Selective Synthesis, Characterization of Isomerically Pure Arylated Benzo[1,2-b:6,5-b′]dithiophenes by Regioselective Suzuki–Miyaura Reaction and Evaluation of the Catalytic Properties of Nickel versus Palladium Complexes

Abstract

Selective synthesis of isomerically pure, angular-shaped benzo[1,2-b:6,5-b′]dithiophenes and various aryl-substituted analogues via the regioselective Suzuki–Miyaura cross-coupling reaction is described. The structural assignments of symmetrical and unsymmetrical derivatives of benzodithiophenes and coumarin-type polyheterocycles are based on X-ray crystallography and spectroscopic studies. A comparative study of nickel versus palladium complexes demonstrated that the nickel complex NiCl₂(dppe) is more effective in terms of reactivity and yields than palladium catalysis in the Suzuki–Miyaura cross-coupling of hindered 3,6-dichlorobenzo[1,2-b:6,5-b′]dithiophenes with arylboronic acids.

Key words

isomeric purity - symmetry - spectroscopy - regioselectivity - benzodithiophenes - Suzuki–Miyaura reaction

• References

• 1a Nakano M, Niimi K, Miyazaki E, Osaka I, Takimiya K. J. Org. Chem. 2012; 77: 8099
• 1b Garnier F. Angew. Chem., Int. Ed. Engl. 1989; 28: 513
• 1c Garnier F, Yassar A, Hajlaoui R, Horowitz G, Deloffre F, Servet B, Ries S, Alnot P. J. Am. Chem. Soc. 1993; 115: 8716
• 1d Garnier F, Hajlaoui R, Yassar A, Srivastava P. Science 1994; 265: 1684
• 1e Dodabalapur A, Torsi L, Katz HE. Science 1995; 268: 270
• 1f Dodabalapur A, Rothberg LJ, Fung AW. P, Katz HE. Science 1996; 272: 1462
• 2a Takimiya K, Shinamura S, Osaka I, Miyazaki E. Adv. Mater. 2011; 23: 4347
• 2b Sista P, Biewer MC, Stefan MC. Macromol. Rapid Commun. 2012; 33: 9
• 3a Shinamura S, Osaka I, Miyazaki E, Takimiya K. Heterocycles 2011; 83: 1187
• 3b Takimiya K, Kunugi Y, Konda Y, Niihara N, Otsubo T. J. Am. Chem. Soc. 2004; 126: 5084
• 3c Takimiya K, Konda Y, Ebata H, Niihara N, Otsubo T. J. Org. Chem. 2005; 70: 10569
• 3d Takimiya K, Kunugi Y, Toyoshima Y, Otsubo T. J. Am. Chem. Soc. 2005; 127: 3605
• 3e Takimiya K, Kunugi Y, Konda Y, Ebata H, Toyoshima Y, Otsubo T. J. Am. Chem. Soc. 2006; 128: 3044
• 3f Yamamoto T, Takimiya K. J. Am. Chem. Soc. 2007; 129: 2224

