- Palladium-catalysed thioetherification of aryl and alkenyl iodides using 1,3,5-trithiane as sulfur source
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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,Rajat Rao, Yalamarti Venkat,Zugó, Alexandra,Pongrácz, Péter
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- Redox-Neutral Organometallic Elementary Steps at Bismuth: Catalytic Synthesis of Aryl Sulfonyl Fluorides
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A Bi-catalyzed synthesis of sulfonyl fluorides from the corresponding (hetero)aryl boronic acids is presented. We demonstrate that the organobismuth(III) catalysts bearing a bis-aryl sulfone ligand backbone revolve through different canonical organometallic steps within the catalytic cycle without modifying the oxidation state. All steps have been validated, including the catalytic insertion of SO2 into Bi-C bonds, leading to a structurally unique O-bound bismuth sulfinate complex. The catalytic protocol affords excellent yields for a wide range of aryl and heteroaryl boronic acids, displaying a wide functional group tolerance.
- Cornella, Josep,Magre, Marc
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p. 21497 - 21502
(2022/01/03)
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- Dechalcogenization of Aryl Dichalcogenides to Synthesize Aryl Chalcogenides via Copper Catalysis
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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
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p. 2707 - 2712
(2020/03/11)
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- Copper-Catalyzed Production of Diaryl Sulfides Using Aryl Iodides and a Disilathiane
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A disilathiane was found to be a novel S1 source for the copper-catalyzed synthesis of diaryl sulfides using aryl iodides. The reaction of iodoarenes and hexamethyldisilathiane, (Me 3 Si) 2 S, in the presence of a catalytic amount of CuI/1,10-phenanthroline provided various types of diaryl sulfides in good yields.
- Ogiwara, Yohei,Maeda, Hiromu,Sakai, Norio
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supporting information
p. 655 - 657
(2017/11/29)
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- Copper-mediated oxidative trifluoromethylthiolation of aryl boronic acids with CF3CO2Na and elemental sulfur
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A practical three-component copper-mediated oxidative trifluoromethylthiolation of aryl boronic acids with cheap and readily available sodium trifluoroacetate and elemental sulfur is reported. A variety of trifluoromethylthio-substituted aromatics are synthesized in moderate yields under mild reaction conditions.
- Zhai, Lijuan,Li, Yaming,Yin, Jun,Jin, Kun,Zhang, Rong,Fu, Xinmei,Duan, Chunying
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p. 10262 - 10266
(2013/11/19)
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- Copper-Catalyzed Cross-Coupling of Aryl Halides and Thiols Using Microwave Heating
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The copper-catalyzed cross-coupling of aryl halides and thiols using microwave heating is described.
- Wu, Yong-Jin,He, Huan
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p. 1789 - 1790
(2007/10/03)
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- Utilisations synthetiques d'une electrode soluble au soufre. IV. Creation de l'enchainement C-S-C a partir d'hydrocarbures aromatiques, d'heterocycles et d'amines aromatiques
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Use of a sacrificial sulfur electrode in electroorganic chemistry.IV.Formation of the C-S-C bond from aromatic hydrocarbons, heterocycles and aromatic amines.The electrophile S2+ was prepared in organic media by oxidation of a carbon-sulfur electrode.This species can react with aromatic hydrocarbons, heterocycles and aromatic amines to produce organic monosulfides. carbon-sulfur electrode / sacrificial electrode / sulfur cation / organic sulfide / electrophilic substitution
- Do, Quang Tho,Elothmani, Driss,Simonet, Jacques,Guillanton, Georges Le
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p. 789 - 793
(2007/10/02)
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- Thioxanthene Dioxide Based Amino-Protecting Groups Sensitive to Pyridine Bases and Dipolar Aprotic Solvents
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In pursuit of an analogy between fluorine and thioxanthene dioxide, the suitability of the D-TMOC and related functions as base-sensitive amino-protecting groups was examined.Such compounds were found to be cleaved by mild pyridine bases against which the analogous FMOC derivatives are stable.Deblocking gives as a byproduct the methylene sulfone 5 or its adducts with an appropriate secondary deblocking amine.Certain solvents such as DMSO, DMF, etc., were also found to deblock the D-TMOC group, especially on warming, whereas the compounds were stable in ordinary nonpolar solvents (e.g., CH2Cl2, benzene, THF).For practical use the D-TMOC function suffers from excessive solvent sensitivity and the low solubility of some derivatives.To overcome this problem tert-butyl groups were introduced into the 2,7-positions of the xanthene nucleus.The resulting DBD-TMOC function proved easier to handle in terms of both solubility and reactivity.The key alcohol 12 was synthesized from diphenyl sulfide 13 by tert-butylation followed by Friedel-Crafts cyclization using methyl dichloromethyl ether to give a 50-50 mixture of thioxanthene 15 and corresponding thioxanthone 16.Without separation of the mixture, oxidation gave a mixture of the dioxides 17 and 18, and again without separation the mixture was reduced by P/HI to give the desired compound 17 in an overall yield of 60-65percent.Formylation of 17 followed by reduction gave 12, from which urethanes 11 were obtained in the normal manner via the chloroformate.The DBD-TMOC group was stable to strong acids (TFA, HBr-HOAc) but deblocked by catalytic hydrogenolysis as well as via mild bases and warming in dipolar aprotic solvents.Upon deblocking of 11 in DMSO the byproduct 27 separated completely, especially if 3-5percent water is present or added subsequently.This process provides a clean solution of the deblocked amine, thus simplifying the use of the DBD-TMOC function in peptide synthesis.An example given is that of leucine enkephalin, in which all coupling steps were effected by acid chlorides and all deblocking steps by warming in DMSO.It was shown with model compounds that coupling could be effected under appropriate conditions without racemization.
- Carpino, Louis A.,Gao, Heau-Shan,Ti, Gen-Shing,Segev, David
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p. 5887 - 5897
(2007/10/02)
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- Process for the synthesis of peptides utilizing thioxanthylmethyloxycarbonyl dioxides
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A composition of the formula: STR1 wherein X is lower alkyl, and Z is an amino acid a peptide residue or a good leaving group, the composition is adaptable as a blocking or protecting group for an amine composition useful in peptide synthesis and a method of protecting an amino group of an organic molecule during a reaction which modifies a portion of the molecule other than the protected amino group.
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