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Current Organic Chemistry

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ISSN (Online): 1875-5348

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Review Article

Recent Progress in the Synthesis of Benzo[b]thiophene

Author(s): Dau Xuan Duc*

Volume 24, Issue 19, 2020

Page: [2256 - 2271] Pages: 16

DOI: 10.2174/1385272824999200820151545

Price: $65

Abstract

Benzo[b]thiophenes are aromatic heterocyclic compounds containing benzene and thiophene rings. This class of heterocycles is present in a large number of natural and non-natural compounds. Benzo[b]thiophene derivatives have a broad range of applications in medicinal chemistry such as antimicrobial, anticancer, antioxidant, anti-HIV and antiinflammatory activities. The use of benzo[b]thiophene derivatives in other fields has also been reported. Various benzo[b]thiophenes compounds have been employed as organic photoelectric materials, while several benzo[b]thiophenes have been used as organic semiconductors. Benzo[b]thiophenes have also been used as building blocks or intermediates for the synthesis of pharmaceutically important molecules.

Due to such a wide range of applicability, the synthesis of benzo[b]thiophene derivatives has attracted intensive research. Numerous mild and efficient approaches for the synthesis of benzo[b]thiophenes have been developed over the years. Different catalysts and substrates have been applied for benzo[b]thiophene synthesis. This review will focus on the studies in the construction of benzo[b]thiophene skeleton, which date back from 2012.

Keywords: Benzo[b]thiophene, cyclization, 2-alkynylanisoles, Sonogashira coupling, alkynes, thiophenols.

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[1]
Croxtall, J.D.; Plosker, G.L. Sertaconazole: a review of its use in the management of superficial mycoses in dermatology and gynaecology. Drugs, 2009, 69(3), 339-359.
[http://dx.doi.org/10.2165/00003495-200969030-00009] [PMID: 19275277]
[2]
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, 2474-2485.
[http://dx.doi.org/10.1016/j.tet.2010.01.069]
[3]
Queiroz, M.J.R.P.; Ferreira, I.C.F.R.; De Gaetano, Y.; Kirsch, G.; Calhelha, R.C.; Estevinho, L.M. Synthesis and antimicrobial activity studies of ortho-chlorodiarylamines and heteroaromatic tetracyclic systems in the benzo[b]thiophene series. Bioorg. Med. Chem., 2006, 14(20), 6827-6831.
[http://dx.doi.org/10.1016/j.bmc.2006.06.035] [PMID: 16843669]
[4]
Naganagowda, G.; Petsom, A. Synthesis and antimicrobial activity of some new 2-(3-chloro-1- benzothiophen-2-yl)-3-(substitutedphenyl)-4- (3H)-quin-azolinones derivatives. J. Sulfur Chem., 2011, 32, 223-233.
[http://dx.doi.org/10.1080/17415993.2011.575943]
[5]
Naganagowda, G.; Thamyongkit, P.; Klai-U-dom, R.; Ariyakriangkrai, W.; Luechai, A.; Petsom, A. Synthesis and biological activity of some more heterocyclic compounds containing benzothiophene moiety. J. Sulfur Chem., 2011, 32, 235-247.
[http://dx.doi.org/10.1080/17415993.2011.583394]
[6]
Clemett, D.; Spencer, C.M. Raloxifene: a review of its use in postmenopausal osteoporosis. Drugs, 2000, 60(2), 379-411.
[http://dx.doi.org/10.2165/00003495-200060020-00013] [PMID: 10983739]
[7]
Overk, C.R.; Peng, K.W.; Asghodom, R.T.; Kastrati, I.; Lantvit, D.D.; Qin, Z.; Frasor, J.; Bolton, J.L.; Thatcher, G.R. Structure-activity relationships for a family of ben-zothiophene selective estrogen receptor modulators including raloxifene and arzoxifene. ChemMedChem, 2007, 2(10), 1520-1526.
[http://dx.doi.org/10.1002/cmdc.200700104] [PMID: 17654759]
[8]
Chen, W.; Dong, G.; He, S.; Xu, T.; Wang, X.; Liu, N.; Zhang, W.; Miao, C.; Sheng, C. Identification of benzothiophene amides as potent inhibitors of human nicotinamide phosphoribosyltransferase. Bioorg. Med. Chem. Lett., 2016, 26(3), 765-768.
