Generic placeholder image

Current Organic Chemistry

Editor-in-Chief

ISSN (Print): 1385-2728
ISSN (Online): 1875-5348

Review Article

An Updated Coverage on the Synthesis of Benzo[b]thiophenes via Transition-metalcatalyzed Reactions: A Review

Author(s): Saba Ejaz, Muhammad Zubair*, Komal Rizwan*, Idris Karakaya, Tahir Rasheed and Nasir Rasool

Volume 25, Issue 1, 2021

Published on: 11 November, 2020

Page: [40 - 67] Pages: 28

DOI: 10.2174/1385272824999201111204317

Price: $65

Abstract

The benzo[b]thiophene nucleus is ubiquitous in biologically and pharmaceutically important compounds. These moieties are highly important in materials science. The synthesis of benzothiophene as a privileged structure has readily become a subject of great interest and actively pursued in recent years. This review focuses on facile and convenient methods of synthesis of benzo[b]thiophene based molecules through different transition metals catalyzed reactions.

Keywords: Benzo[b]thiophene, couplings, transition metals, heterocyclics, palladium, synthesis.

« Previous
Graphical Abstract
[1]
Liang, S.; Shaaban, S.; Liu, N-W.; Hofman, K.; Manolikakes, G. Recent advances in the synthesis of C–S bonds via metal-catalyzed or-mediated functionalization of C–H bonds InAdvances in Organometallic Chemistry; Elsevier, 2018, Vol. 69, pp. 135-207.
[2]
Acharya, A.; Vijay Kumar, S.; Saraiah, B.; Ila, H. One-pot synthesis of functionalized benzo[b]thiophenes and their hetero-fused analogues via intramolecular copper-catalyzed S-arylation of in situ generated enethiolates. J. Org. Chem., 2015, 80(5), 2884-2892.
[http://dx.doi.org/10.1021/acs.joc.5b00032] [PMID: 25658978]
[3]
Acharya, A.; Kumar, S.V.; Ila, H. Diversity-oriented synthesis of substituted benzo[b]thiophenes and their hetero-fused analogues through palladium-catalyzed oxidative C-H functionalization/intramolecular arylthiolation. Chemistry, 2015, 21(47), 17116-17125.
[http://dx.doi.org/10.1002/chem.201501828] [PMID: 26429766]
[4]
Singh, P.P.; Yadav, A.K.; Ila, H.; Junjappa, H. Novel Route to 2, 3-substituted benzo [b] thiophenes via intramolecular radical cyclization. J. Org. Chem., 2009, 74(15), 5496-5501.
[http://dx.doi.org/10.1021/jo900615p] [PMID: 19572579]
[5]
Hou, C.; He, Q.; Yang, C. Direct synthesis of diverse 2-aminobenzo-[b]thiophenes via palladium-catalyzed carbon-sulfur bond formation using Na2S2O3 as the sulfur source. Org. Lett., 2014, 16(19), 5040-5043.
[http://dx.doi.org/10.1021/ol502381e] [PMID: 25229751]
[6]
Paul, N.; Muthusubramanian, S. Domino Vilsmeier–Haack/ring closure sequences: a facile synthesis of 3-chlorobenzo [b] thiophene-2-carbal-dehydes. Tetrahedron Lett., 2011, 52(29), 3743-3746.
[http://dx.doi.org/10.1016/j.tetlet.2011.05.046]
[7]
Młochowski, J.; Potaczek, P. A simple route to benzo [b] thiophenes: sulfanylation-acylation of C-H acids with 2-(chlorosulfanyl) benzoyl chloride. Phosphorus Sulfur Silicon Relat. Elem., 2009, 184(5), 1115-1123.
[http://dx.doi.org/10.1080/10426500902855117]
[8]
Moghaddam, F.M.; Bardajee, G.R.; Dolabi, M. An efficient one-pot synthesis of tri-substituted thiophenes via a multicomponent reaction in water. J. Sulfur Chem., 2010, 31(5), 387-393.
[http://dx.doi.org/10.1080/17415993.2010.496129]
[9]
Gabriele, B.; Mancuso, R.; Lupinacci, E.; Veltri, L.; Salerno, G.; Carfagna, C. Synthesis of benzothiophene derivatives by Pd-catalyzed or radical-promoted heterocyclodehydration of 1-(2-mercaptophenyl)-2-yn-1-ols. J. Org. Chem., 2011, 76(20), 8277-8286.
[http://dx.doi.org/10.1021/jo201471k] [PMID: 21902206]
[10]
Godoi, B.; Schumacher, R.F.; Zeni, G. Synthesis of heterocycles via electrophilic cyclization of alkynes containing heteroatom. Chem. Rev., 2011, 111(4), 2937-2980.
[http://dx.doi.org/10.1021/cr100214d] [PMID: 21425870]
[11]
Yugandar, S.; Konda, S.; Ila, H. Synthesis of substituted benzo[b]thiophenes via sequential one-pot, copper-catalyzed intermolecular C-S bond formation and palladium-catalyzed intramolecular arene-alkene coupling of bis(het)aryl/alkyl-1,3-monothiodiketones and o-bromoiodoarenes. Org. Lett., 2017, 19(7), 1512-1515.
[http://dx.doi.org/10.1021/acs.orglett.7b00273] [PMID: 28299938]
[12]