For reviews, see:
• 4a Katz H, Bao EZ, Gilat SL. Acc. Chem. Res. 2001; 34: 359
• 4b Takimiya K, Kunugi Y, Otsubo T. Chem. Lett. 2007; 36: 578
• 4c Murphy AR, Frechet JM. J. Chem. Rev. 2007; 107: 1066
• 4d Ong BS, Wu Y, Li Y, Liu P, Pan H. Chem. Eur. J. 2008; 14: 4766
• 4e Allard S, Forster M, Souharce B, Thiem H, Scherf U. Angew. Chem. 2008; 120: 4138
• 4f Chen J, Cao Y. Acc. Chem. Res. 2009; 42: 1709
• 5a Cinar ME, Ozturk T. Chem. Rev. 2015; 115: 3036
• 5b Sotzing GA, Invernale MA, Ding Y. US Patent 0235323, 2013
• 6a Tsutsui Y, Sakurai T, Minami S, Hirano K, Satoh K, Matsuda W, Kato K, Takata M, Miura M, Seki S. Phys. Chem. Chem. Phys. 2015; 17: 9624
• 6b Minami S, Ide M, Hirano K, Satoh K, Sakurai T, Kato K, Takata M, Seki S, Miura M. Phys. Chem. Chem. Phys. 2014; 16: 18805
• 6c Ota S, Minami S, Hirano K, Satoh T, Ie Y, Seki S, Aso Y, Miura M. RSC Adv. 2013; 3: 12356
• 6d Miura M, Ota S, Hirano K, Satoh T, Ueda M. PCT Int. Appl WO 2012105517, 2012
• 7a Romain M, Thiery S, Shirinskaya A, Declairieux C, Tondelier D, Geffroy B, Jeannin O, Rault-Berthelot J, Métivier R, Poriel C. Angew. Chem. 2015; 127: 1192
• 7b Romain M, Tondelier D, Vanel J.-C, Geffroy B, Jeannin O, Rault-Berthelot J, Métivier R, Poriel C. Angew. Chem. Int. Ed. 2013; 52: 14147
• 8 Shinamura S, Osaka I, Miyazaki E, Nakao A, Yamagishi M, Takeya J, Takimiya K. J. Am. Chem. Soc. 2011; 133: 5024
• 9 Hassan Z, Reimann S, Wittler K, Ludwig R, Villinger A, Langer P. Adv. Synth. Catal. 2012; 354: 731
• 10a Ried W, Oremek G, Ocakcioglu B. Liebigs Ann. Chem. 1980; 1424
• 10b Ried W, Oremek G. Liebigs Ann. Chem. 1980; 1172
• 10c Malesevic M, Karminski-Zamola G, Bajic M, Boykin DW. Heterocycles 1995; 41: 2691
• 11a Miyasaka M, Hirano K, Satoh T, Miura M. Adv. Synth. Catal. 2009; 351: 2683
• 11b Kumagai J, Hirano K, Satoh T, Seki S, Miura M. J. Phys. Chem. B 2011; 115: 8446
• 11c Kumagai J, Hirano K, Satoh T, Seki S, Miura M. J. Phys. Chem. B 2012; 116: 4115
• 11d Miyasaka M, Hirano K, Satoh T, Miura M. Adv. Synth. Catal. 2012; 354: 957
• 12 CCDC 852980 contains the supplementary crystallographic data for compound 3b in this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.
• 13 Hassan Z, Al-Shidhani S, Al-Ghafri A, Al-Harrasi A, Hussain J, Csuk R. Tetrahedron Lett. 2015; 56: 7141
• 14 Littke AF, Fu GC. Angew. Chem. Int. Ed. 2002; 41: 4176
• 15a Lundgren RJ, Stradiotto M. Chem. Eur. J. 2012; 18: 9758
• 15b Valente C, Calimsiz S, Hoi KH, Mallik D, Sayah M, Organ MG. Angew. Chem. Int. Ed. 2012; 51: 3314
• 16 Littke AF, Dai C, Fu GC. J. Am. Chem. Soc. 2000; 122: 4020
• 17a Reimann S, Ehlers P, Sharif M, Spannenberg A, Langer P. Tetrahedron 2016; 72: 1083
• 17b Ehlers P, Hakobyan A, Neubauer A, Lochbrunner S, Langer P. Adv. Synth. Catal. 2013; 355: 1849
• 17c Reimann S, Ehlers P, Petrosyan A, Kohse S, Spannenberg A, Surkus AE, Ghochikyan TV, Saghyan AS, Lochbrunner S, Kuhn O, Ludwig R, Langer P. Adv. Synth. Catal. 2014; 356: 1987
• 17d Reimann S, Ehlers P, Parpart S, Surkus A, Spannenberg A, Langer P. Tetrahedron 2015; 71: 5371
• 17e Bei X, Crevier T, Guram AS, Jandeleit B, Powers TS, Turner HW, Uno T, Weinberg WH. Tetrahedron Lett. 1999; 40: 3855
• 17f Bei X, Turner HW, Weinberg WH, Guram AS, Petersen JL. J. Org. Chem. 1999; 64: 6797
• 17g Zhang C, Huang J, Trudell ML, Nolan SP. J. Org. Chem. 1999; 64: 3804
• 17h Herrmann WA, Reisinger C.-P, Spiegler M. J. Organomet. Chem. 1998; 557: 93
• 17i Weskamp T, Bohm VP. W, Herrmann WA. J. Organomet. Chem. 1999; 585: 348