Synlett 2015; 26(20): 2843-2848
DOI: 10.1055/s-0035-1560637
letter
© Georg Thieme Verlag Stuttgart · New York

Palladium-Catalyzed Regioselective C–H Bond Acetoxylation–Alkoxylation of Azoxybenzenes

Meng Sun*
Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, Department of Chemistry & Materials Science, Northwest University, Xi’an 710127, P. R. of China   Email: sunmeng@nwu.edu.cn
,
Liang Zhang
Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, Department of Chemistry & Materials Science, Northwest University, Xi’an 710127, P. R. of China   Email: sunmeng@nwu.edu.cn
,
Cheng-Wen Hua
Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, Department of Chemistry & Materials Science, Northwest University, Xi’an 710127, P. R. of China   Email: sunmeng@nwu.edu.cn
,
Zhe Wang
Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, Department of Chemistry & Materials Science, Northwest University, Xi’an 710127, P. R. of China   Email: sunmeng@nwu.edu.cn
,
Le-Kai Hou
Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, Department of Chemistry & Materials Science, Northwest University, Xi’an 710127, P. R. of China   Email: sunmeng@nwu.edu.cn
,
Su-Xian Cai
Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, Department of Chemistry & Materials Science, Northwest University, Xi’an 710127, P. R. of China   Email: sunmeng@nwu.edu.cn
,
Shuang Li
Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, Department of Chemistry & Materials Science, Northwest University, Xi’an 710127, P. R. of China   Email: sunmeng@nwu.edu.cn
› Author Affiliations
Further Information

Publication History

Received: 04 July 2015

Accepted after revision: 31 August 2015

Publication Date:
21 October 2015 (online)


Abstract

Efficient strategies for the regioselective ortho acetoxylation/alkoxylation of C–H bond of azoxybenzenes in the presence of palladium catalysts were developed using PhI(OAc)2 as the teminal oxidant. Under the very similar conditions established, both reactions proceeded smoothly and were tolerated by a variety of functional groups.

Supporting Information

 
  • References


    • For selected reviews, see:
    • 1a Dyker G. Handbook of C-H Transformations: Applications in Organic Synthesis. Wiley-VCH; Weinheim: 2005
    • 1b Activation and Functionalization of C–H Bond, ACS Symposium Series 885. Goldberg KI, Goldman AS. American Chemical Society; Washington: 2004
    • 1c Giri R, Shi B.-F, Engle KM, Maugel N, Yu J.-Q. Chem. Soc. Rev. 2009; 38: 3242
    • 1d Yu J.-Q, Shi Z.-J. C–H Activation . Springer; Berlin: 2010
    • 1e Sarkar SD, Liu W.-P, Kozhushkov SI, Ackermann L. Adv. Synth. Catal. 2014; 356: 1461
    • 2a Murai S, Kakiuchi F, Sekine S, Tanaka Y, Kamatani A, Sonoda M, Chatani N. Nature (London, U.K.) 1993; 366: 529
    • 2b Colby DA, Bergman RG, Ellman JA. Chem. Rev. 2010; 110: 624
    • 2c Conejero S, Paneque M, Poveda ML, Santos LL, Carmona E. Acc. Chem. Res. 2010; 43: 572
    • 2d Daz-Requejo MM, Prez PJ. Chem. Rev. 2008; 108: 3379
    • 2e Herreras CI, Yao X, Li Z, Li C.-J. Chem. Rev. 2007; 107: 2546
    • 2f Sun C.-L, Li B.-J, Shi Z.-J. Chem. Rev. 2011; 111: 1293
    • 2g Yeung CS, Dong VM. Chem. Rev. 2011; 111: 1215
    • 2h Leow D, Li G, Mei T.-S, Yu J.-Q. Nature (London, U.K.) 2012; 486: 518
  • 3 Furuya T, Kamlet AS, Ritter T. Nature (London, U.K.) 2011; 473: 470
    • 4a Schlummer B, Scholz U. Adv. Synth. Catal. 2004; 346: 1599
    • 4b Roughley SD, Jordan AM. J. Med. Chem. 2011; 54: 3451

