- Chain growth mechanism for regioregular nickel-initiated cross-coupling polymerizations
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Chain growth mechanism for nickel-initiated regioregular polymerization of alkylthiophenes was analyzed. The 2-bromo-5-chlorozinc-3-hexylthiophene monomer was used for the analysis. It was observed that molecular weight of the polymer could be obtained by the molar ratio of monomer. An increase in the degree of polymerization was also observed with the conversion. The results show that the polymerization proceeds with the selective oxidative addition to the 2-bromopolythiophene.
- Sheina, Elena E.,Liu, Jinsong,Lovu, Mihaela Corina,Laird, Darin W.,McCullough, Richard D.
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Read Online
- Trithiocarbonate Anion as a Sulfur Source for the Synthesis of 2,5-Disubstituted Thiophenes and 2-Substituted Benzo[ b]thiophenes
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The trithiocarbonate anion (CS32-) was generated in situ from CS2 and KOH in dimethyl sulfoxide by a simple method and used as a novel synthetic equivalent of the S2- synthon for the synthesis of 2,5-disubstituted thiophenes from 1,3-butadiynes. Additionally, this system was employed for the metal-free synthesis of 2-substituted benzo[b]thiophenes from 2-haloalkynyl (hetero)arenes. These compounds were obtained from a cheap and readily available sulfur source in moderate to good yields, with good functional group tolerance.
- Paix?o, Douglas B.,Rampon, Daniel S.,Salles, Helena D.,Soares, Eduardo G. O.,Bilheri, Filipe N.,Schneider, Paulo H.
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supporting information
p. 12922 - 12934
(2020/11/26)
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- C-H Arylation of Thiophenes with Aryl Bromides by a Parts-per-Million Loading of a Palladium NNC-Pincer Complex
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A palladium NNC-pincer complex efficiently catalyzed the direct arylation of thiophene derivatives with extremely low palladium loadings of the order of parts per million. Thus, the reaction of various thiophenes with aryl bromides in the presence of 25-100 mol ppm of chlorido[(2-phenyl-κ- C 2)-9-phenyl-1,10-phenanthroline-κ 2- N, N ′]palladium(II) NNC-pincer complex, K 2CO 3, and pivalic acid in N, N -dimethyl acetamide afforded the corresponding 2- or 5-arylated thiophenes in good to excellent yields. A combination of the present C-H arylation and Hiyama coupling with the same NNC-pincer complex provides an efficient synthesis of unsymmetrical 2,5-thiophenes with catalyst loadings at mol ppm levels.
- Purta, Anggi Eka,Ichii, Shun,Tazawa, Aya,Uozumi, Yasuhiro
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supporting information
p. 1634 - 1638
(2020/08/28)
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- Copper Nanoparticles on Ordered Mesoporous Carbon Nitride Support: a Superior Catalyst for Homo- and Cross-Coupling of Terminal Alkynes under Base-Free Conditions
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A novel ordered mesoporous carbon nitride (OMCN) was synthesized as a functionalized support with 2,4,6-trichloro-1,3,5-triazine and benzidine as starting materials in the presence of SBA-15 as a template. Copper nanoparticles were then loaded on the C–N material to achieve a novel nanocomposite catalyst (Cu NPs-OMCN). The nanocomposite was utilized as a highly efficient catalyst for homo- and cross-coupling of terminal alkynes under base-free conditions in ethanol, and various symmetrical and unsymmetrical 1,3-diynes were obtained with good to excellent yields. Moreover, based on this reaction, a one-pot approach to synthesize 2,5-disubstituted thiophenes and furans from terminal alkynes were developed. Furthermore, the heterogeneous catalyst could be recovered and reused conveniently for several times with satisfactory yields.