González, J.P.; Edgar, M.; Elsegood, M.R.; Weaver, G.W. Synthesis of fluorinated fused benzofurans and benzothiophenes: smiles-type rearrangement and cyclisation of perfluoro(het)aryl ethers and sulfides. Org. Biomol. Chem., 2011, 9(7), 2294-2305.
[http://dx.doi.org/10.1039/c0ob00790k] [PMID: 21321763]
[13]
Li, C-L.; Zhang, X-G.; Tang, R-Y.; Zhong, P.; Li, J-H. Copper-catalyzed thiolation annulations of 1,4-dihalides with sulfides leading to 2-trifluoromethyl benzothiophenes and benzothiazoles. J. Org. Chem., 2010, 75(20), 7037-7040.
[http://dx.doi.org/10.1021/jo101675f] [PMID: 20849131]
[14]
Jacubert, M.; Provot, O.; Peyrat, J-F.; Hamze, A.; Brion, J-D.; Alami, M. p-Toluenesulfonic acid-promoted selective functionalization of unsymmetrical arylalkynes: a regioselective access to various arylketones and heterocycles. Tetrahedron, 2010, 66(21), 3775-3787.
[http://dx.doi.org/10.1016/j.tet.2010.03.055]
[15]
Hussain, M.; Malik, I.; Villinger, A.; Langer, P. Efficient synthesis of functionalized 2, 3-di (alkenyl) benzothiophenes and dibenzothiophenes based on the first Heck reactions of 2, 3-di-and 2, 3, 6-tribromobenzothiophene. Synlett, 2009, 2009(16), 2691-2695.
[http://dx.doi.org/10.1055/s-0029-1217975]
[16]
Gopinath, P.; Nilaya, S.; Debi, T.R.; Ramkumar, V.; Muraleedharan, K.M. As many as six tandem reactions in one step! Unprecedented formation of highly functionalized benzothiophenes. Chem. Commun. (Camb.), 2009, 2009(46), 7131-7133.
[http://dx.doi.org/10.1039/b914424b] [PMID: 19921006]
[17]
Bryan, C.S.; Braunger, J.A.; Lautens, M. Efficient synthesis of benzothiophenes by an unusual palladium-catalyzed vinylic C-S coupling. Angew. Chem. Int. Ed. Engl., 2009, 48(38), 7064-7068.
[http://dx.doi.org/10.1002/anie.200902843] [PMID: 19691079]
[18]
Capperucci, A.; Degl’Innocenti, A.; Nocentini, T.; Pollicino, S. Organothiosilanes in the synthesis of functionalized benzothiophenes and benzofurans. J. Sulfur Chem., 2009, 30(3-4), 319-326.
[http://dx.doi.org/10.1080/17415990902998587]
[19]
Toguem, S-M.T.; Hussain, M.; Malik, I.; Villinger, A.; Langer, P. Synthesis of functionalized benzothiophenes by twofold Heck and subsequent 6π-electrocyclization reactions of 2, 3-dibromothiophene. Tetrahedron Lett., 2009, 50(35), 4962-4964.
[http://dx.doi.org/10.1016/j.tetlet.2009.06.057]
[20]
Jacubert, M.; Hamze, A.; Provot, O.; Peyrat, J-F.; Brion, J-D.; Alami, M. p-Toluenesulfonic acid-mediated cyclization of o-(1-alkynyl) anisoles or thioanisoles: synthesis of 2-arylsubstituted benzofurans and benzothiophenes. Tetrahedron Lett., 2009, 50(26), 3588-3592.
[http://dx.doi.org/10.1016/j.tetlet.2009.03.087]
[21]
Sashida, H.; Sadamori, K.; Tsuchiya, T. A convenient one-pot preparation of benzo [b]-tellurophenes,-selenophenes, and-thiophenes from o-bromo-ethynylbenzenes. Synth. Commun., 1998, 28(4), 713-727.
[http://dx.doi.org/10.1080/00397919808005944]
[22]
Wang, Y.; Parkin, S.R.; Watson, M.D. Benzodichalcogenophenes with perfluoroarene termini. Org. Lett., 2008, 10(20), 4421-4424.
[http://dx.doi.org/10.1021/ol801569m] [PMID: 18800845]
[23]
Takimiya, K.; Konda, Y.; Ebata, H.; Niihara, N.; Otsubo, T. Facile synthesis, structure, and properties of benzo[1,2-b:4,5-b′]dichalcogenophenes. J. Org. Chem., 2005, 70(25), 10569-10571.
[http://dx.doi.org/10.1021/jo051812m] [PMID: 16323873]
[24]
Werner, E. Synthesis of benzothiophenes. Recl. Trav. Chim. Pays Bas, 1949, 68(6), 509-519.
[http://dx.doi.org/10.1002/recl.19490680605]
[25]
Rappoport, Z. Vinyl Cations. In: Reactive Intermediates; Springer, 1983, pp. 427-615.
[http://dx.doi.org/10.1007/978-1-4613-3427-9_7]
[26]
Terpstra, J.W.; Van Leusen, A.M. A new synthesis of benzo [b] thiophenes and benzo [c] thiophenes by annulation of disubstituted thiophenes. J. Org. Chem., 1986, 51(2), 230-238.
[http://dx.doi.org/10.1021/jo00352a019]
[27]
Hessian, K.O.; Flynn, B.L. Iodine-induced reaction cascades for the rapid construction of variously substituted benzothiophenes. Org. Lett., 2003, 5(23), 4377-4380.
[http://dx.doi.org/10.1021/ol035663a] [PMID: 14602004]
[28]
Yan, J.; Pulis, A.P.; Perry, G.J.P.; Procter, D.J. Metal-free synthesis of benzothiophenes by twofold C-H functionalization: direct access to materials-oriented heteroaromatics. Angew. Chem. Int. Ed. Engl., 2019, 58(44), 15675-15679.
[http://dx.doi.org/10.1002/anie.201908319] [PMID: 31479175]
[29]
