Regioselective synthesis of 2bromomethyl5arylthiophene. New shelfstable halo and alkoxysubstituted pyridylboronic acids and their suzuki crosscoupling reactions to yield heteroarylpyridines. Jul 17, 2018 a variety of imine derivatives have been synthesized via suzuki cross coupling of n4bromophenylbromothiophen2ylmethanimine with various arylboronic acids in moderate to good yields 5872%. Solventfree, microwaveassisted synthesis of thiophene. Crosscoupling reaction an overview sciencedirect topics. Pdf palladium0 catalyzed suzuki crosscoupling reaction of 2,5. Alternative carbene precursors for metalcatalyzed cross coupling may expand the portfolio of methods for cc bond construction. Nov 12, 2007 conditions have been identified that enable the onepot double suzuki coupling of 4,5dibromothiophene2carboxaldehyde to proceed in good yield. In the area of synthetic organic chemistry, suzuki crosscoupling. Electronic properties were evaluated by uvvis, cyclic voltammogram, and theoretical calculations. When they tried to do a suzuki cross coupling reaction involving tosylate 2 using pdcl 2 dppf as the catalyst, the reaction failed to give any product, likely due to the oxygencontaining side chain scheme 37.
Suzukimiyaura crosscoupling in acylation reactions. The suzuki reaction is an important type of coupling reaction, a designation that encompasses a variety of processes that combine or couple two hydrocarbon fragments with the aid of a catalyst in the suzuki reaction, palladium in a basic environment. Dec, 2019 alternative carbene precursors for metalcatalyzed cross coupling may expand the portfolio of methods for cc bond construction. Facile synthesis of n 4bromophenyl1 3bromothiophen2. Conclusion in conclusion, we have developed a facile synthesis. A series of carbazole thiophene dimers, p1p9, were synthesized using suzukimiyaura and ullmann coupling reactions. Thiophenebased macrocycles via the suzukimiyaura cross. It is widely used to synthesize poly olefins, styrenes, and substituted biphenyls, and has been extended to incorporate alkyl bromides. Metal catalyzed suzukimiyaura crosscoupling preprints. Synthesis and characterization of new thieno3,2bthiophene. For heterocyclic substrates aqueous catalysis is found to be more efficient than suzuki coupling under anhydrous conditions. Synthesis and photophysical properties of novel biphenyl derivatives containing furan and thiophene groups bao li, bin liu, qian li, haiyan fang, and mingxin yu.
The suzuki reaction applied to the synthesis of novel. Research article open access regioselective synthesis of. Synthesis and photophysical properties of novel biphenyl. Read thiophene based macrocycles via the suzukimiyaura cross coupling reaction, tetrahedron on deepdyve, the largest online rental service for scholarly research with thousands of academic publications available at your fingertips. The suzuki reaction proved a convenient method for cc bond. The suzuki reaction is the coupling of an aryl or vinyl boronic acid with an aryl or vinyl halide or triflate using a palladium catalyst. Efficient double suzuki crosscoupling reactions of 2,5dibromo3. Synthesis of 3substituted5pyrrol2ylindazoles by the suzuki cross.
Letter 93 letterprogrammed synthesis of tetraarylthieno3,2b thiophene by siteselective suzuki cross coupling reactions of tetrabromothieno3,2bthiopheneprogrammed synthesis of tetraarylthieno3,2hien nguyen,a dung xuan nguyen,b thiophene a thinh quang tran,a binh ngoc vo,a thao huong nguyen,a thi minh ha vuong,b tung t. The ease of isolating and purifying these precursors has enabled numerous thiophene based compounds to be synthesized from building blocks with widely different characteristics. These thiophene derivatives were synthesized by using several arylboronic acids via. Synthesis of novel derivatives of carbazolethiophene. Palladium 0 catalyzed suzuki crosscoupling reactions of 2,4.
Thiophene derivatives have shown versatile pharmacological activities. Suzuki coupling publications frontier scientific, inc. Diversityoriented approach to functional thiophene dyes by. The suzuki reaction applied to the synthesis of novel pyrrolyl and. Suzuki cross coupling of solidsupported chloropyrimidines with arylboronic acids.
Letter 93 letterprogrammed synthesis of tetraarylthieno3,2b thiophene by siteselective suzuki crosscoupling reactions of tetrabromothieno3,2bthiopheneprogrammed synthesis of tetraarylthieno3,2hien nguyen,a dung xuan nguyen,b thiophene a thinh quang tran,a binh ngoc vo,a thao huong nguyen,a thi minh ha vuong,b tung t. A wide range of electron donating and withdrawing functional groups were well tolerated in reaction conditions. It is a very effective method for making carbon carbon bonds. Diversityoriented approach to functional thiophene dyes by suzuki couplinglithiation onepot sequences. Here, we present two straightforward, modular and comparative onepot syntheses of diversely functionalized thiophenes with high yields s. Pdpth33 is superior to pdpph34 in catalyzing suzukimiyaura coupling and polymerization of thiophene based derivatives. To the best of our knowledge, no such work on the synthesis and biological activities of 2bromomethyl5arylthiophenes 3ai has been reported to date. Pdcatalyzed crosscoupling reactions using organotins stille coupling 43 and organoborons suzuki coupling 44. A variety of imine derivatives have been synthesized via suzuki cross coupling of n4bromophenylbromothiophen2ylmethanimine with various arylboronic acids in moderate to good yields 5872%. Sep 23, 2014 read thiophene based macrocycles via the suzukimiyaura cross coupling reaction, tetrahedron on deepdyve, the largest online rental service for scholarly research with thousands of academic publications available at your fingertips.
