C−H Arylation of Thiophenes with Aryl Bromides by a Parts-per-Million Loading of a Palladium NNC-Pincer Complex

Anggi Eka Purta; Shun Ichii; Aya Tazawa; Yasuhiro Uozumi

doi:10.1055/s-0040-1707213

Synlett, Inhaltsverzeichnis

Synlett 2020; 31(16): 1634-1638
DOI: 10.1055/s-0040-1707213

letter

C−H Arylation of Thiophenes with Aryl Bromides by a Parts-per-Million Loading of a Palladium NNC-Pincer Complex

Authors

Anggi Eka Purta

^aInstitute for Molecular Science (IMS), Myodaiji, Okazaki 444-0864, Japan
Shun Ichii

^aInstitute for Molecular Science (IMS), Myodaiji, Okazaki 444-0864, Japan

^bThe Graduate University for Advanced Studies, SOKENDAI, Myodaiji, Okazaki 444-0864, Japan eMail: uo@ims.ac.jp
Aya Tazawa

^aInstitute for Molecular Science (IMS), Myodaiji, Okazaki 444-0864, Japan
Yasuhiro Uozumi ∗

^aInstitute for Molecular Science (IMS), Myodaiji, Okazaki 444-0864, Japan

^bThe Graduate University for Advanced Studies, SOKENDAI, Myodaiji, Okazaki 444-0864, Japan eMail: uo@ims.ac.jp

Abstract

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Abstract

A palladium NNC-pincer complex efficiently catalyzed the direct arylation of thiophene derivatives with extremely low palladium loadings of the order of parts per million. Thus, the reaction of various thiophenes with aryl bromides in the presence of 25–100 mol ppm of chlorido[(2-phenyl-κ-C ²)-9-phenyl-1,10-phenanthroline-κ²-N,N′]palladium(II) NNC-pincer complex, K₂CO₃, and pivalic acid in N,N-dimethylacetamide afforded the corresponding 2- or 5-arylated thiophenes in good to excellent yields. A combination of the present C–H arylation and Hiyama coupling with the same NNC-pincer complex provides an efficient synthesis of unsymmetrical 2,5-thiophenes with catalyst loadings at mol ppm levels.

Key words

C–H functionalization - arylation - palladium catalysis - pincer complexes - thiophenes - Hiyama coupling

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Referenzen

References and Notes

1a Torborg C, Beller M. Adv. Synth. Catal. 2009; 351: 3027
1b Magano J, Dunetz JR. Chem. Rev. 2011; 111: 2177
1c Busacca CA, Fandrick DR, Song JJ, Senanayake CH. Adv. Synth. Catal. 2011; 353: 1825
1d Xu S, Kim EH, Wei A, Negishi E.-i. Sci. Technol. Adv. Mater. 2014; 15: 04420

2 ICH; Quality Guidelines; International Council for Harmonisation: Geneva; https://www.ich.org/page/quality-guidelines (accessed Jul 16, 2020)

3a Usluer Ö, Abbas M, Wantz G, Vignau L, Hirsch L, Grana E, Brochon C, Cloutet E, Hadziioannou G. ACS Macro Lett. 2014; 3: 1134
3b Egorova KS, Ananikov VP. Angew. Chem. Int. Ed. 2016; 55: 12150
3c Egorova KS, Ananikov VP. Organometallics 2017; 36: 4071
3d Hayler JD, Leahy DK, Simmons EM. Organometallics 2019; 38: 36

4 Farina V. Adv. Synth. Catal. 2004; 346: 1553
5 Thomé I, Nijs A, Bolm C. Chem. Soc. Rev. 2012; 41: 979
6 Deraedt C, Astruc D. Acc. Chem. Res. 2014; 47: 494
7 Roy D, Uozumi Y. Adv. Synth. Catal. 2018; 360: 602

8a Allard S, Forster M, Souharce B, Thiem V, Scherf U. Angew. Chem. Int. Ed. 2008; 47: 4070
8b Mishra A, Fischer MK. R, Bäuerle P. Angew. Chem. Int. Ed. 2009; 48: 2474
8c Mei J, Diao Y, Appleton AL, Fang L, Bao Z. J. Am. Chem. Soc. 2013; 135: 6724
8d Okamoto K, Zhang J, Housekeeper JB, Marder SR, Luscombe CK. Macromolecules 2013; 46: 8059 ; corrigendum: Macromolecules 2013, 46, 7565
8e Cinar ME, Ozturk T. Chem. Rev. 2015; 115: 3036