- Xu, Hang,Wu, Liangying,Tian, Jing,Wang, Jun,Wang, Peng,Niu, Xiyu,Yao, Xiaoquan
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p. 6690 - 6696
(2019/11/02)
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- A porphyrin porous organic polymer with bicatalytic sites for highly efficient one-pot tandem catalysis
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A novel porphyrin-based porous organic polymer PPOP-1(Pd) with bifunctional catalytic sites was constructed via imine condensation of tetra(4-aminophenyl)porphyrin and acenaphthenequinone. PPOP-1(Pd) containing Pd(ii)-porphyrin and Pd(ii)-α-diimine moieties exhibits excellent catalytic activity and outstanding reusability for tandem catalytic reactions of C-H arylation and Suzuki coupling.
- Dai, Siyuan,Gu, Zhi-Guo,Li, Tao,Li, Yunxing,Liu, Yong,Shen, Rui,Yan, Xiaodong,Zhu, Wei
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supporting information
p. 822 - 825
(2019/01/21)
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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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- Trisulfur Radical Anion (S3?-) Involved [1 + 2 + 2] and [1 + 3 + 1] Cycloaddition with Aromatic Alkynes: Synthesis of Tetraphenylthiophene and 2-Benzylidenetetrahydrothiophene Derivatives
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S3?--mediated [1 + 2 + 2] and [1 + 3 + 1] cycloaddition reactions of aromatic alkynes to give tetraphenylthiophene and 2-benzylidenetetrahydrothiophene derivatives via two C-S bond formations are developed. These two protocols provide new, simple, and straightforward strategies to construct tetraphenylthiophene and 2-benzylidenetetrahydrothiophene derivatives under transition-metal-free conditions. This study also expands the application of S3?- in organic reactions.
- Li, Jing-Hao,Huang, Qi,Wang, Shun-Yi,Ji, Shun-Jun
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supporting information
p. 4704 - 4708
(2018/08/07)
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- PEPPSI-type palladium 1,2,3-triazolin-5-ylidene complexes – Synthesis, structure and catalytic properties in Suzuki-Miyaura coupling
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Palladium complexes of the general formula [PdCl2(tzNHC)(pyridine)] bearing a series 1,2,3-triazolin-5-ylidene (tzNHC) ligands were synthesized and characterized by spectroscopic methods and X-ray analysis. Complexes exhibit catalytic activity in the Suzuki-Miyaura coupling of boronic acids with aryl bromides.
- Ostrowska, Sylwia,Kubicki, Maciej,Pietraszuk, Cezary
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supporting information
p. 317 - 323
(2018/06/29)
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- METHOD FOR PRODUCING 14 GROUP METAL LITHIUM COMPOUND
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PROBLEM TO BE SOLVED: To provide a method for quantitatively producing a group 14 metal lithium compound under a mild condition. SOLUTION: The method for producing a group 14 metal lithium compound represented by formula (4): R4-nMLin comprises reacting a compound represented by formula (1): R4-nMXn and lithium in the presence of a polycyclic aromatic compound represented by formula (2) or formula (3). [In formula (1) and formula (2), R is a hydrocarbon group; M is a metal atom selected from Si, Ge and Sn; X is a halogen atom or R3M- (R and M are the same as mentioned above); and n is 1 or 2] and [R1 is H or a hydrocarbon group; and m is an integer of 0 to 5.] SELECTED DRAWING: None COPYRIGHT: (C)2016,JPOandINPIT
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Paragraph 0085-0087
(2016/10/31)
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- Method for catalyzing terminal alkene and powdered sulfur with copper to react in water phase to generate thiophene ring
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The invention discloses a method for catalyzing terminal alkene and powdered sulfur to react in a pure water phase to prepare a thiophene derivative. A water-soluble complex is used as a catalyst, and a one-pot reaction is conducted in the pure water phas
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Paragraph 0004; 0022
(2016/10/10)
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- Copper-catalyzed direct synthesis of furans and thiophenes via decarboxylative coupling of alkynyl carboxylic acids with H2O or Na2S
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2,5-Diaryl-substituted furans were synthesized from the copper-catalyzed decarboxylative coupling of aryl-substituted aryl propiolic acids in the presence of H2O. The homocoupling of alkynyl carboxylic acids provided 1,4-diaryldiynes, which then reacted with H2O to give the desired furans through cyclization. Addition of the copper catalyst was critical, and the addition of a ligand increased the yield of products in both the homocoupling and cyclization reactions. In addition, thiophenes could be obtained when the reaction was conducted in the presence of Na2S.
