A Versatile Approach for the Synthesis of para-Substituted Arenes via Palladium-Catalyzed C–H Functionalization and Protodecarboxylation of Benzoic Acids

Shulei Pan; Bo Zhou; Yanghui Zhang; Changdong Shao; Guangfa Shi

doi:10.1055/s-0035-1560579

Synlett, Inhaltsverzeichnis

Synlett 2016; 27(02): 277-281
DOI: 10.1055/s-0035-1560579

letter

A Versatile Approach for the Synthesis of para-Substituted Arenes via Palladium-Catalyzed C–H Functionalization and Protodecarboxylation of Benzoic Acids

Authors

Shulei Pan

Shanghai Key Laboratory of Chemical Assessment and Sustainability, Department of Chemical, and UNEP-Tongji Institute of Environment for Sustainable Development, Tongji University, 1239 Siping Road, Shanghai 200092, P. R. of China eMail: zhangyanghui@tongji.edu.cn
Bo Zhou

Shanghai Key Laboratory of Chemical Assessment and Sustainability, Department of Chemical, and UNEP-Tongji Institute of Environment for Sustainable Development, Tongji University, 1239 Siping Road, Shanghai 200092, P. R. of China eMail: zhangyanghui@tongji.edu.cn
Yanghui Zhang*

Shanghai Key Laboratory of Chemical Assessment and Sustainability, Department of Chemical, and UNEP-Tongji Institute of Environment for Sustainable Development, Tongji University, 1239 Siping Road, Shanghai 200092, P. R. of China eMail: zhangyanghui@tongji.edu.cn
Changdong Shao

Shanghai Key Laboratory of Chemical Assessment and Sustainability, Department of Chemical, and UNEP-Tongji Institute of Environment for Sustainable Development, Tongji University, 1239 Siping Road, Shanghai 200092, P. R. of China eMail: zhangyanghui@tongji.edu.cn
Guangfa Shi

Shanghai Key Laboratory of Chemical Assessment and Sustainability, Department of Chemical, and UNEP-Tongji Institute of Environment for Sustainable Development, Tongji University, 1239 Siping Road, Shanghai 200092, P. R. of China eMail: zhangyanghui@tongji.edu.cn

Abstract

Alle Artikel dieser Rubrik

Abstract

While a great number of ortho C–H functionalization reactions have been developed and several breakthroughs have been achieved in meta C–H activation, para C–H functionalization is still in its infancy stage. In this article, a versatile strategy for the synthesis of para-substituted arenes has been developed via a tandem process consisting of palladium-catalyzed C–H functionalization and subsequent copper-catalyzed protodecarboxylation of benzoic acids. Both electron-withdrawing and electron-donating functionalities can be introduced into the para positions of arenes bearing a variety of substituents.

Key words

C–H activation - palladium - decarboxylation - arenes - regioselectivity

Volltext

Referenzen

References and Notes

Reviews on transition-metal-catalyzed C–H activation:

1a Kulkarni AA, Daugulis O. Synthesis 2009; 24: 4087
1b Chen X, Engle KM, Wang DH, Yu J.-Q. Angew. Chem. Int. Ed. 2009; 48: 5094 ; Angew. Chem. 2009, 121, 5196
1c C–H Activation . In Topics in Current Chemistry . Yu J.-Q, Shi Z. Springer; Heidelberg: 2010. Vol. 292
1d Mkhalid IA. I, Barnard JH, Marder TB, Murphy JM, Hartwig JF. Chem. Rev. 2010; 110: 890
1e Liu C, Zhang H, Shi W, Lei A. Chem. Rev. 2011; 111: 1780
1f Yeung CS, Dong VM. Chem. Rev. 2011; 111: 1215
1g Ackermann L. Chem. Rev. 2011; 111: 1315
1h Baudoin O. Chem. Soc. Rev. 2011; 40: 4902
1i Cho SH, Kim JY, Kwak J, Chang S. Chem. Soc. Rev. 2011; 40: 5068
1j Davies HM. L, Morton D. Chem. Soc. Rev. 2011; 40: 1857
1k McMurray L, O’Hara F, Gaunt MJ. Chem. Soc. Rev. 2011; 40: 1885
1l Boorman TC, Larrosa I. Chem. Soc. Rev. 2011; 40: 1910
1m Le Bras J, Muzart J. Chem. Rev. 2011; 111: 1170
1n Sun C.-L, Li B.-J, Shi Z.-J. Chem. Rev. 2011; 111: 1293
1o Yamaguchi J, Yamaguchi AD, Itami K. Angew. Chem. Int. Ed. 2012; 51: 8960 ; Angew. Chem. 2012, 124, 9092
1p Kuhl N, Hopkinson MN, Wencel-Delord J, Glorius F. Angew. Chem. Int. Ed. 2012; 51: 10236 ; Angew. Chem. 2012, 124, 10382
1q Neufeldt SR, Sanford MS. Acc. Chem. Res. 2012; 45: 936
1r Song G, Wang F, Li X. Chem. Soc. Rev. 2012; 41: 3651
1s Arockiam PB, Bruneau C, Dixneuf PH. Chem. Rev. 2012; 112: 5879