9a Dadiboyena S. Eur. J. Med. Chem. 2012; 51: 17
9b Mabkhot YN, Alatibi F, El-Sayed NN. E, Al-Showiman S, Kheder NA, Wadood A, Rauf A, Bawazeer S, Ben Hadda T. Molecules 2016; 21: 222
9c Metil DS, Sonawane SP, Pachore SS, Mohammad A, Dahanukar VH, McCormack PJ, Reddy CV, Bandichhor R. Org. Process Res. Dev. 2018; 22: 27 ; corrigendum: Org. Process. Res. Dev. 2018, 22, 420

10 Ohta A, Akita Y, Ohkuwa T, Chiba M, Fukunaga R, Miyafuji A, Nakata T, Tani N. Heterocycles 1990; 31: 1951

For reviews, see:

11a Roger J, Gottumukkala AL, Doucet H. ChemCatChem 2010; 2: 20
11b Ackermann L. Chem. Rev. 2011; 111: 1315
11c Mercier LG, Leclerc M. Acc. Chem. Res. 2013; 46: 1597
11d Bellina F. Top. Organomet. Chem. 2015; 55: 77
11e Bheeter CB, Chen L, Soulé J.-F, Doucet H. Catal. Sci. Technol. 2016; 6: 2005

For selected examples, see:

12a Join B, Yamamoto T, Itami K. Angew. Chem. Int. Ed. 2009; 48: 3644
12b Liégault B, Lapointe D, Caron L, Vlassova A, Fagnou K. J. Org. Chem. 2009; 74: 1826
12c Liégault B, Petrov I, Gorelsky SI, Fagnou K. J. Org. Chem. 2010; 75: 1047
12d Tamba S, Okubo Y, Tanaka S, Monguchi D, Mori A. J. Org. Chem. 2010; 75: 6998
12e Kamiya H, Yanagisawa S, Hiroto S, Itami K, Shinokubo H. Org. Lett. 2011; 13: 6394
12f Baghbanzadeh M, Pilger C, Kappe CO. J. Org. Chem. 2011; 76: 8138
12g Schipper DJ, Fagnou K. Chem. Mater. 2011; 23: 1594
12h Ghosh D, Lee HM. Org. Lett. 2012; 14: 5534
12i Gorelsky SI, Lapointe D, Fagnou K. J. Org. Chem. 2012; 77: 658
12j Jia N.-N, Tian X.-C, Qu X.-X, Chen X.-X, Cao Y.-N, Yao Y.-X, Gao F, Zhou X.-L. Sci. Rep. 2017; 7: 43758
12k Li H.-H, Maitra R, Kuo Y.-T, Chen J.-H, Hu C.-H, Lee HM. Appl. Organomet. Chem. 2018; 32: e3956
12l Mao S, Shi X, Soulé J.-F, Doucet H. Adv. Synth. Catal. 2018; 360: 3306

13a Roy D, Mom S, Beaupérin M, Doucet H, Hierso J.-C. Angew. Chem. Int. Ed. 2010; 49: 6650
13b Martin AR, Chartoire A, Slawin AM. Z, Nolan SP. Beilstein J. Org. Chem. 2012; 8: 1637
13c Yamada YM. A, Yuyama Y, Sato T, Fujikawa S, Uozumi Y. Angew. Chem. Int. Ed. 2014; 53: 127
13d Li Y, Wang J, Huang M, Wang Z, Wu Y, Wu Y. J. Org. Chem. 2014; 79: 2890
13e Luo B.-T, Liu H, Lin Z.-J, Jiang J, Shen DS, Liu R.-Z, Ke Z, Liu F.-S. Organometallics 2015; 34: 4881
13f Ouyang J.-S, Li Y.-F, Shen D.-S, Ke Z, Liu F.-S. Dalton Trans. 2016; 45: 14919
13g Colletto C, Panigrahi A, Fernández-Casado J, Larrosa I. J. Am. Chem. Soc. 2018; 140: 9638

14a Roger J, Požgan F, Doucet H. Green Chem. 2009; 11: 425
14b Roger J, Požgan F, Doucet H. Adv. Synth. Catal. 2010; 352: 696
14c Bheeter CB, Bera JK, Doucet H. J. Org. Chem. 2011; 76: 6407
14d Zhao L, Bruneau C, Douchet H. Tetrahedron 2013; 69: 7082