Gao, L.; Chang, B.; Qiu, W.; Wang, L.; Fu, X.; Yuan, R. Potassium hydroxide/dimethyl sulfoxide superbase‐promoted transition metal‐free synthesis of 2‐substituted benzothiophenes under visible light. Adv. Synth. Catal., 2016, 358(8), 1202-1207.
[http://dx.doi.org/10.1002/adsc.201501136]
[30]
Yuan, X-Y.; Zeng, F-L.; Zhu, H-L.; Liu, Y.; Lv, Q-Y.; Chen, X-L.; Peng, L.; Yu, B. A metal-free visible-light-promoted phosphorylation/cyclization reaction in water towards 3-phosphorylated benzothiophenes. Org. Chem. Front., 2020, 7(14), 1884-1889.
[http://dx.doi.org/10.1039/D0QO00222D]
[31]
Yao, J.; Xie, Y.; Zhang, L.; Li, Y.; Zhou, H. Synthesis of benzothiophene and indole derivatives through metal-free propargyl-allene rearrangement and allyl migration. Beilstein J. Org. Chem., 2017, 13(1), 1866-1870.
[http://dx.doi.org/10.3762/bjoc.13.181] [PMID: 29062405]
[32]
Nguyen, T.B.; Retailleau, P. DIPEA-promoted reaction of 2-nitrochalcones with elemental sulfur: an unusual approach to 2-benzoylbenzothiophenes. Org. Lett., 2017, 19(18), 4858-4860.
[http://dx.doi.org/10.1021/acs.orglett.7b02321] [PMID: 28840729]
[33]
Hartwig, J. Handbook of Organopalladium Chemistry for Organic Synthesis; Negishi, E.I., Ed.; John Wiley & Sons, 2002.
[34]
Hartwig, J.F. Carbon-heteroatom bond formation catalysed by organometallic complexes. Nature, 2008, 455(7211), 314-322.
[http://dx.doi.org/10.1038/nature07369] [PMID: 18800130]
[35]
Fu, G.C. The development of versatile methods for palladium-catalyzed coupling reactions of aryl electrophiles through the use of P(t-Bu)3 and PCy3 as ligands. Acc. Chem. Res., 2008, 41(11), 1555-1564.
[http://dx.doi.org/10.1021/ar800148f] [PMID: 18947239]
[36]
Stacy, G.W.; Villaescusa, F.W.; Wollner, T.E. 2-Aminobenzo [b] thiophene. An aromatic ring tautomer1, 2. J. Org. Chem., 1965, 30(12), 4074-4078.
[http://dx.doi.org/10.1021/jo01023a021]
[37]
Del Amo, V.; Dubbaka, S.R.; Krasovskiy, A.; Knochel, P. General preparation of primary, secondary, and tertiary aryl amines by the oxidative coupling of polyfunctional aryl and heteroaryl amidocuprates. Angew. Chem. Int. Ed. Engl., 2006, 45(46), 7838-7842.
[http://dx.doi.org/10.1002/anie.200603089] [PMID: 17075951]
[38]
Androsov, D.A.; Solovyev, A.Y.; Petrov, M.L.; Butcher, R.J.; Jasinski, J.P. A convenient approach towards 2-and 3-aminobenzo [b] thiophenes. Tetrahedron, 2010, 66(13), 2474-2485.
[http://dx.doi.org/10.1016/j.tet.2010.01.069]
[39]
Ablenas, F.; George, B.; Maleki, M.; Jain, R.; Hopkinson, A.; Lee-Ruff, E. Destabilized carbocations. Nuclear magnetic resonance detection and reactivities of aryl α-thioformamidyl cations. Can. J. Chem., 1987, 65(8), 1800-1803.
[http://dx.doi.org/10.1139/v87-302]
[40]
Magdesieva, T.V.; Nikitin, O.M.; Yakimansky, A.V.; Goikhman, M.Y.; Podeshvo, I.V. New heterobimetallic Cu (I)–Pd (II)-containing polymer complexes: electrochemical synthesis and application in catalysis. Electrochim. Acta, 2011, 56(10), 3666-3672.
[http://dx.doi.org/10.1016/j.electacta.2010.10.075]
[41]
Wu, L.; Shi, X.; Xu, X.; Liang, F.; Huang, G. Microwave-assisted efficient synthesis of 2-arylbenzo [b] furans and 2-ferrocenylbenzo [b] furans from readily prepared propargylic alcohols and o-iodophenols. J. Chem. Sci., 2011, 123(5), 697-702.
[http://dx.doi.org/10.1007/s12039-011-0137-9]
[42]
Liang, Y.; Tang, S.; Zhang, X-D.; Mao, L-Q.; Xie, Y-X.; Li, J-H. Novel and selective palladium-catalyzed annulations of 2-alkynylphenols to form 2-substituted 3-halobenzo[b]furans. Org. Lett., 2006, 8(14), 3017-3020.
[http://dx.doi.org/10.1021/ol060908f] [PMID: 16805541]
[43]
Ma, D.; Xie, S.; Xue, P.; Zhang, X.; Dong, J.; Jiang, Y. Efficient and economical access to substituted benzothiazoles: copper-catalyzed coupling of 2-haloanilides with metal sulfides and subsequent condensation. Angew. Chem. Int. Ed. Engl., 2009, 48(23), 4222-4225.
[http://dx.doi.org/10.1002/anie.200900486] [PMID: 19425042]
[44]
Campos, J.F.; Queiroz, M.J.R.; Berteina‐Raboin, S. Synthesis of new thieno [3, 2‐b] pyridines and thieno [2, 3‐b] pyrazines by palladium cross‐coupling. ChemistrySelect, 2017, 2(24), 6945-6948.
[http://dx.doi.org/10.1002/slct.201701054]
[45]
Sadig, J.E.; Willis, M.C. Palladium-and copper-catalyzed aryl halide amination, etherification and thioetherification reactions in the synthesis of aromatic heterocycles. Synthesis, 2011, 2011(1), 1-22.