Reviews on directed C–H activation:

2a Lyons TW, Sanford MS. Chem. Rev. 2010; 110: 1147
2b Engle KM, Mei T.-S, Wasa M, Yu J.-Q. Acc. Chem. Res. 2012; 45: 788
2c Colby DA, Tsai AS, Bergman RG, Ellman JA. Acc. Chem. Res. 2012; 45: 814
2d Rouquet G, Chatani N. Angew. Chem. Int. Ed. 2013; 52: 11726 ; Angew. Chem. 2013, 125, 11942
2e Zhang F, Spring DR. Chem. Soc. Rev. 2014; 43: 6906

3a Yang J. Org. Biomol. Chem. 2015; 13: 1930
3b Yizhi Y, Song S, Ning J. Acta Chim. Sin. (Engl. Ed.) 2015; 73 in press; DOI: 10.6023/A15050319

4a Cho J.-Y, Tse MK, Holmes Maleczka Jr DR. E, Smith MR. III. Science 2002; 295: 305
4b Ishiyama T, Takagi J, Ishida K, Miyaura N, Anastasi NR, Hartwig JF. J. Am. Chem. Soc. 2002; 124: 390
4c Tzschucke CC, Murphy JM, Hartwig JF. Org. Lett. 2007; 9: 761
4d Hull KL, Sanford MS. J. Am. Chem. Soc. 2007; 129: 11904
4e Zhang Y.-H, Shi B.-F, Yu J.-Q. J. Am. Chem. Soc. 2009; 131: 5072
4f Hartwig JF. Acc. Chem. Res. 2012; 45: 864
4g Liu T, Shao X, Wu Y, Shen Q. Angew. Chem. Int. Ed. 2012; 51: 540 ; Angew. Chem. 2012, 124, 555
4h Robbins DW, Hartwig JF. Angew. Chem. Int. Ed. 2013; 52: 933 ; Angew. Chem. 2013, 125, 967

5a Phipps RJ, Gaunt MJ. Science 2009; 323: 1593
5b Duong HA, Gilligan RE, Cooke ML, Phipps RJ, Gaunt MJ. Angew. Chem. Int. Ed. 2011; 50: 463 ; Angew. Chem. 2011, 123, 483
5c Chen B, Hou XL, Li YX, Wu YD. J. Am. Chem. Soc. 2011; 133: 7668

6a Saidi O, Marafie J, Ledger AE, Liu PM, Mahon MF, Kociok-Kohn G, Whittlesey MK, Frost CG. J. Am. Chem. Soc. 2011; 133: 19298
6b Juliá-Hernández F, Simonetti M, Larrosa I. Angew. Chem. Int. Ed. 2013; 52: 114580 ; Angew. Chem. 2013, 125, 11670
6c Hofmann N, Ackermann L. J. Am. Chem. Soc. 2013; 135: 5877

7a Leow D, Li G, Mei T.-S, Yu J.-Q. Nature (London, U.K.) 2012; 486: 518
7b Lee S, Lee H, Tan KL. J. Am. Chem. Soc. 2013; 135: 18778
7c Dai H.-X, Li G, Zhang X.-G, Stepan AF, Yu J.-Q. J. Am. Chem. Soc. 2013; 135: 7567
7d Wan L, Dastbaravardeh N, Li G, Yu J.-Q. J. Am. Chem. Soc. 2013; 135: 18056
7e Bera M, Modak A, Patra T, Maji A, Maiti D. Org. Lett. 2014; 16: 5760
7f Tang R.-Y, Li G, Yu J.-Q. J. Am. Chem. Soc. 2014; 507: 215
7g Yang G, Lindovska P, Zhu D, Kim J, Wang P, Tang R.-Y, Movassaghi M, Yu J.-Q. J. Am. Chem. Soc. 2014; 136: 10807
7h Deng Y, Yu J.-Q. Angew. Chem. Int. Ed. 2015; 54: 888 ; Angew. Chem. 2015, 127, 902

8a Wang X.-C, Gong W, Fang L.-Z, Zhu R.-Y, Li S, Engle KM, Yu J.-Q. Nature (London, U.K.) 2015; 519: 334
8b Dong Z, Wang J, Dong G. J. Am. Chem. Soc. 2015; 137: 5887