- Irudayanathan, Francis Mariaraj,Edwin Raja, Gabriel Charles,Lee, Sunwoo
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p. 4418 - 4425
(2015/06/08)
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- Stannyl-Lithium: A Facile and Efficient Synthesis Facilitating Further Applications
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We have developed a highly efficient, practical, polycyclic aromatic hydrocarbon (PAH)-catalyzed synthesis of stannyl lithium (Sn-Li), in which the tin resource (stannyl chloride or distannyl) is rapidly and quantitatively transformed into Sn-Li reagent at room temperature without formation of any (toxic) byproducts. The resulting Sn-Li reagent can be stored at ambient temperature for months and shows high reactivity toward various substrates, with quantitative atom efficiency.
- Wang, Dong-Yu,Wang, Chao,Uchiyama, Masanobu
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supporting information
p. 10488 - 10491
(2015/09/28)
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- Trisulfur radical anion as the key intermediate for the synthesis of thiophene via the interaction between elemental sulfur and NaO t Bu
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A facile base-promoted sulfur-centered radical generation mode and a single-step protocol for the synthesis of thiophene derivatives using 1,3-diynes via the interaction between elemental sulfur and NaOtBu has been reported. EPR experiments revealed that the trisulfur radical anion acts as a key intermediate of this process. A plausible mechanism has been proposed.
- Zhang, Guoting,Yi, Hong,Chen, Hong,Bian, Changliang,Liu, Chao,Lei, Aiwen
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supporting information
p. 6156 - 6159
(2015/01/16)
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- Direct C-H arylation of thiophenes at low catalyst loading of a phosphine-free bis(alkoxo)palladium complex
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An efficient phosphine-free direct C-H arylation of thiophenes at the α-position has been developed at low catalyst loading of bis(alkoxo)palladium complex (Cat.I, 0.1-0.2 mol %). The developed synthetic method can be applied to the synthesis of α-aryl/heteroaryl thiophenes from aryl or heteroaryl bromides in good to excellent yields and is compatible with the substrates bearing electron-donating or electron-withdrawing groups. The reactivities of the 2- and 5-positions of thiophenes are equivalent and not dependent on steric hindrance under optimal conditions. This condition can also be applied to other heterocyclic moieties such as benzothiophene, benzofuran, and pyrrole with high conversion yields.
- Li, Yabo,Wang, Jingran,Huang, Mengmeng,Wang, Zhiwei,Wu, Yusheng,Wu, Yangjie
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p. 2890 - 2897
(2014/05/06)
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- Sulfur heterocyclization and 1,3-migration of silicon in reaction of 1,3-diynes with sodium triisopropylsilanethiolate: One-pot synthesis of 2,5-disubstituted 3-(triisopropylsilyl)thiophenes
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Sulfur heterocyclization and 1,3-migration of silicon have been realized in the reactions of a range of 1,3-diynes with sodium triisopropylsilanethiolate in N,N-dimethylformamide. These provided 40-72% yields of 2,5-disubstituted 3-(triisopropylsilyl)thiophenes and up to 50% yield of 2,5-disubstituted thiophenes. Georg Thieme Verlag Stuttgart, New York.
- Tang, Jialiang,Ming, Ling,Zhao, Xiaoming
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p. 1713 - 1718
(2013/07/25)
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- Copper(I)-catalyzed synthesis of 2,5-disubstituted furans and thiophenes from haloalkynes or 1,3-diynes
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A regioselective synthesis of 2,5-disubstituted furans using copper(I) catalyst from haloalkynes in a one-pot procedure has been reported. This chemistry proceeds through the hydration reaction of 1,3-diynes, which can be readily prepared from the coupling reaction of haloalkynes in the presence of CuI. The procedure also can be used for the facile synthesis of 2,5-disubstituted thiophenes.