[http://dx.doi.org/10.1055/s-0030-1258294]
[46]
Saraiah, B.; Gautam, V.; Acharya, A.; Pasha, M.A.; Hiriyakkanavar, I. One‐pot synthesis of 2‐(aryl/alkyl) amino‐3‐cyanobenzo [b] thiophenes and their hetero‐fused analogues by Pd‐catalyzed intramolecular oxidative C–H functionalization/arylthiolation. Eur. J. Org. Chem., 2017, 2017(37), 5679-5688.
[http://dx.doi.org/10.1002/ejoc.201700963]
[47]
Che, R.; Wu, Z.; Li, Z.; Xiang, H.; Zhou, X. Synthesis of dibenzothiophenes by Pd-catalyzed dual C-H activation from diaryl sulfides. Chemistry, 2014, 20(24), 7258-7261.
[http://dx.doi.org/10.1002/chem.201402265] [PMID: 24829172]
[48]
Saravanan, P.; Anbarasan, P. Palladium catalyzed aryl(alkyl)thiolation of unactivated arenes. Org. Lett., 2014, 16(3), 848-851.
[http://dx.doi.org/10.1021/ol4036209] [PMID: 24437617]
[49]
Kong, Y.; Yu, L.; Fu, L.; Cao, J.; Lai, G.; Cui, Y.; Hu, Z.; Wang, G. Electrophilic cyclization of o-anisole-and o-thioanisole-substituted ynamides: synthesis of 2-amidobenzofurans and 2-amidobenzothiophenes. Synthesis, 2013, 45(14), 1975-1982.
[http://dx.doi.org/10.1055/s-0033-1338481]
[50]
Ebata, H.; Miyazaki, E.; Yamamoto, T.; Takimiya, K. Synthesis, properties, and structures of benzo[1,2-b:4,5-b′]bis[b]benzothiophene and benzo[1,2-b:4,5-b′]bis[b]benzoselenophene. Org. Lett., 2007, 9(22), 4499-4502.
[http://dx.doi.org/10.1021/ol701815j] [PMID: 17914833]
[51]
Flynn, B.L.; Verdier-Pinard, P.; Hamel, E. A novel palladium-mediated coupling approach to 2,3-disubstituted benzo(b)thiophenes and its application to the synthesis of tubulin binding agents. Org. Lett., 2001, 3(5), 651-654.
[http://dx.doi.org/10.1021/ol0067179] [PMID: 11259028]
[52]
Chen, J.; Xiang, H.; Yang, L.; Zhou, X. Synthesis of 2-substituted benzo [b] thiophene via a Pd-catalyzed coupling of 2-iodothiophenol with phenylacetylene. RSC Advances, 2017, 7(13), 7753-7757.
[http://dx.doi.org/10.1039/C6RA26611H]
[53]
Idris, I.; Derridj, F.; Djebbar, S.; Soul, Ú.J-F.; Doucet, H. Synthesis of symmetrical and unsymmetrical 1, 3-diheteroarylbenzenes through palladium-catalyzed direct arylation of benzene-1, 3-disulfonyl dichloride and 3-bromobenzenesulfonyl chlorides. Tetrahedron, 2015, 71(52), 9617-9625.
[http://dx.doi.org/10.1016/j.tet.2015.10.082]
[54]
Qiao, Z.; Wei, J.; Jiang, X. Direct cross-coupling access to diverse aromatic sulfide: palladium-catalyzed double C-S bond construction using Na2S2O3 as a sulfurating reagent. Org. Lett., 2014, 16(4), 1212-1215.
[http://dx.doi.org/10.1021/ol500112y] [PMID: 24555790]
[55]
Inamoto, K.; Arai, Y.; Hiroya, K.; Doi, T. Palladium-catalysed direct synthesis of benzo[b]thiophenes from thioenols. Chem. Commun. (Camb.), 2008, 2008(43), 5529-5531.
[http://dx.doi.org/10.1039/b811362a] [PMID: 18997941]
[56]
Guilarte, V.; Fernández-Rodríguez, M.A.; García-García, P.; Hernando, E.; Sanz, R. A practical, one-pot synthesis of highly substituted thiophenes and benzo[b]thiophenes from bromoenynes and o-alkynylbromobenzenes. Org. Lett., 2011, 13(19), 5100-5103.
[http://dx.doi.org/10.1021/ol201970m] [PMID: 21882814]
[57]
Masuya, Y.; Tobisu, M.; Chatani, N. Palladium-catalyzed synthesis of 2, 3-disubstituted benzothiophenes via the annulation of aryl sulfides with alkynes. Org. Lett., 2016, 18(17), 4312-4315.
[http://dx.doi.org/10.1021/acs.orglett.6b02055] [PMID: 27548301]
[58]
Mori, T.; Nishimura, T.; Yamamoto, T.; Doi, I.; Miyazaki, E.; Osaka, I.; Takimiya, K. Consecutive thiophene-annulation approach to π-extended thienoacene-based organic semiconductors with [1]benzothieno[3,2-b][1]-benzothiophene (BTBT) substructure. J. Am. Chem. Soc., 2013, 135(37), 13900-13913.
[http://dx.doi.org/10.1021/ja406257u] [PMID: 24010738]
[59]
Kuhn, M.; Falk, F.C.; Paradies, J. Palladium-catalyzed C-S coupling: access to thioethers, benzo[b]thiophenes, and thieno[3,2-b]thiophenes. Org. Lett., 2011, 13(15), 4100-4103.
[http://dx.doi.org/10.1021/ol2016093] [PMID: 21732682]
[60]
Likhar, P.R.; Salian, S.M.; Roy, S.; Kantam, M.L.; Sridhar, B.; Mohan, K.V.; Jagadeesh, B. Intramolecular thiopalladation of thioanisole-substituted propargyl imines: synthesis of benzothiophene-based palladacycles. Organometallics, 2009, 28(14), 3966-3969.
[http://dx.doi.org/10.1021/om9003658]
