The Synthesis of Unsymmetrical Arylated Tetrathiafulvalenes Extended with an Anthraquinoid Spacer via Pd-Catalyzed C–H Arylation

Aya Yoshimura; Yuto Aso; Ryosuke Utsumi; Fuma Tosa; Yohji Misaki

doi:10.1055/a-2416-2206

Synlett, Inhaltsverzeichnis

Synlett 2025; 36(07): 859-863
DOI: 10.1055/a-2416-2206

letter

Thieme Chemistry Journals Awardees 2024

The Synthesis of Unsymmetrical Arylated Tetrathiafulvalenes Extended with an Anthraquinoid Spacer via Pd-Catalyzed C–H Arylation

Aya Yoshimura ∗

^aDepartment of Applied Chemistry, Graduate School of Science and Engineering, Ehime University, 3 Bunkyo-cho, Matsuyama, Ehime 790-8577, Japan

,

Yuto Aso

^aDepartment of Applied Chemistry, Graduate School of Science and Engineering, Ehime University, 3 Bunkyo-cho, Matsuyama, Ehime 790-8577, Japan

,

Ryosuke Utsumi

^aDepartment of Applied Chemistry, Graduate School of Science and Engineering, Ehime University, 3 Bunkyo-cho, Matsuyama, Ehime 790-8577, Japan

,

Fuma Tosa

^aDepartment of Applied Chemistry, Graduate School of Science and Engineering, Ehime University, 3 Bunkyo-cho, Matsuyama, Ehime 790-8577, Japan

,

Yohji Misaki ∗

^aDepartment of Applied Chemistry, Graduate School of Science and Engineering, Ehime University, 3 Bunkyo-cho, Matsuyama, Ehime 790-8577, Japan

^bResearch Unit for Materials Development for Efficient Utilization and Storage of Energy (RU:E-USE), Ehime University, 2-5 Bunkyo-cho, Matsuyama, Ehime 790-8577, Japan

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Abstract

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Abstract

We synthesized diarylated 10-(1,3-dithiol-2-ylidene)anthracene-9-(10H)-one derivatives, which serve as important precursors of unsymmetrical arylated TTFAQs, via the palladium-catalyzed direct C–H arylation. Unsymmetrical diarylated TTFAQs were synthesized by the Horner–Wadsworth–Emmons reaction using diarylated 10-(1,3-dithiol-2-ylidene)anthracene-9-(10H)-one as the starting materials. Additionally, we have successfully synthesized unsymmetrical tetraarylated TTFAQs by a second palladium-catalyzed C–H arylation of diarylated TTFAQs.

Key words

tetrathiafulvalene - extended TTF - anthraquinoid spacer - unsymmetrical arylated compounds - palladium-catalyzed direct C–H arylation - X-ray structure analysis - redox behavior

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References and Notes
1 TTF Chemistry-Fundamental and Applications of Tetrathiafulvalene. Yamada J, Sugimoto T. Kodansha-Springer; Tokyo: 2004: 3

2a Canevet D, Sallé M, Zhang G, Zhang D, Zhu D. Chem. Commun. 2009; 2245
2b Gorgues A, Hudhomme P, Sallé M. Chem. Rev. 2004; 104: 5151
2c Segura JL, Martín N. Angew. Chem. Int. Ed. 2001; 40: 1372
2d Iyoda M, Hasegawa M, Miyake Y. Chem. Rev. 2004; 104: 5085
2e Lorcy D, Bellec N, Fourmigué M, Avarvari N. Coord. Chem. Rev. 2009; 253: 1398
2f Bergkamp JJ, Decurtins S, Liu S.-X. Chem. Soc. Rev. 2015; 44: 863
2g Pop F, Avarvari N. Chem. Commun. 2016; 52: 7906
2h Hasegawa M, Iyoda M. In Organic Redox Systems, Chapt. 4. Nishinaga T. Wiley; Hoboken: 2016: 89
2i Zhao B, Tao J, Chen X, Zhu W. Chin. J. Org. Chem. 2017; 37: 1964
2j Liang X, Wang L, Jeong K, Lee M. Chin. Chem. Lett. 2019; 30: 123

3a Akiba K, Ishikawa K, Inamoto N. Bull. Chem. Soc. Jpn. 1978; 51: 2674
3b Bryce MR, Moore AJ. Synth. Met. 1988; 25: 203
3c Bryce MR, Moore AJ, Hasan M, Ashwell GJ, Fraser AT, Clegg W, Hursthouse MB, Karaulov AI. Angew. Chem., Int. Ed. 1990; 29: 1450
3d Barthelmes K, Sittig M, Winter A, Schubert US. Eur. J. Inorg. Chem. 2017; 3698
3e Hachem H, Vacher A, Dorcet V, Lorcy D. Organometallics 2017; 36: 2208
3f Bryce MR, Finn T, Moore AJ, Batsanov AS, Howard JA. K. Eur. J. Org. Chem. 2000; 51
3g Jones AE, Christensen CA, Perepichka DF, Batsanov AS, Beeby A, Low PJ, Bryce MR, Parker AW. Chem. Eur. J. 2001; 7: 973