[http://dx.doi.org/10.1016/j.bmcl.2015.12.101] [PMID: 26755394]
[9]
Queiroz, M.J.; Ferreira, I.C.F.R.; Calhelha, R.C.; Estevinho, L.M. Synthesis and antioxidant activity evaluation of new 7-aryl or 7-heteroarylamino-2,3-dimethylbenzo[b]thiophenes obtained by Buchwald-Hartwig C-N cross-coupling. Bioorg. Med. Chem., 2007, 15(4), 1788-1794.
[http://dx.doi.org/10.1016/j.bmc.2006.11.035] [PMID: 17166720]
[10]
Sharma, H.; Patil, S.; Sanchez, T.W.; Neamati, N.; Schinazi, R.F.; Buolamwini, J.K. Synthesis, biological evaluation and 3D-QSAR studies of 3-keto salicylic acid chalcones and related amides as novel HIV-1 integrase inhibitors. Bioorg. Med. Chem., 2011, 19(6), 2030-2045.
[http://dx.doi.org/10.1016/j.bmc.2011.01.047] [PMID: 21371895]
[11]
Clouser, C.L.; Chauhan, J.; Bess, M.A.; van Oploo, J.L.; Zhou, D.; Dimick-Gray, S.; Mansky, L.M.; Patterson, S.E. Anti-HIV-1 activity of resveratrol derivatives and synergistic inhibition of HIV-1 by the combination of resveratrol and decitabine. Bioorg. Med. Chem. Lett., 2012, 22(21), 6642-6646.
[http://dx.doi.org/10.1016/j.bmcl.2012.08.108] [PMID: 23010273]
[12]
Fakhr, I.M.I.; Radwan, M.A.A.; el-Batran, S.; Abd el-Salam, O.M.E.; el-Shenawy, S.M. Synthesis and pharmacological evaluation of 2-substituted benzo[b]thiophenes as anti-inflammatory and analgesic agents. Eur. J. Med. Chem., 2009, 44(4), 1718-1725.
[http://dx.doi.org/10.1016/j.ejmech.2008.02.034] [PMID: 18433939]
[13]
Isloor, A.M.; Kalluraya, B.; Sridhar Pai, K. Synthesis, characterization and biological activities of some new benzo[b]thiophene derivatives. Eur. J. Med. Chem., 2010, 45(2), 825-830.
[http://dx.doi.org/10.1016/j.ejmech.2009.11.015] [PMID: 19945198]
[14]
Barbarella, G.; Favaretto, L.; Zanelli, A.; Gigli, G.; Mazzeo, M.; Anni, M. Bongini. A. V-Shaped thiophene-based oligomers with improved electroluminescence properties. Adv. Funct. Mater., 2005, 15, 664-670.
[http://dx.doi.org/10.1002/adfm.200400172]
[15]
(a) Pan, Z.; Liu, Y.; Fan, F.; Chen, Y.; Li, Y.; Zhan, X.; Song, Y. Self-assembled π-extended condensed benzothiophene nanoribbons for field-effect transistors. Chemistry,, 2013, 19(30), 9771-9774.
[http://dx.doi.org/10.1002/chem.201300603] [PMID: 23813498]
(b) Takimiya, K.; Ebata, H.; Sakamoto, K.; Izawa, T.; Otsubo, T.; Kunugi, Y. 2,7-Diphenyl[1]benzothieno[3,2-b]benzothiophene, a new organic semiconductor for air-stable organic field-effect transistors with mobilities up to 2.0 cm2 V-1 s-1. J. Am. Chem. Soc. 2006, 128(39), 12604-12605.
[http://dx.doi.org/10.1021/ja064052l] [PMID: 17002327]
(c) Ebata, H.; Izawa, T.; Miyazaki, E.; Takimiya, K.; Ikeda, M.; Kuwabara, H.; Yui, T. Highly soluble [1]benzothieno[3,2-b]benzothiophene (BTBT) derivatives for high-performance, solution-processed organic field-effect transistors. J. Am. Chem. Soc., 2007, 129(51), 15732-15733.
[http://dx.doi.org/10.1021/ja074841i] [PMID: 18044892]
[16]
(a) Qian, D.; Liu, B.; Wang, S.; Himmelberger, S.; Linares, M.; Vagin, M.Y.; Muller, C.; Ma, Z.; Fabiano, S.; Berggren, M. Modulating molecular aggregation by facile heteroatom substitution of diketopyrrolopyrrole based small molecules for efficient organic solar cells. J. Mater. Chem. 2015, 3, 24349-24357.
[http://dx.doi.org/10.1039/C5TA06501A]
(b) Nakano, M.; Niimi, K.; Miyazaki, E.; Osaka, I.; Takimiya, K. . Isomerically pure anthra[2,3-b:6,7-b′]-difuran (anti-ADF), -dithiophene (anti-ADT), and -diselenophene (anti-ADS): selective synthesis, electronic structures, and application to organic field-effect transistors. J. Org. Chem., 2012, 17(18), 8099-8111.