A free powerpoint ppt presentation displayed as a flash slide show on id. Conditions have been identified that enable the onepot double suzuki coupling of 4,5dibromothiophene2carboxaldehyde to proceed in good yield. Heteroaromatic substrates, such as unprotected indole and dibenzob,dthiophene were successfully converted to the corresponding products in. An efficient suzuki cross coupling protocol enables the reaction of nhetero and normal aryl chlorides with thiophene and furanboronic acids. Attempts by negishi1,2 to crosscouple organoboron reagents with organic halides failed because the neutral threecoordinate boron species were not nucleophilic enough to efficiently transmetalate. Synthesis of,linked penta and septaheterocycles by tandem. Suzuki and miyaura3,4 postulated that activation of the boron using a. Palladiumcatalyzed suzukimiyaura coupling of thioureas.
Thiophene based macrocycles via the suzukimiyaura cross coupling reaction article in tetrahedron 7038. Pdf thiophene derivatives have shown versatile pharmacological activities. A facile synthesis of new 5arylthiophenes bearing sulfonamide. The suzuki reaction is an organic reaction, classified as a crosscoupling reaction, where the coupling partners are a boronic acid and an organohalide catalyzed by a palladium0 complex. Letter 93 letterprogrammed synthesis of tetraarylthieno3,2b thiophene by siteselective suzuki crosscoupling reactions of tetrabromothieno3,2bthiopheneprogrammed synthesis of tetraarylthieno3,2hien nguyen,a dung xuan nguyen,b thiophene a thinh quang tran,a binh ngoc vo,a thao huong nguyen,a thi minh. Suzuki polycondensation was applied to synthesize a set of three polymers with differing lengths of the ethylene glycol sidechains. Aqueous and anhydrous synthesis of ferrocenecapped thiophene. Myers the suzuki reaction chem 115 harvard university. The key to success in these reactions is the use of minimal amounts of water to avoid significant amounts. The extension of this methodology to variously c3 functionalized indazole derivatives by using pyrrole and thiophene boronic acids is currently under investigation. Zerovalent palladium complex, pdpth33, with three tri2thienylphosphine ligands was prepared and characterized. Solventfree, microwaveassisted synthesis of thiophene oligomers via suzuki coupling article pdf available in the journal of organic chemistry 6725. On the basis of these positive results, we extended the scope of the suzuki cross coupling to the.
As outlined in the reaction scheme 1, the first step in the. In p1p9, carbazolethiophenes were linked at the n9 position for different core groups via biphenyl, dimethylbiphenyl, and phenyl. The suzuki reaction proved a convenient method for cc bond formations in organic molecules. The stille coupling reaction was used instead of the suzuki one to synthesize compound 3 because our attempts to synthesize pure 5,5. Thiophenes derivaties are valuable building blocks for many natural and. Regioselective synthesis of 2bromomethyl5aryl thiophene derivatives via palladium 0 catalyzed suzuki crosscoupling reactions. Synthesis and thinfilm transistor performance of fluorene. Dangc,1 a department of chemistry, hanoi national university of. Suzuki coupling the suzuki reaction is the organic reaction of an aryl or vinyl boronic acid with an aryl or vinyl halide catalyzed by a palladium0 complex.
New shelfstable halo and alkoxysubstituted pyridylboronic acids and their suzuki cross coupling reactions to yield heteroarylpyridines. Suzukimiyaura crosscoupling in acylation reactions, scope. Suzuki and miyaura3,4 postulated that activation of the boron using a negatively. Mar 21, 2008 an efficient suzuki crosscoupling protocol enables the reaction of nhetero and normal aryl chlorides with thiophene and furanboronic acids. Coupling is effected in aqueous nbutanol as the solvent in near quantitative yield with a catalyst loading of 0. Alkylation, boration, coupling reaction, suzuki coupling, and halogenation of fluorenyl bromide chaingrowth catalyst transfer polycondensation of conjugated alternating copolymer ferric perchloratepromoted reaction of fullerene to give fullerenyl boronic esters ligandfree suzuki, sonogashira, and heck crosscoupling reactions. An important difference between two polymers is a position of alkyl side chains attached to thiophene units. We have investigated the suzuki cross coupling reactions of 2bromo5bromomethyl thiophene 2 with various aryl boronic acids under optimized conditions. Suzuki polycondensation spc is one of the methods of choice for synthesis of poly.