[61]
Tobisu, M.; Masuya, Y.; Baba, K.; Chatani, N. Palladium(II)-catalyzed synthesis of dibenzothiophene derivatives via the cleavage of carbon-sulfur and carbon-hydrogen bonds. Chem. Sci. (Camb.), 2016, 7(4), 2587-2591.
[http://dx.doi.org/10.1039/C5SC04890G] [PMID: 28660030]
[62]
Nicolaus, N.; Franke, P.T.; Lautens, M. Modular synthesis of naphthothiophenes by Pd-catalyzed tandem direct arylation/Suzuki coupling. Org. Lett., 2011, 13(16), 4236-4239.
[http://dx.doi.org/10.1021/ol201585a] [PMID: 21793545]
[63]
Shen, C.; Spannenberg, A.; Auer, M.; Wu, X.F. Utilizing an encapsulated solution of reagents to achieve the four‐component synthesis of (benzo) thiophene derivatives. Adv. Synth. Catal., 2017, 359(6), 941-946.
[http://dx.doi.org/10.1002/adsc.201601343]
[64]
Wang, Y.; Burton, D.J. Site-specific preparation of 4-substituted-6-fluoro (carboalkoxyl) benzo [b] furans and benzo [b] thiophenes via base-catalyzed cyclization of enyne derivatives. J. Fluor. Chem., 2007, 128(9), 1052-1057.
[http://dx.doi.org/10.1016/j.jfluchem.2007.05.019]
[65]
Nogi, K.; Yorimitsu, H. Aromatic metamorphosis: conversion of an aromatic skeleton into a different ring system. Chem. Commun. (Camb.), 2017, 53(29), 4055-4065.
[http://dx.doi.org/10.1039/C7CC00078B] [PMID: 28225122]
[66]
Laha, J.K.; Sharma, S. Palladium-catalyzed intramolecular oxidative arylations for the synthesis of fused biaryl sulfones. ACS Omega, 2018, 3(5), 4860-4870.
[http://dx.doi.org/10.1021/acsomega.8b00628] [PMID: 31458702]
[67]
Samanta, R.; Antonchick, A.P. Palladium-catalyzed double C-H activation directed by sulfoxides in the synthesis of dibenzothiophenes. Angew. Chem. Int. Ed. Engl., 2011, 50(22), 5217-5220.
[http://dx.doi.org/10.1002/anie.201100775] [PMID: 21506222]
[68]
Willis, M.C.; Taylor, D.; Gillmore, A.T. Palladium-catalysed intramolecular enolate O-arylation and thio-enolate S-arylation: synthesis of benzo [b] furans and benzo [b] thiophenes. Tetrahedron, 2006, 62(49), 11513-11520.
[http://dx.doi.org/10.1016/j.tet.2006.05.004]
[69]
Yin, B.; Zhang, X.; Zhang, X.; Peng, H.; Zhou, W.; Liu, B.; Jiang, H. Access to polysubstituted indoles or benzothiophenes via palladium-catalyzed cross-coupling of furfural tosylhydrazones with 2-iodoanilines or 2-iodothiophenols. Chem. Commun. (Camb.), 2015, 51(28), 6126-6129.
[http://dx.doi.org/10.1039/C5CC00267B] [PMID: 25743623]
[70]
Yue, D.; Larock, R.C. Synthesis of 2,3-disubstituted benzo[b]thiophenes via palladium-catalyzed coupling and electrophilic cyclization of terminal acetylenes. J. Org. Chem., 2002, 67(6), 1905-1909.
[http://dx.doi.org/10.1021/jo011016q] [PMID: 11895409]
[71]
Li, Z.; Zhang, J.; Zhang, W.; Guo, L.; Huang, J.; Yu, G.; Wong, M.S. Effect of fluorine substitution on naphtho [2, 1-b: 3, 4-b′] bis [1]-benzothiophene-derived semiconductors for transistor application. Org. Electron., 2016, 32, 47-53.
[http://dx.doi.org/10.1016/j.orgel.2016.02.008]
[72]
Zeng, F.; Alper, H.; Palladium-Catalyzed Domino, C-S. Palladium-catalyzed domino C-S coupling/carbonylation reactions: an efficient synthesis of 2-carbonylbenzo[b]thiophene derivatives. Org. Lett., 2011, 13(11), 2868-2871.
[http://dx.doi.org/10.1021/ol200880m] [PMID: 21545086]
[73]
Pinto, E.; Queiroz, M-J.R.; Vale-Silva, L.A.; Oliveira, J.F.; Begouin, A.; Begouin, J-M.; Kirsch, G. Antifungal activity of synthetic di(hetero)-arylamines based on the benzo[b]thiophene moiety. Bioorg. Med. Chem., 2008, 16(17), 8172-8177.
[http://dx.doi.org/10.1016/j.bmc.2008.07.042] [PMID: 18678498]
[74]
Romagnoli, R.; Baraldi, P.G.; Kimatrai Salvador, M.; Preti, D.; Aghazadeh Tabrizi, M.; Bassetto, M.; Brancale, A.; Hamel, E.; Castagliuolo, I.; Bortolozzi, R.; Basso, G.; Viola, G. Synthesis and biological evaluation of 2-(alkoxycarbonyl)-3-anilinobenzo[b]thiophenes and thieno[2,3-b]pyridines as new potent anticancer agents. J. Med. Chem., 2013, 56(6), 2606-2618.
[http://dx.doi.org/10.1021/jm400043d] [PMID: 23445496]
[75]
Lee, S.; Lee, H.; Yi, K.Y.; Lee, B.H.; Yoo, S.E.; Lee, K.; Cho, N.S. 4-Substituted (benzo[b]thiophene-2-carbonyl)guanidines as novel Na+/H+ exchanger isoform-1 (NHE-1) inhibitors. Bioorg. Med. Chem. Lett., 2005, 15(12), 2998-3001.
[http://dx.doi.org/10.1016/j.bmcl.2005.04.046] [PMID: 15914000]
[76]