      Selected examples:
    • 5a Garcia-Rubia A, Fernandez-Ibanez MA, Arrayas RG, Carretero JC. Chem. Eur. J. 2011; 17: 3567
    • 5b Garcia-Rubia A, Urone B, Arrays RG, Carretero JC. Angew. Chem. Int. Ed. 2011; 50: 10927
    • 5c Kim J, Chang S. J. Am. Chem. Soc. 2010; 132: 10272
    • 5d Li Y, Li BJ, Wang WH, Huang WP, Zhang XS, Cheng K, Shi Z.-J. Angew. Chem. Int. Ed. 2011; 50: 2115
    • 5e Stowers KJ, Sanford MS. Org. Lett. 2009; 11: 4584
    • 5f Desai LV, Malik HA, Sanford MS. Org. Lett. 2006; 8: 1141
    • 5g Kalyani D, Sanford MS. Org. Lett. 2005; 7: 4149
    • 5h Wang W, Luo F, Zhang S, Cheng J. J. Org. Chem. 2010; 75: 2415
    • 5i Powers DC, Xiao DY, Geibel MA. L, Ritter T. J. Am. Chem. Soc. 2010; 132: 14530
    • 5j Powers DC, Geibel MA. L, Klein JE. M. N, Ritter T. J. Am. Chem. Soc. 2009; 131: 17050
    • 5k Dick AR, Hull KL, Sanford MS. J. Am. Chem. Soc. 2004; 126: 2300

    • For similar directing-group-assisted strategies, see:
    • 5l Shi W, Shi Z.-J. Chin. J. Chem. 2014; 32: 974
    • 5m Shi S, Kuang C. J. Org. Chem. 2014; 79: 6105

      Selected examples:
    • 6a Chan C.-W, Zhou Z, Chan AS. C, Yu W.-Y. Org. Lett. 2010; 12: 3926
    • 6b Han S, Sharma S, Park J, Kim M, Shin Y, Mishra NK, Bae JJ, Kwak JH, Jung YH, Kim IS. J. Org. Chem. 2014; 79: 275
    • 6c Kim M, Park J, Sharma S, Kim A, Park E, Kwak JH, Jung YH, Kim IS. Chem. Commun. 2013; 49: 925
    • 6d Thirunavukkarasu VS, Parthasarathy K, Cheng C.-H. Chem. Eur. J. 2010; 16: 1436
    • 6e Too PC, Wang Y.-F, Chiba S. Org. Lett. 2010; 12: 5688
    • 6f Guimond N, Gorelsky SI, Fagnou K. J. Am. Chem. Soc. 2011; 133: 6449
    • 6g Ng K.-H, Zhou Z, Yu W.-Y. Org. Lett. 2012; 14: 272
    • 6h Ng K.-H, Zhou Z, Yu W.-Y. Chem. Commun. 2013; 49: 7031
    • 6i Ryu J, Shin K, Park SH, Kim JY, Chang S. Angew. Chem. Int. Ed. 2012; 51: 9904
    • 6j Sun C.-L, Liu N, Li B.-J, Yu D.-G, Wang Y, Shi Z.-J. Org. Lett. 2010; 12: 184
    • 6k Gong T.-J, Xiao B, Cheng W.-M, Su W, Xu J, Liu Z.-J, Liu L, Fu Y. J. Am. Chem. Soc. 2013; 135: 10630
    • 6l Zhang W, Lou S, Liu Y, Xu Z. J. Org. Chem. 2013; 78: 5932
    • 6m Desai LV, Hull KL, Sanford MS. J. Am. Chem. Soc. 2004; 126: 9542

