presence of 4-toluenesulfonic acid. Through this procedure, Markovnikov-type sulfides were synthesized in excellent yields, and the formation of anti-Markovnikov-
Visible-Light-Mediated Organocatalyzed Thiol-Ene Reaction Initiated by a Proton-Coupled Electron Transfer
Levin, Vitalij V.,Dilman, Alexander D.
, p. 8337 - 8343 (2019/06/27)
A convenient method for performing a thiol-ene reaction is described. The reaction is performed under blue-light irradiation and catalyzed by photoactive Lewis basic molecules such as acridine orange or naphthalene-fused N-acylbenzimidazole. It is believed that the process is initiated by a proton-coupled electron transfer process within the complex between the thiol and the Lewis basic catalyst.
A concerted addition mechanism in [Hmim]Br-triggered thiol-ene reactions: a typical “ionic liquid effect” revealed by DFT and experimental studies
Feng, Lin,Ye, Renlong,Yuan, Tao,Zhang, Xiao,Lu, Guo-ping,Zhou, Baojing
supporting information, p. 5752 - 5758 (2019/04/17)
A concerted one-step addition mechanism for anti-Markovnikov hydrothiolation in [Hmim]Br catalyzed thiol-ene reactions is revealed by a combined DFT and experimental study for the first time. This special mechanism represents a typical “ionic liquid effec
Zn-catalyzed dihydrosulfenylation of alkynes using thiols
Taniguchi, Nobukazu,Kitayama, Kenji
, p. 739 - 741 (2019/04/30)
Zinc-catalyzed hydrosulfenylation of alkenes afforded regioselectively the corresponding sulfides in good yields. Furthermore, the method can promote dihydrosulfenylation of alkynes. The procedure could produce anti-Markovnikov type dithioacetals in excellent yields.