[http://dx.doi.org/10.1021/jo301438t] [PMID: 22889196]
(c) Takase, K.; Noguchi, K.; Nakano, K. Circularly polarized luminescence from chiral spiro molecules: synthesis and optical properties of 10,10′-spirobi(indeno[1,2-b][1]benzothiophene) derivatives. Org. Lett., 2017, 19(19), 5082-5085.
[http://dx.doi.org/10.1021/acs.orglett.7b02337] [PMID: 28926271]
[17]
(a) Tang, M.L.; Okamoto, T.; Bao, Z. High-performance organic semiconductors: asymmetric linear acenes containing sulphur. J. Am. Chem. Soc., 2006, 128(50), 16002-16003.
[http://dx.doi.org/10.1021/ja066824j] [PMID: 17165730]
(b) Yuan, Q.; Mannsfeld, S.C.B.; Tang, M.L.; Toney, M.F.; Lüning, J.; Bao, Z. Thin film structure of tetraceno[2,3-b]thiophene characterized by grazing incidence X-ray scattering and near-edge X-ray absorption fine structure analysis. J. Am. Chem. Soc. 2008, 130(11), 3502-3508.
[http://dx.doi.org/10.1021/ja0773002] [PMID: 18293975]
(c) Laquindanum, J.G.; Katz, H.E.; Lovinger, A.J. Synthesis, morphology, and field-effect mobility of anthradithiophenes. J. Am. Chem. Soc 1998, 120, 664-672.
[http://dx.doi.org/10.1021/ja9728381]
(d) Dimitrakopoulos, C.D.; Malenfant, P.R.L. Organic thin film transistors for large area electronics. Adv. Mater., 2002, 14, 99-177.
[http://dx.doi.org/10.1002/1521-4095(20020116)14:299::AIDADMA99> 3.0.CO;2-9]
(e) Ni, Y.; Nakajima, K.; Kanno, K.; Takahashi, T. Zirconium-mediated coupling reaction for synthesis of substituted thiophene-fused acenes. Org. Lett.,, 2009, 11(16), 3702-3705.
[http://dx.doi.org/10.1021/ol900903w] [PMID: 19637862]
(f) Huang, J.; Luo, H.; Wang, L.; Guo, Y.; Zhang, W.; Chen, H.; Zhu, M.; Liu, Y.; Yu, G. Dibenzoannelated tetrathienoacene: synthesis, characterization, and applications in organic field-effect transistors. Org. Lett., 2012, 14(13), 3300-3303.
[http://dx.doi.org/10.1021/ol3012748] [PMID: 22690853]
(g) Mori, T.; Nishimura, T.; Yamamoto, T.; Doi, I.; Miyazaki, E.; Osaka, I.; Takimiya, K. Consecutive thiophene-annulation approach to π-extended thienoacene-based or-ganic 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]
[18]
(a) Tietze, L.F.; Lohmann, J.K.; Stadler, C. Synthesis of novel highly active thiophene and benzothiophene containing diphosphine ligands and their use in the asymmetric allylation of catechol. Synlett., 2004, 6, 1113-1116.
[http://dx.doi.org/10.1055/s-2004-822891]
(b) Tietze, L.F.; Thede, K.; Schimpf, R.; Sannicolo, F. Enantioselective synthesis of tetrahydroisoquinolines and benzazepines by silane terminated Heck reactions with the chiral ligands (+)-TMBTP and (R)-BITIANP. Chem. Commun. (Camb.), 2000, 2000(7), 583-584.
[http://dx.doi.org/10.1039/a909689b ]
[19]
(a) Guinchard, X.; Denis, J.N. Reactions of in situ generated N-Boc nitrones with aromatic and heteroaromatic grignard reagents: application to the synthesis of zileuton. J. Org. Chem. 2008, 73(5), 2028-2031.
[http://dx.doi.org/10.1021/jo7025838 ] [PMID: 18269293]
(b) Dyker, G.; Kreher, R.P. 2,3-Dihydro-2,3-bismethylenbenzo[b]thiophen, ein anelliertes reaktives Dien. Chem. Ber. 1988, 121, 1203-1205.
[http://dx.doi.org/10.1002/cber.19881210629]
(c) Kiselyov, A.S.; Strekowski, L. An unconventional synthetic approach to fluoro heteroaromatic compounds by a novel transformation of an anionically activated trifluoromethyl group. Tetrahedron Lett., 1994, 35, 7597-7600.