      Selected examples:
    • 7a Patureau FW, Glorius F. J. Am. Chem. Soc. 2010; 132: 9982
    • 7b Giri R, Lam JK, Yu J.-Q. J. Am. Chem. Soc. 2010; 132: 686
    • 7c Tobisu M, Ano Y, Chatani N. Org. Lett. 2009; 11: 3250
    • 7d Stuart DR, Megan B.-L, Burgess KM. N, Fagnou K. J. Am. Chem. Soc. 2008; 130: 16474
    • 7e Li B.-J, Tian S.-L, Fang Z, Shi Z.-J. Angew. Chem. Int. Ed. 2008; 47: 1115
    • 7f Yang SD, Li B.-J, Wan XB, Shi Z.-J. J. Am. Chem. Soc. 2007; 129: 6066
    • 7g Wang XB, Ma ZX, Li BJ, Zhang KY, Cao SK, Zhang SW, Shi Z.-J. J. Am. Chem. Soc. 2006; 128: 7416
    • 7h Daugulis O, Zaitsev VG. Angew. Chem. Int. Ed. 2005; 44: 4046
    • 7i Zaitsev VG, Daugulis O. J. Am. Chem. Soc. 2005; 127: 4156
    • 7j Wang G.-W, Yuan T.-T, Wu X.-L. J. Org. Chem. 2008; 73: 4717

      Selected examples:
    • 8a Wang H.-L, Hu R.-B, Zhang H, Zhou A.-X, Yang S.-D. Org. Lett. 2013; 15: 5302
    • 8b Zhang H.-Y, Yi H.-M, Wang G.-W, Yang B, Yang S.-D. Org. Lett. 2013; 15: 6186
    • 8c Ma Y.-N, Tian Q.-P, Zhang H.-Y, Zhou A.-X, Yang S.-D. Org. Chem. Front. 2014; 1: 284
    • 8d Zhang H, Hu R.-B, Zhang X.-Y, Li S.-X, Yang S.-D. Chem. Commun. 2014; 50: 4686
    • 8e Hu R.-B, Zhang H, Zhang X.-Y, Yang S.-D. Chem. Commun. 2014; 50: 2193
    • 8f Ma Y.-N, Zhang H.-Y, Yang S.-D. Org. Lett. 2015; 17: 2034

      Selected examples:
    • 9a Li W, Xu ZP, Sun PP, Jiang XQ, Fang M. Org. Lett. 2011; 13: 1286
    • 9b Du BN, Jiang XQ, Sun PP. J. Org. Chem. 2013; 78: 2786
    • 9c Li W, Sun PP. J. Org. Chem. 2012; 77: 8362

      Selected examples:
    • 10a Anand M, Sunoj RB. Org. Lett. 2011; 13: 4802
    • 10b Wang G.-W, Yuan T.-T. J. Org. Chem. 2010; 75: 476
    • 10c Yin Z, Jiang X, Sun P. J. Org. Chem. 2013; 78: 10002
    • 10d Jiang T.-S, Wang G.-W. J. Org. Chem. 2012; 77: 9504
    • 10e Zhang S.-Y, He G, Zhao Y, Wright K, Nack WA, Chen G. J. Am. Chem. Soc. 2012; 134: 7313

      Selected examples:
    • 11a Wu Y, Feng L.-J, Lu X, Kwong FY, Luo H.-B. Chem. Commun. 2014; 50: 15352
    • 11b Liu B, Song C, Sun C, Zhou S, Zhu J. J. Am. Chem. Soc. 2013; 135: 16625
    • 11c Liu B, Fan Y, Gao Y, Sun C, Xu C, Zhu J. J. Am. Chem. Soc. 2013; 135: 468
    • 11d Gao T, Sun P. J. Org. Chem. 2014; 79: 9888
    • 11e Wang C, Huang Y. Org. Lett. 2013; 15: 5294