Palladium 0 catalyzed suzuki crosscoupling reactions of 2. Prior to the event, wherever and whenever chemists met, these names, of course among select others, were frequently overheard as potential candidates since their discoveries laid the foundations of the field of palladiumcatalyzed crosscoupling. The present study reports a convenient approach for the synthesis of thiophene sulfonamide derivatives 3a3k via suzuki cross coupling reaction. Palladium0 catalyzed suzuki crosscoupling reaction of 2,5. Diversityoriented approach to functional thiophene dyes by suzuki coupling lithiation onepot sequences.
The bpin and cl groups serve as suzuki coupling sites for elaborating the thiophene core, and the trimethylsilyl substituent is transformed to br in the final step. Heteroaromatic substrates, such as unprotected indole and dibenzob,d thiophene were successfully converted to the corresponding products in. Diversityoriented approach to functional thiophene dyes by suzuki couplinglithiation onepot sequences lars may, a sven daniel a and thomas j. Synthesis and photophysical properties of novel biphenyl derivatives containing furan and thiophene groups bao li, bin liu, qian li, haiyan fang, and mingxin yu journal of chemical research 2010 34. Palladiumcatalyzed suzukimiyaura coupling of thioureas or.
The dibrominated derivatives of thiophene itself, 15 of bi and terthiophene 16 as well as of 10ethyl3,7dithienyl10hphenothiazine see supplementary data are easily accessible and thus, considered as attractive candidates for macrocyclization reactions by suzuki crosscoupling procedures. An efficient suzuki crosscoupling protocol enables the reaction of nhetero and normal aryl chlorides with thiophene and furanboronic acids. On the basis of these positive results, we extended the scope of the suzuki crosscoupling to the. The scheme above shows the first published suzuki coupling, which is the palladiumcatalysed cross coupling between organoboronic acid and halides. The key to success in these reactions is the use of minimal amounts of water to avoid significant amounts of dehalogenation during the first coupling. It was first published in 1979 by akira suzuki and he shared the 2010 nobel prize in chemistry with richard f. Cc bond formation via the suzukimiyaura reaction is one of the most powerful and thoroughly explored facets of pdcatalyzed crosscoupling. Pdpth 3 3 is superior to pdpph 3 4 in catalyzing suzuki. Research article open access regioselective synthesis of 2bromomethyl5aryl thiophene derivatives via palladium 0 catalyzed suzuki crosscoupling reactions. The purpose of this study was to obtain a rapid, efficient, and environmentally friendly methodology for the synthesis of highly pure thiophene oligomers. Suzukimiyaura reaction by heterogeneously supported pd in. Download limit exceeded you have exceeded your daily download allowance.
Thiophene derivatives using sm crosscouplings 9658 6. The boronbased nucleophiles utilized in this reaction offer distinct advantages over other organometallic coupling reagents. An indolyl phosphine ligand plays an important role in this transformation. When they tried to do a suzuki crosscoupling reaction involving tosylate 2 using pdcl 2 dppf as the catalyst, the reaction failed to give any product, likely due to the oxygencontaining side chain scheme 37.
Recent catalyst and methods developments have broadened the possible applications enormously, so that the scope of the reaction partners is not restricted to aryls, but includes. Since the bpin group is present in compound 2, the roles of the electrophile and nucleophile are swapped. Palladium0 catalyzed suzuki crosscoupling reaction of 2. Suzukimiyaura crosscoupling in acylation reactions, scope and recent developments marco blangetti 1, helena rosso 2, cristina prandi 2, annamaria deagostino 2 and paolo venturello 2 1 centre for synthesis and chemical biology, school of chemistry and chemical biology. It is widely used to synthesize polyolefins, styrenes, and substituted biphenyls. Molecules 2012, 17 4511 easy removal of the boc group would make the coupling product 5d a valuable building block in the synthesis of new interesting indazolebased molecules. The solventfree, microwaveassisted coupling of thienyl boronic acids and esters with thienyl bromides, using aluminum oxide as the solid support, allowed us to rapidly check the reaction trends on changing times, temperature, catalyst, and. Akira suzuki3 figure 1c was a monumental event that was applauded by chemists worldwide. In many publications this reaction also goes by the name suzukimiyaura reaction and is also referred to as the suzuki coupling. Fortunately, a survey of catalyst systems revealed that 1,3bisdiphenylphosphinopropane dppp was a suitable ligand for this. Suzukimiyaura reaction by heterogeneously supported pd in water. To explore the structural properties, density functional theory dft. As suzukimiyaura coupling is the most widely used method for cc bond forming heteroaryl elaboration 19, the ability to use heterocycles is. Suzuki crosscoupling of solidsupported chloropyrimidines with arylboronic acids.
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