[http://dx.doi.org/10.1016/S0040-4039(00)78352-3]
(d) Zhao, L.; Bruneau, C.; Doucet, H. Phosphine-free palladium-catalysed direct C2-arylation of benzothiophenes with aryl bromides. Tetrahedron, 2013, 69, 7082-7089.
[http://dx.doi.org/10.1016/j.tet.2013.06.037]
[20]
Mikami, S.; Tanaka, H.; Kishi, H.; Yoshida, S.; Toyota, K. Silica gel-assisted preparation of 2,4,7-trihalobenzo[b]thiophenes and 4,7- dihalobenzo[b]thiophenes. Phosphorus Sulfur Silicon Relat. Elem., 2019, 194, 768-770.
[http://dx.doi.org/10.1080/10426507.2019.1603725]
[21]
Eberhart, A.J.; Shrives, H.; Zhang, Y.; Carrër, A.; Parry, A.V.S.; Tate, D.J.; Turner, M.L.; Procter, D.J. Sulfoxide-directed metal-free cross-couplings in the expedient synthesis of benzothiophene-based components of materials. Chem. Sci. (Camb.), 2016, 7(2), 1281-1285.
[http://dx.doi.org/10.1039/C5SC03823E] [PMID: 29910885]
[22]
Ma, W.; Huang, J.; Huang, X.; Meng, S.; Yang, Z.; Li, C.; Wang, Y.; Qi, T.; Li, B. Direct construction of 2,3-unsubstituted benzofurans and benzothiophenes via a metal free catalyzed intramolecular Friedel-Crafts reaction. Org. Chem. Front., 2019, 6, 493-497.
[http://dx.doi.org/10.1039/C8QO01204K]
[23]
Lumbroso, A.; Behra, J.; Kolleth, A.; Dakas, P.; Karadeniz, U.; Catak, S.; Mossé, S.S.; De Mesmaeker, A. Access to functionalized 3-amino-benzothiophenes using keteniminium intermediates. Tetrahedron Lett., 2015, 56, 6541-6545.
[http://dx.doi.org/10.1016/j.tetlet.2015.09.103]
[24]
Kolleth, A.; Müller, S.; Lumbroso, A.; Tanriver, G.; Catak, S.; Sulzer-Mossé, S.; De Mesmaeker, A. Access to 3-aminobenzothiophenes and 3-aminothiophenes fused to 5-membered heteroaromatic rings through 6p-electrocyclization reaction of keteniminium salts. Tetrahedron Lett., 2018, 59, 3242-3248.
[http://dx.doi.org/10.1016/j.tetlet.2018.06.049]
[25]
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, 1866-1870.
[http://dx.doi.org/10.3762/bjoc.13.181] [PMID: 29062405]
[26]
Kwak, S.H.; Lim, S-J.; Yoo, H-J.; Ha, J-E.; Gong, Y-D. Intramolecular Mizoroki–Heck reaction of 2-thiosubstituted acrylates for the synthesis of 3-substituted ben-zo[b]thiophene-2-carboxylates. Synthesis, 2016, 48, 4131-4142.
[http://dx.doi.org/10.1055/s-0035-1562613]
[27]
Pan, B.; Ren, P.; Song, H.; Wang, Z. Facile synthesis of 2-substituted benzo[b]thiophene-3-ols in water. Synth. Commun., 2013, 43, 1337-1344.
[http://dx.doi.org/10.1080/00397911.2011.633203]
[28]
Labarrios, E.; Jerezano, A.; Jiménez, F.; Cruz, M.C.; Delgado, F.; Zepeda, L.G.; Tamariz, J. Efficient synthetic approach to substituted benzo[b]furans and ben-zo[b]thiophenes by iodine-promoted cyclization of enaminones. J. Heterocycl. Chem., 2014, 51, 954-971.
[http://dx.doi.org/10.1002/jhet.1686]
[29]
Lin, C-H.; Chen, C-C.; Wu, M-J. Mercury(II)-catalyzed cyclization of 2-alkynylphenyl alkyl sulfoxides provides 3-acylbenzo[b]thiophenes. Chemistry, 2013, 19(8), 2578-2581.
[http://dx.doi.org/10.1002/chem.201202704] [PMID: 23335203]
[30]
Hashmi, A.S.K.; Yang, W.; Rominger, F. Gold(I)-catalyzed rearrangement of 3-silyloxy-1,5-enynes: an efficient synthesis of benzo[b]thiophenes, dibenzothiophenes, dibenzofurans, and indole derivatives. Chemistry, 2012, 18(21), 6576-6580.