4a Martín N, Sańchez L, Herranz MÁ, Illescas B, Guldi DM. Acc. Chem. Res. 2007; 40: 1015
4b Wenger S, Bouit P.-A, Chen Q, Teuscher J, Censo DD, Humphry-Baker R, Moser J.-E, Delgado JL, Martín N, Zakeeruddin SM, Grätzel M. J. Am. Chem. Soc. 2010; 132: 5164
4c Ogi D, Fujita Y, Kato M, Yamauchi T, Shirahata T, Yao M, Misaki Y. Eur. J. Org. Chem. 2019; 2725
4d Hardouin-Lerouge M, Chesneau B, Allain M, Hudhomme P. J. Org. Chem. 2012; 77: 2441
4e Isla H, Gallego M, Peŕez EM, Viruela R, Ortí E, Martín N. J. Am. Chem. Soc. 2010; 132: 1772
4f Bivaud S, Goeb S, Croué V, Dron PI, Allain M, Sallé M. J. Am. Chem. Soc. 2013; 135: 10018
4g Abdollahi MF, Zhao Y. J. Org. Chem. 2021; 86: 14855

5a Gordillo MA, Benavides PA, Panda DK, Saha S. ACS Appl. Mater. Interfaces 2020; 12: 12955
5b Yoshimura A, Henmi K, Kimura H, Sakakibara R, Ochi R, Shirahata T, Yorimitsu H, Misaki Y. Synthesis 2021; 53: 326
5c Colomban C, Szalóki G, Allain M, Goméz L, Goeb S, Sallé M, Costas M, Ribas X. Chem. Eur. J. 2017; 23: 3016
5d Colomban C, Fuertes-Espinosa C, Goeb S, Sallé M, Costas M, Blancafort L, Ribas X. Chem. Eur. J. 2018; 24: 4371

6a Hu L, Qin j, Zhu R.-M, Li Y.-Z, Zuo J.-L, You X.-Z. Eur. J. Inorg. Chem. 2012; 2494
6b Illescas BM, Santos J, Díaz MC, Martín N, Atienza CM, Guldi DM. J. Eur. J. Org. Chem. 2007; 5027
6c Hachem H, Vacher A, Dorcet V, Lorcy D. Organometallics 2017; 36: 2208
6d Perepichka DF, Bryce MR, Perepichka IF, Lyubchik SB, Christensen CA, Godbert N, Batsanov AS, Levillain E, Mclnnes EJ. L, Zhao JP. J. Am. Chem. Soc. 2002; 124: 14227
6e Godbert N, Bryce MR. J. Mater. Chem. 2002; 12: 27
6f Godbert N, Bryce MR. Dahaoui S, Batsanov AS, Howard JA. K, Hazendonk P. Eur. J. Org. Chem. 2001; 749
6g Godbert N, Batsanov AS, Bryce MR. Howard J. A. K. J. Org. Chem. 2001; 66: 713

7a Mitamura Y, Yorimitsu H, Oshima K, Osuka A. Chem. Sci. 2011; 2: 2017
7b Yorimitsu H, Yoshimura A, Misaki Y. Synthesis 2020; 52: 3326
7c Yoshimura A, Misaki Y. Chem. Rec. 2021; 21: 3520

8 Bryce MR, Moore AJ, Lorcy D, Dhindsa AS, Robert A. J. Chem. Soc., Chem. Commun. 1990; 470
9 Batsanov AS, Bryce MR, Coffin MA, Green A, Hester RE, Howard JA. K, Lednev IK, Martín N, Moore AJ, Moore JN, Ortí E, Sánchez L, Savirón M, Viruela PM, Viruela R, Ye T.-Q. Chem. Eur. J. 1998; 4: 2580

10a Christensen CA, Bryce MR, Batsanov AS, Howard JA. K, Jeppesen JO, Becher J. Chem. Commun. 1999; 2433
10b Christensen CA, Bryce MR, Batsanov AS, Becher J. Org. Biomol. Chem. 2003; 1: 511

11a Moore AJ, Bryce MR. J. Chem. Soc., Perkin Trans. 1 1991; 157
11b Märkl G, Bruns D, Dietl H, Kreitmeier P. Helv. Chim. Acta 2001; 84: 2220

12a Yoshimura A, Hemmi K, Moriwaki H, Sakakibara R, Kimura H, Aso Y, Kinoshita N, Suizu R, Shirahata T, Yao M, Yorimitsu H, Awaga K, Misaki Y. ACS. Appl. Mater. Interfaces 2022; 14: 35978
12b Yoshimura A, Yoshinouchi M, Hemmi K, Aso Y, Utsumi R, Shirahata T, Yao M, Misaki Y. New J. Chem. 2023; 47: 11760

13 Ueno R, Fujino R, Yorimitsu H, Osuka A. Chem. Eur. J. 2013; 19: 7156
14 Synthesis of unsymmetrical arylated TTFs via a selective magnesiation of 1,3-dithiole-2-thiones using TMPMgCl·LiCl (Scheme S2) was also reported; however, this method is difficult to apply the synthesis of unsymmetrical arylated TTFAQs because of the competitive homocoupling of 1,3-dithiole-2-thiones. See: Nafe J, Knochel P. Synthesis 2016; 48: 103

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