9a Guo X, Li C.-J. Org. Lett. 2011; 13: 4977
9b Wang X, Leow D, Yu J.-Q. J. Am. Chem. Soc. 2011; 133: 13864
9c Ciana C.-L, Phipps RJ, Brandt JR, Meyer F.-M, Gaunt MJ. Angew. Chem. Int. Ed. 2011; 50: 458 ; Angew. Chem. 2011, 123, 478
9d Wu Z, Luo F, Chen S, Li Z, Xiang H, Zhou X. Chem. Commun. 2013; 49: 7653

10a Maehara A, Tsurugi H, Satoh T, Miura M. Org. Lett. 2008; 10: 1159
10b Mochida S, Hirano K, Satoh T, Miura M. Org. Lett. 2010; 12: 57769
10c Mochida S, Hirano K, Satoh T, Miura M. J. Org. Chem. 2011; 76: 3024
10d Cornella J, Righi M, Larrosa I. Angew. Chem. Int. Ed. 2011; 50: 9429 ; Angew. Chem. 2011, 123, 9601
10e Bhadra S, Dzik WI, Gooßen LJ. Angew. Chem. Int. Ed. 2013; 52: 2959 ; Angew. Chem. 2013, 125, 3031
10f Luo J, Preciado S, Larrosa I. J. Am. Chem. Soc. 2014; 136: 4109
10g Shi X.-Y, Liu K.-Y, Fan J, Dong X.-F, Wei J.-F, Li C.-J. Chem. Eur. J. 2015; 21: 1900
10h Lee D, Chang S. Chem. Eur. J. 2015; 21: 5364

11 Rodriguez N, Gooßen K, Gooßen LJ. Angew. Chem. Int. Ed. 2008; 47: 3100 ; Angew. Chem. 2008, 120, 3144

12a Rodríguez N, Gooßen LJ. Chem. Soc. Rev. 2011; 40: 5030
12b Dzik WI, Lange PP, Gooßen LJ. Chem. Sci. 2012; 3: 2671
12c Shang R, Liu L. Sci. China: Chem. 2011; 54: 1670

13 Shi G, Zhang Y. Adv. Synth. Catal. 2014; 356: 1419

14a Chiong HA, Pham Q.-N, Daugulis O. J. Am. Chem. Soc. 2007; 129: 9879
14b Arroniz C, Ironmonger A, Rassias G, Larrosa I. Org. Lett. 2013; 15: 910

15a Linder C, Rodríguez N, Lange PP, Fromm A, Gooßen LJ. Chem. Commun. 2009; 46: 7173
15b Lu P, Sanchez C, Cornella J, Larrosa I. Org. Lett. 2009; 11: 5710
15c Cornella J, Sanchez C, Banawa D, Larrosa I. Chem. Commun. 2009; 46: 7176
15d Seo S, Taylor JB, Greaney MF. Chem. Commun. 2012; 48: 8270

16 Thiel WR, Rodríguez N, Linder C, Melzer B, Gooßen LJ. Adv. Synth. Catal. 2007; 349: 2241

17a Miao J, Ge H. Org. Lett. 2013; 15: 2930
17b Mamone P, Danoun G, Gooßen LJ. Angew. Chem. Int. Ed. 2013; 52: 6704 ; Angew. Chem. 2013, 125, 6836