[http://dx.doi.org/10.1002/chem.201200314] [PMID: 22517669]
[31]
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, 6305-6312.
[http://dx.doi.org/10.1016/j.tet.2013.04.099]
[32]
Ji, Y.; Li, P.; Zhang, X.; Wang, L. Trace amount Cu (ppm)-catalyzed intramolecular cyclization of 2-(gem-dibromovinyl)phenols(thiophenols) to 2-bromobenzofurans(thiophenes). Org. Biomol. Chem., 2013, 11(24), 4095-4101.
[http://dx.doi.org/10.1039/c3ob40531a] [PMID: 23673902]
[33]
Zhang, J.; Zhuang, Y.; Ma, Y.; Yang, X.; Szostak, M. Palladium-catalyzed synthesis of benzothiophenes via cross dehydrogenative coupling of 4-arylthiocoumarins and pyrones. Adv. Synth. Catal., 2019, 361, 5709-5714.
[http://dx.doi.org/10.1002/adsc.201901058]
[34]
Xia, X-F.; He, W.; Zhang, G-W.; Wang, D. Iron-catalyzed reductive cyclization reaction of 1,6-enynes for the synthesis of 3-acylbenzofurans and thiophenes. Org. Chem. Front., 2019, 6, 342-346.
[http://dx.doi.org/10.1039/C8QO01190G]
[35]
Toguem, S.T.; Malik, I.; Hussain, M.; Iqbal, J.; Villinger, A.; Langer, P. Synthesis of functionalized benzothiophenes and dibenzothiophenes by twofold Heck and subse-quent 6p-electrocyclization reactions of 2,3-dibromothiophenes and 2,3-dibromobenzothiophenes. Tetrahedron, 2013, 69, 160-173.
[http://dx.doi.org/10.1016/j.tet.2012.10.050]
[36]
Kitamura, T.; Morita, K.; Nakamori, H.; Oyamada, J. Synthesis of [1]benzothieno[3,2- b][1]benzothiophene derivatives via successive iodocyclization/photocyclization of alkynes. J. Org. Chem., 2019, 84(7), 4191-4199.
[http://dx.doi.org/10.1021/acs.joc.9b00213] [PMID: 30843398]
[37]
Danilkina, N.A.; Kulyashova, A.E.; Khlebnikov, A.F.; Bräse, S.; Balova, I.A. Electrophilic cyclization of aryldiacetylenes in the synthesis of functionalized enediynes fused to a heterocyclic core. J. Org. Chem., 2014, 79(19), 9018-9045.
[http://dx.doi.org/10.1021/jo501396s] [PMID: 25162655]
[38]
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, 4373-4376.
[http://dx.doi.org/10.1016/j.tetlet.2013.05.139]
[39]
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]
[40]
Kesharwani, K.; Kornman, C.T.; Tonnaer, A.L.; Royappa, A.D. Green synthesis of benzo[b]thiophenes via iron(III) mediated 5-endo-dig iodocyclization of 2-alkynylthioanisoles. Tetrahedron Lett., 2016, 57, 411-414.
[http://dx.doi.org/10.1016/j.tetlet.2015.12.037]
[41]
Yamauchi, T.; Shibahara, F.; Murai, T. Pd/phenanthroline-catalyzed arylative cyclization of o-(1-alkynyl)thioanisoles: synthesis of 3-arylated benzo[b]thiophenes. Tetrahedron Lett., 2016, 57, 2945-2948.
[http://dx.doi.org/10.1016/j.tetlet.2016.05.033]
[42]
Sheng, J.; Fan, C.; Wu, J. A facile and general route to 3-((trifluoromethyl)thio)benzofurans and 3-((trifluoromethyl)thio)benzothio-phenes. Chem. Commun. (Camb.), 2014, 50(41), 5494-5496.
[http://dx.doi.org/10.1039/c4cc01904k] [PMID: 24723094]
[43]
Xu, J.; Yu, X.; Yan, J.; Song, Q. Synthesis of 3-(arylsulfonyl)-benzothiophenes and benzoselenophenes via TBHP-initiated radical cyclization of 2-alkynylthioanisoles or -selenoanisoles with sulfinic acids. Org. Lett., 2017, 19(23), 6292-6295.
[http://dx.doi.org/10.1021/acs.orglett.7b02971] [PMID: 29160713]
[44]
Yan, J.; Xu, J.; Zhou, Y.; Chen, J.; Song, Q. Photoredox-catalyzed cascade annulation of methyl(2-(phenylethynyl)phenyl)sulfanes and me-thyl(2(phenylethynyl)phenyl)selanes with sulfonyl chlorides: synthsis of benzothiophenes and benzoselenophenes. Org. Chem. Front., 2018, 5, 1483-1487.