Toguem, S-M.T.; Malik, I.; Hussain, M.; Iqbal, J.; Villinger, A.; Langer, P. Synthesis of functionalized benzothiophenes and dibenzothiophenes by twofold Heck and subsequent 6π-electrocyclization reactions of 2, 3-dibromothiophenes and 2, 3-dibromobenzothiophenes. Tetrahedron, 2013, 69(1), 160-173.
[http://dx.doi.org/10.1016/j.tet.2012.10.050]
[77]
Bowman, W.R.; Heaney, H.; Smith, P.H. Intramolecular aromatic substitution (SRN1) reactions; use of entrainment for the preparation of benzothiazoles. Tetrahedron Lett., 1982, 23(48), 5093-5096.
[http://dx.doi.org/10.1016/S0040-4039(00)85581-1]
[78]
Kesharwani, T.; Kornman, C.; Tonnaer, A.; Hayes, A.; Kim, S.; Dahal, N.; Romero, R.; Royappa, A. Sodium halides as the source of electrophilic halogens in green synthesis of 3-halo- and 3,n-dihalobenzo[b]thiophenes. Tetrahedron, 2018, 74(24), 2973-2984.
[http://dx.doi.org/10.1016/j.tet.2018.04.080] [PMID: 30886445]
[79]
Kim, S.; Dahal, N.; Kesharwani, T. Environmentally benign process for the synthesis of 2, 3-disubstituted benzo [b] thiophenes using electrophilic cyclization. Tetrahedron Lett., 2013, 54(33), 4373-4376.
[http://dx.doi.org/10.1016/j.tetlet.2013.05.139]
[80]
Newman, S.G.; Aureggi, V.; Bryan, C.S.; Lautens, M. Intramolecular cross-coupling of gem-dibromoolefins: a mild approach to 2-bromo benzofused heterocycles. Chem. Commun. (Camb.), 2009, (35), 5236-5238.
[http://dx.doi.org/10.1039/b912093a] [PMID: 19707631]
[81]
Sangeetha, S.; Sekar, G. Synthesis of 2-acylbenzo[b]thiophenes via Cu-catalyzed α-C-H functionalization of 2-halochalcones using xanthate. Org. Lett., 2017, 19(7), 1670-1673.
[http://dx.doi.org/10.1021/acs.orglett.7b00462] [PMID: 28333469]
[82]
Wang, C.; Sun, L-L.; Hu, B-L.; Zhang, X-G.; Chen, F. A facile one-pot synthesis of benzothiophenes via copper-catalyzed thiolation annulations of o-halostyrenes with NaSH. Tetrahedron, 2014, 70(43), 7969-7972.
[http://dx.doi.org/10.1016/j.tet.2014.08.049]
[83]
Prasad, D.J.; Sekar, G. Cu-catalyzed in situ generation of thiol using xanthate as a thiol surrogate for the one-pot synthesis of benzothiazoles and benzothiophenes. Org. Biomol. Chem., 2013, 11(10), 1659-1665.
[http://dx.doi.org/10.1039/c3ob26915a] [PMID: 23358646]
[84]
Li, Y.; Nie, C.; Wang, H.; Li, X.; Verpoort, F.; Duan, C. A highly efficient method for the copper‐catalyzed selective synthesis of diaryl chalcogenides from easily available chalcogen sources. Eur. J. Org. Chem., 2011, 2011(36), 7331-7338.
[http://dx.doi.org/10.1002/ejoc.201101121]
[85]
Yu, H.; Zhang, M.; Li, Y. Copper-catalyzed synthesis of benzo[b]thiophenes and benzothiazoles using thiocarboxylic acids as a coupling partner. J. Org. Chem., 2013, 78(17), 8898-8903.
[http://dx.doi.org/10.1021/jo401353w] [PMID: 23957712]
[86]
Huang, H.; Dang, P.; Wu, L.; Liang, Y.; Liu, J. Copper-catalyzed synthesis of benzo [b] thiophene-fused imidazopyridines via the cleavage of C–H bond and C–X bond. Tetrahedron Lett., 2016, 57(5), 574-577.
[http://dx.doi.org/10.1016/j.tetlet.2015.12.091]
[87]
Sun, L-L.; Deng, C-L.; Tang, R-Y.; Zhang, X-G. CuI/TMEDA-catalyzed annulation of 2-bromo alkynylbenzenes with Na2S: synthesis of benzo[b]thiophenes. J. Org. Chem., 2011, 76(18), 7546-7550.
[http://dx.doi.org/10.1021/jo201081v] [PMID: 21812478]
[88]
Zheng, Z.; Chen, L.; Qian, C.; Zhu, X.; Yang, Y.; Liu, J.; Yang, Y.; Liang, Y. Copper-catalyzed synthesis of 2-acylbenzo[b]thiophenes from 3-(2-iodophenyl)-1-arylpropan-1-ones and potassium sulfide under aerobic conditions. Org. Biomol. Chem., 2018, 16(43), 8020-8024.
[http://dx.doi.org/10.1039/C8OB02315H] [PMID: 30334048]
[89]
Chatani, N. Nickel-catalyzed C–H bond functionalization utilizing an N, N′-bidentate directing group. In: C-H Bond Activation and Catalytic Functionalization II; Springer, 2015, pp. 19-46.
[http://dx.doi.org/10.1007/3418_2015_117]
[90]
Tang, X-Q.; Montgomery, J. Nickel-catalyzed preparation of bicyclic heterocycles: Total synthesis of (+)-allopumiliotoxin 267A,(+)-allopumiliotoxin 339A, and (+)-allopumiliotoxin 339B. J. Am. Chem. Soc., 2000, 122(29), 6950-6954.
[http://dx.doi.org/10.1021/ja001440t]
[91]
Liu, C-C.; Parthasarathy, K.; Cheng, C-H. Synthesis of highly substituted isoquinolone derivatives by nickel-catalyzed annulation of 2-halobenzamides with alkynes. Org. Lett., 2010, 12(15), 3518-3521.