18 Zhang Y.-H, Yu J.-Q. J. Am. Chem. Soc. 2009; 131: 14654
19 Synthesis of para-Arylated Arenes A mixture of m-toluic acid (68.0 mg, 0.50 mmol), iodobenzene (167.2 μL, 1.50 mmol), Ag₂CO₃ (76.0 mg, 0.28 mmol), K₂CO₃ (35.0 mg, 0.25 mmol), and Pd(OAc)₂ (2.3 mg, 0.01 mmol) in AcOH (130.0 μL) was heated under an atmosphere of N₂ at 120 °C for 24 h. After cooling down to r.t., the reaction mixture was quenched by addition of 2.0 M aq HCl (10 mL), diluted with EtOAc (10 mL), and then filtered through a pad of Celite. The filtrate was washed with brine, dried over Na₂SO₄, and concentrated in vacuo, yielding crude 2-phenylbenzoic acid derivatives. A mixture of the crude product, Cu₂O (3.6 mg, 0.025 mmol), and 1,10-phenanthroline (9.0 mg, 0.050 mmol) in a solution of NMP (1.5 mL) and quinoline (0.5 mL) was heated under an atmosphere of N₂ at 170 °C for 24 h. The reaction mixture was quenched by addition of 0.2 M aq HCl (10 mL), diluted with EtOAc (10 mL), and then filtered through a pad of Celite. The filtrate was washed with brine (10 mL), dried over Na₂SO₄, and concentrated in vacuo. The residue was purified by silica gel preparative TLC to give 4-methylbiphenyl. ¹H NMR (400 MHz, CDCl₃): δ = 7.59–7.57 (m, 2 H), 7.51–7.49 (m, 2 H), 7.45–7.41 (m, 2 H), 7.34–7.31 (m, 1 H), 7.26–7.24 (m, 2 H), 2.40 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 141.14, 138.34, 136.99, 129.45, 128.68, 126.97, 126.95, 21.08. HRMS (ESI-TOF): m/z calcd for C₁₃H₁₃ ⁺: 169.1012 [M + H]⁺; found: 169.0938.
20 Synthesis of para-Benzoylated Arenes A mixture of m-toluic acid (27.2 mg, 0.20 mmol), benzoylformic acid (90.1 mg, 0.60 mmol), Pd(TFA)₂ (6.6 mg, 0.020 mmol), and Ag₂CO₃ (165.5 mg, 0.60 mmol) in DME (2 mL) was heated at 150–165 °C for 24–48 h. After cooling down to r.t., the reaction mixture was diluted by addition of EtOAc (10 mL) and then filtered through a pad of Celite. The filtrate was concentrated in vacuo to afford 2-benzoylbenzoic acid derivatives. A mixture of the crude product, Cu₂O (1.4 mg, 0.010 mmol), and 1,10-phenanthroline (3.6 mg, 0.020 mmol) in a solution of NMP (1.5 mL) and quinoline (0.5 mL) was heated under an atmosphere of N₂ at 170 °C for 24 h. The reaction mixture was quenched by addition of 0.2 M aq HCl (10 mL), diluted with EtOAc (10 mL), and then filtered through a pad of Celite. The filtrate was washed with brine (10 mL), dried over Na₂SO₄, and concentrated in vacuo. The residue was purified by silica gel preparative TLC to give phenyl(p-tolyl)methanone. ¹H NMR (400 MHz, CDCl₃): δ = 7.78 (d, J = 7.1 Hz, 2 H), 7.72 (d, J = 8.1 Hz, 2 H), 7.58 (t, J = 7.4 Hz, 1 H), 7.48 (t, J = 7.5 Hz, 2 H), 7.28 (d, J = 7.9 Hz, 2 H), 2.44 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 196.50, 143.22, 137.95, 134.87, 132.13, 130.29, 129.91, 128.95, 128.18, 21.64. HRMS (ESI-TOF): m/z calcd for C₁₄H₁₂NaO⁺: 219.0780 [M + Na]⁺; found: 219.0774.
21 Synthesis of para-Hydroxylated Arenes A 50 mL Schlenk-type tube (with a Teflon high-pressure valve and side arm) was charged with m-toluic acid (68.0 mg, 0.50 mmol), benzoquinone (54.0 mg, 0.50 mmol), KOAc (98.0 mg, 1.00 mmol), Pd(OAc)₂ (11.2 mg, 0.050 mmol), and N,N-dimethylacetamide (1.5 mL). The reaction tube was evacuated and back-filled with O₂ (3×, ballon). After the reaction mixture was stirred at 115 °C for 15 h, it was allowed to cool down to r.t. The reaction mixture was diluted with EtOAc (10 mL) and then filtered through a pad of Celite. The filtrate was concentrated in vacuo to yield crude 2-hydroxylbenzoic acid. A mixture of the crude product, Cu₂O (3.6 mg, 0.025 mmol), and 1,10-phenanthroline (9.0 mg, 0.050 mmol) in a solution of NMP (1.5 mL) and quinoline (0.5 mL) was heated under an atmosphere of N₂ at 220 °C for 12 h. The reaction mixture was quenched by addition of 0.2 M aq HCl (10 mL), diluted with EtOAc (10 mL), and then filtered through a pad of Celite. The filtrate was washed with brine (10 mL), dried over Na₂SO₄, and concentrated in vacuo. The residue was purified by silica gel preparative TLC to give p-cresol. ¹H NMR (400 MHz, CDCl₃): δ = 7.05 (d, J = 8.3 Hz, 2 H), 6.75 (d, J = 8.3 Hz, 2 H), 4.95 (br, 1 H), 2.29 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 153.18, 130.03, 129.92, 115.06, 20.43. HRMS (ESI-TOF): m/z calcd for C₇H₉O⁺: 109.0648 [M + H]⁺; found: 109.0657.

Zusatzmaterial

Supporting Information (PDF)