- Jiang, Huanfeng,Zeng, Wei,Li, Yibiao,Wu, Wanqing,Huang, Liangbing,Fu, Wei
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scheme or table
p. 5179 - 5183
(2012/07/03)
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- Synthesis of 2-aryl- and 2,5-diarylfurans and thiophenes by Suzuki-Miyaura reactions using potassium trifluoroborate salts and heteroaryltellurides
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The Suzuki-Miyaura cross-coupling reaction of 2-(butyltellanyl) or 2,5-bis-(butyltellanyl)furans and thiophenes with potassium aryltrifluoroborate salts catalyzed by palladium afforded 2-aryl- or 2,5-diaryl-furans and thiophenes in moderate to good yields.
- Botteselle, Giancarlo V.,Hough, Thomas L. S.,Venturoso, Raphael C.,Cella, Rodrigo,Vieira, Adriano S.,Stefani, Helio A.
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experimental part
p. 870 - 873
(2009/04/11)
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- A new facile approach to the synthesis of 3-methylthio-substituted furans, pyrroles, thiophenes, and related derivatives
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(Chemical Equation Presented) 2-(Methylthio)-1,4-diaryl-2-butene-1,4-dione (3) are prepared from readily available aryl methyl ketones in the presence of copper(II) oxide, iodine, and dimethyl sulfoxide. The success of the cross-coupling reaction of 4-chloroacetophenone with 2-acetylthiophene confirms a proposed self-sorting tandem reaction mechanism. Both Z- and E-isomers of compound 3 are readily converted into the corresponding 3-methylthio 2,5-diaryl furan 7 in good yield through a domino process involving the reduction of the double bond followed by the Paal-Knorr furan synthesis. Meanwhile, 4-bromo-3-methylthio 2,5-diaryl furan 10 is obtained either by the treatment of furan 7 with molecular bromine or by the treatment of diketone 3 with 30% hydrogen bromide in acetic acid solution in one pot. Removal of the methylthio group is accomplished by the treatment of 7 with Raney Ni in ethanol, which affords the diaryl-substituted furan 11 in excellent isolated yield. Selective reduction of the double bond of compound 3 leads to the formation of the saturated 1,4-diketone 13, which is easily converted to the corresponding 3-methylthio-2,5-diaryl-substituted pyrrole 14 and thiophene 15 via the Paal-Knorr cyclization reaction.
- Yin, Guodong,Wang, Zihua,Chen, Aihua,Gao, Meng,Wu, Anxin,Pan, Yuanjiang
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p. 3377 - 3383
(2008/09/21)
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- Preferential oxidative addition in palladium(0)-catalyzed suzuki cross-coupling reactions of dihaloarenes with arylboronic acids
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The study of Pd(0)-/t-Bu3P system as a powerful catalyst for the cross-coupling of n,m-dihaloarenes with 1 equiv of arylboronic acids is described. Our work demonstrated that the fate of the regenerated Pd(0) catalyst can be controlled when the appropriate ligand is employed. The results described here may lead to the development of new, efficient processes to conjugate polymers with controlled length which are potentially useful in molecular electronics. Copyright
- Dong, Cheng-Guo,Hu, Qiao-Sheng
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p. 10006 - 10007
(2007/10/03)
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- 1,2-Dithiines and precursors, XVI: Synthesis, structure, and reactivity of non-anellated 1,2-dithiines
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Various monocyclic 1,2-dithiines 6a,b,d-t were prepared via (Z,Z)-1,4-difunctionalized butadienes (4-11,19,20). A twisted cyclic structure A is unequivocally proved rather than of the ringopened valence isomer B. The reactivity of these 1,2-dithiines is d
- Schroth, Werner,Dunger, Simona,Billig, Frank,Spitzner, Roland,Herzschuh, Rainer,Vogt, Almut,Jende, Thomas,Israel, Gunter,Barche, Jens,Stroehl, Dieter,Sieler, Joachim
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p. 12677 - 12698
(2007/10/03)
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