[http://dx.doi.org/10.1021/ol101371c] [PMID: 20608667]
[92]
Shiota, H.; Ano, Y.; Aihara, Y.; Fukumoto, Y.; Chatani, N. Nickel-catalyzed chelation-assisted transformations involving ortho C-H bond activation: regioselective oxidative cycloaddition of aromatic amides to alkynes. J. Am. Chem. Soc., 2011, 133(38), 14952-14955.
[http://dx.doi.org/10.1021/ja206850s] [PMID: 21875095]
[93]
Iwasaki, M.; Miki, N.; Tsuchiya, Y.; Nakajima, K.; Nishihara, Y. Synthesis of benzoisoselenazolone derivatives by nickel-catalyzed dehydrogenative direct selenation of C(sp2)-H bonds with elemental selenium in air. Org. Lett., 2017, 19(5), 1092-1095.
[http://dx.doi.org/10.1021/acs.orglett.7b00116] [PMID: 28211695]
[94]
Wu, X.; Zhao, Y.; Ge, H. Nickel-catalyzed site-selective amidation of unactivated C(sp3)-H bonds. Chemistry, 2014, 20(31), 9530-9533.
[http://dx.doi.org/10.1002/chem.201403356] [PMID: 24965178]
[95]
Yan, S-Y.; Liu, Y-J.; Liu, B.; Liu, Y-H.; Shi, B-F. Nickel-catalyzed thiolation of unactivated aryl C-H bonds: efficient access to diverse aryl sulfides. Chem. Commun. (Camb.), 2015, 51(19), 4069-4072.
[http://dx.doi.org/10.1039/C4CC10446C] [PMID: 25661824]
[96]
Yokota, A.; Chatani, N. Ni (II)-catalyzed sulfonylation of ortho C–H bonds in aromatic amides utilizing an N, N-bidentate directing group. Chem. Lett., 2015, 44(7), 902-904.
[http://dx.doi.org/10.1246/cl.150239]
[97]
Inami, T.; Baba, Y.; Kurahashi, T.; Matsubara, S. Nickel-catalyzed cycloadditions of thiophthalic anhydrides with alkynes. Org. Lett., 2011, 13(8), 1912-1915.
[http://dx.doi.org/10.1021/ol200336c] [PMID: 21381687]
[98]
Bandyopadhyay, D.; Thirupathi, A.; Dhage, N.M.; Mohanta, N.; Peruncheralathan, S. Nickel catalyzed site selective C-H functionalization of α-aryl-thioamides. Org. Biomol. Chem., 2018, 16(35), 6405-6409.
[http://dx.doi.org/10.1039/C8OB01712C] [PMID: 30178810]
[99]
Zheng, Q.Z.; Jiao, N. Coupling reactions and C-H functionalization In: Silver Catalysis in Organic Synthesis, 2019, pp. 331-406..
[100]
Liu, J.; Liu, Z.; Liao, P.; Bi, X. Modular synthesis of sulfonyl benzoheteroles by silver-catalyzed heteroaromatization of propargylic alcohols with p-toluenesulfonylmethyl isocyanide (TosMIC): dual roles of TosMIC. Org. Lett., 2014, 16(23), 6204-6207.
[http://dx.doi.org/10.1021/ol5031316] [PMID: 25402338]
[101]
Cai, T.; Liu, J.; Zhang, H.; Wang, X.; Feng, J.; Shen, R.; Gao, Y. Ag-Mediated radical cyclization of 2-alkynylthio(seleno)anisoles: direct synthesis of 3-phosphinoylbenzothio(seleno)phenes. Org. Lett., 2019, 21(12), 4605-4608.
[http://dx.doi.org/10.1021/acs.orglett.9b01510] [PMID: 31145626]
[102]
Ramesh, E.; Shankar, M.; Dana, S.; Sahoo, A.K. Silver-mediated oxidative annulation of N-arylthio succinimides with alkynes: direct access to benzo [b] thiophenes. Org. Chem. Front., 2016, 3(9), 1126-1130.
[http://dx.doi.org/10.1039/C6QO00259E]
[103]
Abbiati, G.; Rossi, E. Silver and gold-catalyzed multicomponent reactions. Beilstein J. Org. Chem., 2014, 10(1), 481-513.
[http://dx.doi.org/10.3762/bjoc.10.46] [PMID: 24605168]
[104]
Gorin, D.J.; Toste, F.D. Relativistic effects in homogeneous gold catalysis. Nature, 2007, 446(7134), 395-403.
[http://dx.doi.org/10.1038/nature05592] [PMID: 17377576]
[105]
Fürstner, A.; Davies, P.W. Catalytic carbophilic activation: catalysis by platinum and gold π acids. Angew. Chem. Int. Ed. Engl., 2007, 46(19), 3410-3449.
[http://dx.doi.org/10.1002/anie.200604335] [PMID: 17427893]
[106]
Nakamura, I.; Sato, T.; Yamamoto, Y. Gold-catalyzed intramolecular carbothiolation of alkynes: synthesis of 2,3-disubstituted benzothiophenes from (α-alkoxy alkyl) (ortho-alkynyl phenyl) sulfides. Angew. Chem. Int. Ed. Engl., 2006, 45(27), 4473-4475.
[http://dx.doi.org/10.1002/anie.200601178] [PMID: 16767784]
[107]
Nakamura, I.; Sato, T.; Terada, M.; Yamamoto, Y. Gold-catalyzed cyclization of (ortho-alkynylphenylthio)silanes: intramolecular capture of the vinyl-Au intermediate by the silicon electrophile. Org. Lett., 2007, 9(20), 4081-4083.
[http://dx.doi.org/10.1021/ol701951n] [PMID: 17784768]
[108]
Shen, H.C.; Graham, T.H. Gold-catalyzed formation of heterocycles - an enabling new technology for medicinal chemistry. Drug Discov. Today. Technol., 2013, 10(1), e3-e14.
[http://dx.doi.org/10.1016/j.ddtec.2012.10.014] [PMID: 24050224]