[http://dx.doi.org/10.1039/C8QO00147B]
[45]
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]
[46]
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, 1975-1982.
[http://dx.doi.org/10.1055/s-0033-1338481]
[47]
Yang, D.; Yan, K.; Wei, W.; Tian, L.; Li, Q.; You, J.; Wang, H. Metal-free n-Et4NBr-catalyzed radical cyclization of disulfides and alkynes leading to benzothiophenes under mild conditions. RSC Advances, 2014, 4, 48547-48553.
[http://dx.doi.org/10.1039/C4RA08260E]
[48]
Ye, L-M.; Qian, L.; Chen, Y-Y.; Zhang, X-J.; Yan, M. A practical synthesis of benzothiophenes via visible-light-promoted cyclization of disulfides and alkynes. Org. Biomol. Chem., 2017, 15(3), 550-554.
[http://dx.doi.org/10.1039/C6OB02461K] [PMID: 27935619]
[49]
Xie, X.; Li, P.; Shi, Q.; Wang, L. Visible-light-induced tandem cyclization of 2-alkynylanilines with disulfides: a convenient method for accessing benzothiophenes under transition-metal-free and photocatalyst-free conditions. Org. Biomol. Chem., 2017, 15(36), 7678-7684.
[http://dx.doi.org/10.1039/C7OB01747B] [PMID: 28871291]
[50]
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, 1126-1130.
[http://dx.doi.org/10.1039/C6QO00259E]
[51]
Ramesh, E.; Guntreddi, T.; Sahoo, A.K. AlCl3-Catalyzed intermolecular annulation of thiol derivatives and alkynes by 1,2-sulfur migration: construction of 6- substituted benzo[b]thiophenes. Eur. J. Org. Chem., 2017, 4405-4413.
[http://dx.doi.org/10.1002/ejoc.201700607]
[52]
Wang, X.; Gensch, T.; Glorius, F. Highly selective synthesis of 6-substituted benzothiophenes byv Sc(OTf)2-catalyzed intermolecular cyclization and sulfur migration. Org. Chem. Front., 2016, 3, 1619-1623.
[http://dx.doi.org/10.1039/C6QO00477F]
[53]
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]
[54]
Yan, K.; Yang, D.; Zhang, M.; Wei, M.; Liu, Y.; Tian, L.; Wang, H. Facile access to benzothiophenes through metal-free iodinecatalyzed intermolecular cyclization of thiophenols and alkynes. Synlett, 2015, 26, 1890-1894.
[http://dx.doi.org/10.1055/s-0034-1378841]
[55]
Xia, X-F.; Zhang, G-W.; Zhu, S-L. Visible-light-induced synthesis of benzothiophenes and benzoselenophenes via the annulation of thiophenols or 1,2-diphenyldiselane with alkynes. Tetrahedron, 2017, 73, 2727-2730.
[http://dx.doi.org/10.1016/j.tet.2017.03.053]
[56]
Wang, Y.; Wu, R.; Zhao, S.; Quan, Z.; Su, Y.; Huo, C. Air promoted annulation of thiophenols with alkynes leading to benzothiophenes. Org. Biomol. Chem., 2018, 16(10), 1667-1671.
[http://dx.doi.org/10.1039/C8OB00010G] [PMID: 29446414]
[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]
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, 1202-1207.
[http://dx.doi.org/10.1002/adsc.201501136]
[59]
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, 7753-7757.
[http://dx.doi.org/10.1039/C6RA26611H]
[60]
Zang, H.; Sun, J-G.; Dong, X.; Li, P.; Zhang, B. Preparation of benzothiophenes and benzoselenophenes from arylamines and alkynes via radical cascade reactions. Adv. Synth. Catal., 2016, 358, 1746-1752.
[http://dx.doi.org/10.1002/adsc.201501102]
[61]
Hari, D.P.; Hering, T.; König, B. Visible light photocatalytic synthesis of benzothiophenes. Org. Lett., 2012, 14(20), 5334-5337.
[http://dx.doi.org/10.1021/ol302517n] [PMID: 23039199]
[62]
Karkhelikar, M.V.; Racharlawar, S.S.; Salian, S.M.; Sridhar, B.; Likhar, P.R. Heck-type coupling of intramolecularly-generated thiopalladacycles with alkenes: one pot syntheses of 3-alkenylbenzo[b]thiophenes. J. Organomet. Chem., 2012, 706-707, 128-134.
