- Complexes of palladium(II) with N-heterocyclic carbenes from adamantylimidazole as precatalysts for thiophene and imidazole arylation
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Complexes of palladium(II) with N-heterocyclic carbenes of the PEPPSI-type were synthesized by the reaction of PdCl2 with 1-adamantyl-3-(R-methyl)-1H-imidazolium salts. These complexes were used as productive precatalysts for substituted thioph
- Denisov,Dmitriev,Gorbunov,Glushkov
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- Cu-catalyzed [2 + 2 + 1] cascade annulation of vinyl iodonium salts with elemental sulfur/selenium for the modular synthesis of thiophenes and selenophenes
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A [2 + 2 + 1] annulation protocol has been established for the modular synthesis of 2,4-disubstituted thiophenes/selenophenes, with excellent regioselectivity. The reactions have been catalyzed by copper salt with elemental sulfur and selenium serving as
- Chen, Chao,Wang, Fei,Wu, Chao,Wu, Yaxing
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p. 945 - 949
(2022/02/01)
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- Hexafluoroisopropanol as solvent and promotor in the Paal-Knorr synthesis of N-substituted diaryl pyrroles
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An additive-free synthesis of challenging N-substituted aryl pyrroles from the often poorly soluble corresponding 1,4-diketones by means of the Paal-Knorr pyrrole synthesis is reported, which makes use of the unique properties of 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) as a solvent and reaction promotor. Our procedure offers simple execution and purification as well as easy scale-up and can be applied in the Paal-Knorr synthesis of a large number of structurally diverse pyrroles including the synthetically challenging tetra- and penta-substituted pyrroles in moderate to excellent yields. HFIP can also be used as solvent in the Paal-Knorr synthesis of furans and thiophenes; however, the solvent effect is more pronounced in synthesis of pyrroles.
- Schirmacher, Robert H.E.,R?sch, Daniel,Thomas, Franziska
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- Access to Substituted Thiophenes through Xanthate-Mediated Vinyl C(sp2)-Br Bond Cleavage and Heterocyclization of Bromoenynes
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An environmentally sustainable strategy for the chemoselective heterocyclization of bromoenynes through a transition-metal-free sulfuration/cyclization process is reported. Using inexpensive and safe EtOCS2K as a thiol surrogate and tetrabutylphosphonium bromide and H2O as a mixed solvent, the reaction provided a range of substituted thiophenes in moderate to good yields. In addition, 2,3,4,5-tetrasubstituted thiophenes were able to be prepared under mild reaction conditions by electrophilic heterocyclization with NH4I and EtOCS2K in good yields.
- Huang, Guoling,Li, Jian,Li, Jianrong,Li, Jiaming,Sun, Minghua,Zhou, Peng,Chen, Lu,Huang, Yubing,Jiang, Shaohua,Li, Yibiao
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p. 13037 - 13049
(2020/11/26)
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- A trisulfur radical anion (S3-) involved sulfur insertion reaction of 1,3-enynes: Sulfide sources control chemoselective synthesis of 2,3,5-trisubstituted thiophenes and 3-thienyl disulfides
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Cascade cyclization reactions of S3-in situ generated from S2- with 1,3-enynes for the chemoselective synthesis of 2,3,5-trisubstituted thiophenes and 3-thienyl disulfides controlled by sulfide salts are develop
- Li, Jing-Hao,Huang, Qi,Rao, Weidong,Wang, Shun-Yi,Ji, Shun-Jun
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p. 7808 - 7811
(2019/07/08)
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- Adamantanyl-substituted PEPPSI-type palladium(II) N-heterocyclic carbene complexes: synthesis and catalytic application for CH activation of substituted thiophenes
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[Figure not available: see fulltext.] Starting from 1-adamantanyl-3-imidazole, a number of new 1-adamantanyl-3-benzylimidazolium salts and corresponding unsymmetrically substituted Pd(II) PEPPSI-type complexes were prepared, including dichloride, dibromide, and diiodide. Single crystal X-ray crystallography confirmed solid state structures in six cases. The complexes reported in this work displayed moderate activities as precatalysts for CH activation/arylation reaction of substituted thiophenes.
- Glushkov, Vladimir A.,Denisov, Michail S.,Gorbunov, Aleksey A.,Myalitzin, Yurii A.,Dmitriev, Maksim V.,Slepukhin, Pavel A.
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p. 217 - 228
(2019/05/15)
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- Transition-Metal-Free Sulfuration/Annulation of Alkenes: Economical Access to Thiophenes Enabled by the Cleavage of Multiple C-H Bonds
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A novel, atom economical, and transition-metal-free strategy for the synthesis of thiophenes from substituted buta-1-enes with potassium sulfide has been presented. The reaction achieves double C-S bond formations via cleavage of multiple C-H bonds and provides an efficient approach to access various functionalized thiophenes. Moreover, the strategy can also be used for the synthesis of thiophenes from 1,4-diaryl-1,3-dienes. Mechanistically, DMSO plays a role of oxidant and S3?- in situ generated from K2S is involved.