[109]
Qiu, Y.; Ma, D.; Fu, C.; Ma, S. General approach to benzo [b] thiophenes, benzo [b] furans, and dibenzofurans via gold-catalyzed cyclization of 1-heteroarylalka-2, 3-dienyl acetates. Tetrahedron, 2013, 69(30), 6305-6312.
[http://dx.doi.org/10.1016/j.tet.2013.04.099]
[110]
Tran, L.D.; Daugulis, O. Iron-catalyzed heterocycle and arene deprotonative alkylation. Org. Lett., 2010, 12(19), 4277-4279.
[http://dx.doi.org/10.1021/ol101684u] [PMID: 20825168]
[111]
Hapke, M.; Hilt, G. Introduction to cobalt chemistry and catalysis In: Cobalt Catalysis in Organic Synthesis: Methods and Reactions; Wiley-VCH Verlag GmbH & Co., 2020, pp. 1-23..
[112]
Wang, T.; Chen, J.; Wang, J.; Xu, S.; Lin, A.; Yao, H.; Jiang, S.; Xu, J. Cobalt-catalyzed carbon-sulfur/selenium bond formation: synthesis of benzo-[b]thio/selenophene-fused imidazo[1,2-a]pyridines. Org. Biomol. Chem., 2018, 16(20), 3721-3725.
[http://dx.doi.org/10.1039/C8OB00743H] [PMID: 29737996]
[113]
Huang, S.; Li, H.; Xie, T.; Wei, F.; Tung, C-H.; Xu, Z. Scandium-catalyzed electrophilic alkene difunctionalization: regioselective synthesis of thiosulfone derivatives. Org. Chem. Front., 2019, 6(10), 1663-1666.
[http://dx.doi.org/10.1039/C9QO00138G]
[114]
Wang, X.; Gensch, T.; Glorius, F. Highly selective synthesis of 6-substituted benzothiophenes by Sc(OTf)3-catalyzed intermolecular cyclization and sulfur migration. Org. Chem. Front., 2016, 3(12), 1619-1623.
[http://dx.doi.org/10.1039/C6QO00477F]
[115]
Kaur, N.; Verma, Y.; Grewal, P.; Bhardwaj, P.; Devi, M. Application of titanium catalysts for the syntheses of heterocycles. Synth. Commun., 2019, 49(15), 1847-1894.
[http://dx.doi.org/10.1080/00397911.2019.1606922]
[116]
Roberts, C.F.; Hartley, R.C. Titanium reagents for the synthesis of 2-substituted benzo[b]thiophenes on the solid phase. J. Org. Chem., 2004, 69(18), 6145-6148.
[http://dx.doi.org/10.1021/jo049344o] [PMID: 15373505]
[117]
Migulin, V.A.; Krayushkin, M.M.; Barachevsky, V.A.; Kobeleva, O.I.; Novikov, V.V.; Lyssenko, K.A. Synthesis and studies of symmetric dibenzothienylcyclopentenes. Tetrahedron, 2015, 71(4), 584-598.
[http://dx.doi.org/10.1016/j.tet.2014.12.036]
[118]
Carney, J.R.; Dillon, B.R.; Thomas, S.P. Recent advances of manganese catalysis for organic synthesis. Eur. J. Org. Chem., 2016, 2016(23), 3912-3929.
[http://dx.doi.org/10.1002/ejoc.201600018]
[119]
Liu, K.; Jia, F.; Xi, H.; Li, Y.; Zheng, X.; Guo, Q.; Shen, B.; Li, Z. Direct benzothiophene formation via oxygen-triggered intermolecular cyclization of thiophenols and alkynes assisted by manganese/PhCOOH. Org. Lett., 2013, 15(8), 2026-2029.
[http://dx.doi.org/10.1021/ol400719d] [PMID: 23578091]
[120]
Yuan, C.; Liu, B. Total synthesis of natural products via iridium catalysis. Org. Chem. Front., 2017, 5(1), 106-131.
[http://dx.doi.org/10.1039/C7QO00664K]
[121]
Anxionnat, B.; Gomez Pardo, D.; Ricci, G.; Rossen, K.; Cossy, J. Iridium-catalyzed hydrogen transfer: synthesis of substituted benzofurans, benzothiophenes, and indoles from benzyl alcohols. Org. Lett., 2013, 15(15), 3876-3879.
[http://dx.doi.org/10.1021/ol401610e] [PMID: 23859265]
[122]
Murahashi, S-I. Ruthenium in Organic Synthesis; John Wiley & Sons, 2006.
[123]
Gong, X.; Wang, M.; Ye, S.; Wu, J. Synthesis of 3-(Methylsulfonyl)benzo[ b]thiophenes from methyl(2-alkynylphenyl)sulfanes and sodium metabisulfite via a radical Relay Strategy. Org. Lett., 2019, 21(4), 1156-1160.
[http://dx.doi.org/10.1021/acs.orglett.9b00100] [PMID: 30698982]
[124]
Wessjohann, L.A.; Scheid, G. Recent advances in chromium (II)-and chromium (III)-mediated organic synthesis. Synthesis, 1999, 1999(01), 1-36.
[http://dx.doi.org/10.1055/s-1999-3672]
[125]
Tian, Q.; Bai, J.; Chen, B.; Zhang, G. Chromium-catalyzed asymmetric dearomatization addition reactions of halomethyl heteroarenes. Org. Lett., 2016, 18(8), 1828-1831.
[http://dx.doi.org/10.1021/acs.orglett.6b00559] [PMID: 27043431]
[126]
Moon, S.; Kato, M.; Nishii, Y.; Miura, M. Synthesis of benzo [b] thiophenes through rhodium‐catalyzed three‐component reaction using elemental sulfur. Adv. Synth. Catal., 2020, 362(8), 1669-1673.
[http://dx.doi.org/10.1002/adsc.202000112]

Rights & Permissions Print Export Cite as
© 2022 Bentham Science Publishers | Privacy Policy