[http://dx.doi.org/10.1016/j.jorganchem.2012.02.009]
[63]
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]
[64]
Acharya, A.; Kumar, S.V.; 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]
[65]
Sandhya, N.C.; Nandeesh, K.N.; Rangappa, K.S.; Ananda, S. One-pot synthesis of 2,3-substituted benzo[b]thiophenes via Cu(I) catalysed intramolecular cyclisation from dithioesters. RSC Advances, 2015, 5, 29939-29946.
[http://dx.doi.org/10.1039/C5RA02114F]
[66]
Soria-Castro, S.M.; Bisogno, F.R.; Peñéñory, A.B. Versatile one-pot synthesis of benzo-fused thiacycles by copper catalysis. Org. Chem. Front., 2017, 4, 1533-1540.
[http://dx.doi.org/10.1039/C6QO00776G]
[67]
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]
[68]
Garg, P.; Singh, A. Unmasking dipole character of acyl ketene dithioacetals via a Cascade reaction with arynes: synthesis of benzo[b]thiophenes. Org. Lett., 2018, 20(5), 1320-1323.
[http://dx.doi.org/10.1021/acs.orglett.8b00053] [PMID: 29446635]
[69]
Zhou, Y.; Wang, Y.; Lou, Y.; Song, Q. Cu-Catalyzed denitrogenative transannulation of 3-aminoindazoles to assemble 1-aminoisoquinolines and 3-aminobenzothiophenes. Org. Lett., 2019, 21(22), 8869-8873.
[http://dx.doi.org/10.1021/acs.orglett.9b02288] [PMID: 31432684]
[70]
Skrzyn’ska, A.; Albrecht, A.; Albrecht, L. Aminocatalytic strategy for the synthesis of optically active benzothiophene derivatives. Adv. Synth. Catal., 2016, 358, 2838-2844.
[http://dx.doi.org/10.1002/adsc.201600269]
[71]
Saktura, M.; Joachim, B.; Grzelak, P.; Albrech, L. Aromatizative inverse-electron-demand hetero-Diels-Alder reaction in the synthesis of benzothiophene derivatives. Eur. J. Org. Chem., 2019, 2019(39), 6592-6596.
[http://dx.doi.org/10.1002/ejoc.201900884]
[72]
Li, S.; Yu, A.; Li, J.; Meng, X. Synthesis of benzothiophene-fused pyran derivatives via piperidine promoted Domino reaction. Heteroatom Chem., 2019, 2019, 1-6.
[http://dx.doi.org/10.1155/2019/4361410]
[73]
Ding, W.; Zhang, Y.; Yu, A.; Zhang, L.; Meng, X. Substrate-controlled Domino reactions of crotonate-derived sulfur ylides: synthesis of benzothiophene derivatives. J. Org. Chem., 2018, 83(22), 13821-13833.
[http://dx.doi.org/10.1021/acs.joc.8b02152] [PMID: 30372063]
[74]
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]
[75]
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]
[76]
Bonagiri, S.; Acharya, A.; Pasha, M.A.; Ila, H. A metal-free, one-pot route to substituted benzo[b]thiophenes and their hetero-fused analogs via iodine mediated intramolecular arylthiolation of in situ generated β-(het)aryl-β-cyanoenethiolates. Tetrahedron Lett., 2017, 58, 4577-4582.
[http://dx.doi.org/10.1016/j.tetlet.2017.10.028]
[77]
Saraiah, B.; Gautam, V.; Acharya, A.; Pasha, M.A.; Ila, H. 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]
[78]
Zhang, X.; Zeng, W.; Yang, Y.; Huang, H.; Liang, Y. Transition-metal-free method for the synthesis of benzo[b]thiophenes from o-halovinylbenzenes and K2S via direct SNAr-type reaction, cyclization, and dehydrogenation process. Synlett, 2013, 24, 1687-1692.
[http://dx.doi.org/10.1055/s-0033-1339289]
[79]
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, 7969-7972.
[http://dx.doi.org/10.1016/j.tet.2014.08.049]
[80]
Prasad, D.J.C.; 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]
[81]
Li, Y.; Cheng, L.; Li, B.; Jiang, S.; Chen, L.; Shao, Y. Transition-metal-free thiolation annulation of 2-fluorophenylacetylene derivatives: expedient synthesis of ben-zo[b]thiophenes sing Na2S.9H2O. ChemistrySelect, 2016, 5, 1092-1095.