- Chen, Liang,Min, Hao,Zeng, Weilan,Zhu, Xiaoming,Liang, Yun,Deng, Guobo,Yang, Yuan
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supporting information
p. 7392 - 7395
(2019/01/03)
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- In-Depth Assessment of the Palladium-Catalyzed Fluorination of Five-Membered Heteroaryl Bromides
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A thorough investigation of the challenging Pd-catalyzed fluorination of five-membered heteroaryl bromides is presented. Crystallographic studies and density functional theory (DFT) calculations suggest that the challenging step of this transformation is
- Milner, Phillip J.,Yang, Yang,Buchwald, Stephen L.
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supporting information
p. 4775 - 4780
(2015/10/28)
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- Cu-catalyzed double S-alkenylation of potassium sulfide: A highly efficient method for the synthesis of various thiophenes
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An efficient synthetic approach to variously substituted thiophenes has been developed through copper-catalyzed tandem S-alkenylation of potassium sulfide with 1,4-diiodo-1,3-dienes.
- You, Wei,Yan, Xiaoyu,Liao, Qian,Xi, Chanjuan
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supporting information; experimental part
p. 3930 - 3933
(2010/11/02)
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- Palladium-catalyzed perarylation of 3-thiophene- and 3-furancarboxylic acids accompanied by C-H bond cleavage and decarboxylation
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3-Thiophene- and 3-furancarboxylic acids efficiently undergo perarylation accompanied by cleavage of the three C-H bonds and decarboxylation upon treatment with excess aryl bromides in the presence of a palladium catalyst to give the corresponding tetraarylated products in good yields.
- Nakano, Masaya,Tsurugi, Hayato,Satoh, Tetsuya,Miura, Masahiro
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body text
p. 1851 - 1854
(2009/04/10)
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- Selective palladium-catalysed ipso arylation of α,α- disubstituted benzo[b]thien-2-ylmethanols with aryl bromides using PCy 3 as ligand
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α,α-Diphenylbenzo[b]thien-2-ylmethanol was treated with a series of aryl bromides in the presence of palladium(II) acetate and tricyclohexylphosphane to give the appropriate 2-aryl-benzo[b]thiophenes in good to excellent yield with concomitant formation o
- Biro, A. Beatrix,Kotschy, Andras
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p. 1364 - 1368
(2008/09/18)
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- Diels-alder reaction and double phenylation in reaction of thiophenes with diphenyliodonium triflate
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The reaction of 2,5-dimethylthiophene with diphenyliodonium triflate in the presence of N-phenylmaleimide and a catalytic amount of Cu(OAc)2 gave 1:1 and 1:2 cycloadducts with N-phenylmaleimide. The similar reactions of 2,5-bis(trimethylsilyl)thiophene, 3-phenylthiophene, and thiophene afforded 2,5-diphenylthiophene, 2,3,5-triphenylthiophene, and 2,5-diphenylthiophene, respectively. The cycloadducts and 2,5-diphenylated thiophenes are considered to be formed via S-phenylation of thiophenes affording 1-phenylthiophenium triflates.
- Zhang, Bian-Xiang,Nuka, Takato,Fujiwara, Yuzo,Yamaji, Teizo,Hou, Zhaomin,Kitamura, Tsugio
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p. 199 - 206
(2007/10/03)
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- Palladium-catalyzed multiple arylation of thiophenes
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Secondary 2-thiophenecarboxamides efficiently undergo unique triarylation accompanied by formal decarbamoylation under palladium catalysis. 3-Substituted thiophenes, especially having an electron-withdrawing group, can also be triarylated. Copyright
- Okazawa, Toru,Satoh, Tetsuya,Miura, Masahiro,Nomura, Masakatsu
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p. 5286 - 5287
(2007/10/03)
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- Preparation and reactivity of 1,3-bis(alkylthio)allenes and tetrathiacyclic bisallenes
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Reactions of Ph2C3 dianion, prepared from 1,3-diphenylpropyne and n- butyllithium, with alkyl thiocyanates or alkane dithiocyanates gave 1,3- bis(alkylthio)allenes 1 or tetrathiacyclic bisallenes 2, respectively. Thermal reactions of 1 gave thiophenes 4 and 7, benzothiepin 5, 1,2- bis(benzylidene)cyclobutane 6, thiete 8, and α,β-unsaturated ketone 9, and the reactions of tetrathiacyclic bisallenes 2a gave a cyclic dimer, 1,2- bis(benzylidene)cyclobutane derivative 10, quantitatively. Irradiation of 1,3-bis(alkylthio)allenes 1 and tetrathiacyclic bisallenes 2a caused rearrangement to give alkynes 18, 20, and 21. In the irradiation of the cyclic bisallenes 2a, isomerizations from dl to meso and meso to dl isomers were also found. In the reactions of allenes 1 and cyclic bisallenes 2a with diphenyl diazomethane, the diazomethane reacted selectively with the double bond rather than with the sulfur atom.