15a Takenaka K, Uozumi Y. Adv. Synth. Catal. 2004; 346: 1693
15b Takenaka K, Minakawa M, Uozumi Y. J. Am. Chem. Soc. 2005; 127: 12273
15c Sarkar SM, Uozumi Y, Yamada YM. A. Angew. Chem. Int. Ed. 2011; 50: 9437
15d Yamada YM. A, Sarkar SM, Uozumi Y. J. Am. Chem. Soc. 2012; 134: 3190
15e Yamada YM. A, Sarkar SM, Uozumi Y. J. Am. Chem. Soc. 2012; 134: 9285
15f Sato T, Ohno A, Sarkar SM, Uozumi Y, Yamada YM. A. ChemCatChem 2015; 7: 2141
15g Hamasaka G, Roy D, Tazawa A, Uozumi Y. ACS Catal. 2019; 9: 11640

16a Hamasaka G, Sakurai F, Uozumi Y. Chem. Commun. 2015; 51: 3886
16b Hamasaka G, Ichii S, Uozumi Y. Adv. Synth. Catal. 2018; 360: 1833
16c Ichii S, Hamasaka G, Uozumi Y. Chem. Asian J. 2019; 14: 3850

17 C–H Arylation of 1-Benzothiophene (1); General Procedure A Schlenk tube containing a magnetic stirrer bar was charged with 1-benzothiophene (1; 2 mmol), the appropriate aryl bromide 2 (1 mmol), K₂CO₃ (0.5 mmol), pivalic acid (0.3 mmol), a 0.5 mM solution of DPP-NNC in anhyd DMA (100 μL; 5 ×10^–5 mmol Pd), and anhyd DMA (1.9 mL). The resulting mixture was degassed and stirred vigorously at 150 °C under N₂ for 20 h. The mixture was then cooled to r.t., diluted with EtOAc, transferred to a separatory funnel, and washed with water (×3). The organic layer was dried (Na₂SO₄) and concentrated in vacuo, and the resulting residue was purified by chromatography (silica gel, hexane/AcOEt).
18 2-(2,6-Dimethylphenyl)benzo[b]thiophene (3j) White solid; yield: 218 mg (92%). ¹H NMR (396 MHz, CDCl₃): δ = 7.81 (d, J = 8.3 Hz, 1 H), 7.75 (d, J = 7.1 Hz, 1 H), 7.52 (s, 1 H), 7.36–7.24 (m, 4 H), 6.98 (s, 1 H), 2.37 (s, 6 H). ¹³C NMR (100 MHz, CDCl₃): δ = 144.6, 140.7, 139.4, 138.5, 134.1, 130.1, 124.4, 124.3, 124.1, 123.5, 122.2, 119.2, 21.26. HRMS (FAB): m/z [M⁺] calcd for C₁₆H₁₄S: 238.0816; found: 238.0823. 2-(2-Isopropylphenyl)benzo[b]thiophene (3n) Colorless oil; yield: 152 mg (60%). ¹H NMR (396 MHz, CDCl₃): δ = 7.84 (d, J = 7.9 Hz, 1 H), 7.79 (d, J = 7.1 Hz, 1 H), 7.42–7.31 (m, 5 H), 7.22–7.20 (m, 1 H), 7.18 (s, 1 H), 3.38–3.31 (m, 1 H), 1.22 (d, J = 6.7 Hz, 6 H). ¹³C NMR (100 MHz, CDCl₃): δ = 147.8, 143.3, 140.3, 140.0, 133.0, 131.0, 129.0, 125.7, 125.4, 124.3, 124.0, 123.4, 123.1, 122.0, 29.7, 24.4. EI-MS: m/z = 252 [M⁺]. HRMS (FAB): m/z [M⁺] calcd for C₁₇H₁₆S: 252.0973; found: 252.0961. 2-(2,6-Difluorophenyl)benzo[b]thiophene (3o) White solid; yield: 152 mg (62%). ¹H NMR (396 MHz, CDCl₃): δ = 7.88–7.83 (m, 2 H), 7.74 (s, 1 H), 7.38–7.35 (m, 2 H), 7.31–7.25 (m, 1 H), 7.10–7.00 (m, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 160.1 (dd, J = 252.9, 6.8 Hz), 140.3 (t, J = 2.9 Hz), 139.2, 129.7 (t, J = 2.8 Hz), 129.2 (t, J = 10.5 Hz), 126.2 (t, J = 5.7 Hz), 124.8, 124.3, 123.9, 121.8, 112.1 (q, J = 17.2 Hz), 111.9 (dd, J = 24.9, 1.9 Hz). EI-MS: m/z = 246 [M⁺]. HRMS (FAB): m/z [M⁺] calcd for C₁₄H₈F₂S: 246.0315; found: 246.0323.
19 King WJ, Nord FF. J. Org. Chem. 1949; 14: 638

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