[http://dx.doi.org/10.1002/slct.201600270]
[82]
Reddy, C.R.; Valleti, R.R.; Sathish, P. [4 + 2] Benzannulation of 3-alkenylpyrroles/thiophenes with propargylic alcohols: access to substituted indoles, benzothiophenes, and aza[5]helicenes. J. Org. Chem., 2017, 82(5), 2345-2354.
[http://dx.doi.org/10.1021/acs.joc.6b02637] [PMID: 28195471]
[83]
Dhayalan, V.; Mohanakrishnan, A.K. Lewis acid–mediated Domino reaction of 3-bromomethyl thiophene with arenes/heteroarenes. Synth. Commun., 2012, 42, 2149-2160.
[http://dx.doi.org/10.1080/00397911.2011.554063]
[84]
Debray, J.; Lemaire, M.; Popowycz, F. Straightforward synthesis of 2-acetyl-substituted benzo[b]thiophenes. Synlett, 2013, 24, 37-40.
[http://dx.doi.org/10.1055/s-0032-1317674]
[85]
Kunz, T.; Knochel, P. Synthesis of functionalized benzo[b]thiophenes by the intramolecular copper-catalyzed carbomagnesiation of alkynyl(aryl)-thioethers. Angew. Chem. Int. Ed. Engl., 2012, 51(8), 1958-1961.
[http://dx.doi.org/10.1002/anie.201106734] [PMID: 22253072]
[86]
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]
[87]
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]
[88]
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]
[89]
Jana, S.; Verma, A.; Kadu, R.; Kumar, S. Visible-light-induced oxidant and metal-free dehydrogenative cascade trifluoromethylation and oxidation of 1,6-enynes with water. Chem. Sci. (Camb.), 2017, 8(9), 6633-6644.
[http://dx.doi.org/10.1039/C7SC02556D] [PMID: 28989690]
[90]
Zhao, X.; Li, Q.; Xu, J.; Wang, D.; Negrerie, D.Z.; Du, Y. Cascade synthesis of benzothieno[3,2- b]indoles under oxidative conditions mediated by CuBr and tert-butyl hydroperoxide. Org. Lett., 2018, 20(18), 5933-5937.
[http://dx.doi.org/10.1021/acs.orglett.8b02614] [PMID: 30211558]
[91]
Kesharwani, T.; Craig, J.; Rosario, C.D.; Shavnore, R.; Kornman, C. Synthesis of 3-iodobenzo[b]thiophenes via iodocyclization/etherification reaction sequence. Tetrahedron Lett., 2014, 55, 6812-6816.
[http://dx.doi.org/10.1016/j.tetlet.2014.10.064]
[92]
An, C.; Li, C-Y.; Huang, X-B.; Gao, W-X.; Zhou, Y-B.; Liu, M-C.; Wu, H-Y. Selenium radical mediated cascade cyclization: concise synthesis of selenated benzofurans (benzothiophenes). Org. Lett., 2019, 21(17), 6710-6714.
[http://dx.doi.org/10.1021/acs.orglett.9b02315] [PMID: 31407585]
[93]
Jiang, P.; Che, X.; Liao, Y.; Huang, H.; Deng, G.J. Three-component 2-aryl substituted benzothiophene formation under transition-metal free conditions. RSC Advances, 2016, 6, 41751-41754.
[http://dx.doi.org/10.1039/C6RA07730G]
[94]
Adib, M.; Bayanati, M.; Soheilizad, M.; Ghazvini, H.J.; Tajbakhsh, M.; Amanlou, M. A simple synthesis of alkyl 2-aminobenzo[b]thiophene-3-carboxylates via an unexpected dehydrogenation of alkyl 2-amino-4,5,6,7-tetrahydrobenzo[b]- thiophene-3-carboxylates. Synlett, 2014, 25, 2918-2922.
[http://dx.doi.org/10.1055/s-0034-1379475]
[95]
Adib, M.; Soheilizad, M.; Rajai-daryasaraei, S.; Mirzaei, P. An efficient aromatization of 2-amino-4,5,6,7-tetrahydrobenzo- [b]thiophene-3-carboxylates in dimethyl sulfoxide catalyzed by p-toluenesulfonic acid. Synlett, 2015, 26, 1101-1105.
[http://dx.doi.org/10.1055/s-0034-1379998]
[96]
Wu, B.; Yoshikai, N. Versatile synthesis of benzothiophenes and benzoselenophenes by rapid assembly of arylzinc reagents, alkynes, and elemental chalcogens. Angew. Chem. Int. Ed. Engl., 2013, 52(40), 10496-10499.
[http://dx.doi.org/10.1002/anie.201304546] [PMID: 23960030]

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