- Shimizu, Toshio,Sakamaki, Kensuke,Miyasaka, Daisuke,Kamigata, Nobumasa
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p. 1721 - 1728
(2007/10/03)
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- Preparation and thermal reaction of 1,3-bis(alkylthio)allenes
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Reactions of Ph2C3 dianion with alkyl thiocyanates or ethylene 1,2-dithiocyanate give 1,3-bis(alkylthio)allenes or tetrathiacyclic bisallene, respectively. Thermal reactions of 1,3-bis(benzylthio)allene and tetrathiacyclic bisallene afford 2,3,5-triphenylthiophene and 1,2-bismethylidene cyclobutane derivatives, respectively.
- Shimizu, Toshio,Sakamaki, Kensuke,Kamigata, Nobumasa
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p. 8529 - 8532
(2007/10/03)
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- Synthesis of unsymmetrical 2,3-diaryl- and 2,4-diarylthiophenes starting from 2,5-dichlorothiophene
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Unsymmetrically substituted 2,4-diaryl- and 2,3-diarylthiophenes were synthesized from 2,5-dichlorothiophene via 4-aryl-2-chlorothiophenes in two and four steps including Ni-mediated cross-coupling, respectively. Aluminum chloride-catalyzed reaction of 3-aryl-2-chlorothiophenes with some aromatic ethers unexpectedly led to the formation of the corresponding 2,4-isomers.
- Sone,Sato,Umetsu,Yoshino,Takahashi
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p. 2187 - 2194
(2007/10/02)
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- Reactions of α,β-Unsaturated Thiones with Diphenylcyclopropenone and Diphenylcyclopropenethione
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2-(Arylmethylene)tetralin-1-thione and 1-aryl-3-phenyl-2-propene-1-thione (thiochalcone) reacted with diphenylcyclopropenone across the =C-CO bond giving a thiophene derivative and a polysubstituted phenol with the arylketene/sulfur elimination, whereas the reaction with diphenylcyclopropenethhione took place as the C=S bond affording a spiro compound.
- Karakasa, Takayuki,Takeda, Satoshi,Saito, Takao,Motoki, Shinichi
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p. 3279 - 3280
(2007/10/02)
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- Thermolytic Reaction of Chalcone with Sulphur: Formation of a Sulphur Heterocycle
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Two of the four products isolated in the thermolytic reaction of chalcone with sulphur have been characterized as dihydrochalcone and 4,5-dibenzoyl-3,6-diphenyl-1,2-dithi-4-ene on the basis of UV, IR, PMR and mass data.
- Joshi, Sunita,Dhar, Durga Nath
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p. 852 - 853
(2007/10/02)
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- A Novel Thermolytic Reaction of Chalcone with Sulphur
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The formation of 2,4,5-triphenylthiophene in the thermolytic reaction of chalcone with sulphur is described.
- Dhar, Durga N.,Bhatia, Bindu
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- ETUDE DE LA REACTIVITE DE L'ION AZTURE VIS A VIS DE CATIONS HETEROCYCLIQUES-III REARRANGEMENTS THERMIQUES ET PHOTOCHIMIQUES DES AZIDES COVALENTS RESULTANT DE L'ION AZOTURE SUR DES CATIONS PYRYLIUM ET THIOPYRYLIUM DIVERSEMENT SUBSTITUES. NOUVEL ACCES A DES HETEROAZEPINES
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Azidopyrans rearrange at room temperature to 1,3-oxazepins but azidothiopyrans need heating to form unstable thiazepins. these intermediate thiazepins give the competitive formation of the corresponding pyridines after sulphur extrusion or of the corresponding thiophens after elimination of benzonitrile. Photochemical attempts to obtain thiazepins from azidothiopyrans were unsuccessful.
- Desbene, P.-L.,Cherton, J.-C.
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p. 3559 - 3565
(2007/10/02)
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- Reaction of 2,4-Bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane-2,4-disulphide with Substituted Butane-1,4-diones: Part II - Novel Synthesis of Substituted Thiophenes and Furans
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The reaction of substituted butane-1,4-diones (2) with 2,4-bis(4-methoxyphenyl)1,3,2,4-dithiadiphosphetane-2,4-disulphides (1; Lawesson reagent) has been investigated.While the reaction of 1,2-diacylethane (2k) with 1 leads exclusively to the formation of the corresponding 2,5-disubstituted thiophene (4k) in excellent yield, the interaction of tri- and tetrasubstituted butane-1,4-diones (2a-j) with 1 under identical conditions invariably results in the formation of a mixture of the corresponding thiophenes (4) and furans (3) in varying proportions.The identity of 3 and 4 and also their molar percentages in the product mixtures have been established by GLC and PMR spectral analyses.
- Shridhar, D. R.,Jogibhukta, M.,Rao, P. Shanthan,Handa, Vijay K.
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p. 1187 - 1190
(2007/10/02)
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- Thiophenes useful in control of acarids
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Substituted thiophenes of the following formula, some of which are new compounds, are useful in controlling certain pests, particularly mites: STR1 wherein A, Y and Z are various substituents such as phenyl and substituted phenyl.
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