      For recent selected reviews, see:
    • 12a Krylov LB, Vil’ VA, Terent’ev AO. Beilstein J. Org. Chem. 2015; 11: 92
    • 12b Neufeldt SR, Sanford MS. Acc. Chem. Res. 2012; 45: 936
    • 12c Bras JL, Muzart J. Chem. Soc. Rev. 2014; 43: 3003
    • 12d Enthaler S, Company A. Chem. Soc. Rev. 2011; 40: 4912
    • 12e Liu B, Shi B.-F. Tetrahedron Lett. 2015; 56: 15
    • 13a Sun M, Hou L.-K, Chen X.-X, Yang X.-J, Sun W, Zang Y.-S. Adv. Synth. Catal. 2014; 356: 3789
    • 13b Hou L, Chen X, Li S, Cai S, Zhao Y, Sun M, Yang X.-J. Org. Biomol. Chem. 2015; 13: 4160
    • 14a Huang JM, Kuo JF, Chen CY. J. Appl. Polym. Sci. 1995; 55: 1217
    • 14b Campbell D, Dix LR, Rostron P. Dyes Pigm. 1995; 29: 77
  • 15 Ikeda T, Tsu O. Science 1995; 268: 1873

    • Selected examples, see:
    • 16a Hou Z, Fujiware Y, Taniguchi H. J. Org. Chem. 1988; 53: 3118
    • 16b Sakai N, Fuji K, Nabeshima S, Ikeda R, Konakahara T. Chem. Commun. 2010; 46: 3173
    • 17a Li HJ, Li PH, Zhao Q, Wang L. Chem. Commun. 2013; 49: 9170
    • 17b Li HJ, Xie XY, Wang L. Chem. Commun. 2014; 50: 4218
    • 17c Yi M, Cui X, Zhu C, Pi C, Zhu W, Wu Y. Asian J. Org. Chem. 2015; 4: 38
  • 18 During the preparation of this manuscript, a similar ortho acetoxylation or alkoxylation of azoxy compounds has been reported. See: Zhang D, Cui X, Yang F, Zhang Q, Zhu Y, Wu Y. Org. Chem. Front. 2015; 2: 951
  • 19 General Catalytic Procedure for ortho Acetoxylation of Azoxybenzenes Pd(OAc)2 (2.2 mg, 0.01 mmol, 5 mol%), azoxybenzene (39.6 mg, 0.2 mmol, 1.0 equiv), PhI(OAc)2 (193.2 mg, 0.6 mmol, 3.0 equiv), and AcOH (1.0 mL) were added in a 10 mL sealed tube with a Teflon-lined cap. The vessel was heated in an oil bath at 60 °C for 20 h followed by cooling. The contents were subjected to flash chromatography to give the corresponding product (88%) as a pale yellow oil. The purified material was dried under an oil-pump vacuum. 2-(2-Acetoxyphenyl)-2-oxo-1-phenylhydrazin-2-ium-1-ide (2aa) Pale yellow oil. 1H NMR (400 MHz, CDCl3): δ = 8.11–8.09 (d, J = 8.0 Hz, 2 H), 7.95–7.93 (d, J = 8.0 Hz, 1 H), 7.54–7.46 (m, 3 H), 7.42–7.36 (m, 2 H), 7.24–7.22 (d, J = 8.0 Hz, 1 H), 2.27 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 168.66, 143.86, 142.95, 141.79, 131.44, 130.00, 128.74, 126.43, 125.24, 125.07, 124.53, 20.81. ESI-HRMS: m/z [M + Na]+ calcd for C14H12N2O3Na+: 279.0746; found: 279.0746.
  • 20 Under these conditions, no to a trace amount of ortho-acetoxylated product was observed by GC–MS.
  • 21 General Catalytic Procedure for ortho Alkoxylation of Azoxybenzenes Pd(OAc)2 (2.2 mg, 0.01 mmol, 5 mol%), azoxybenzene (39.6 mg, 0.2 mmol, 1.0 equiv), alcohol (50.0 equiv), PhI(OAc)2 (128.8 mg, 0.4 mmol, 2.0 equiv), and AcOH (1.0 mL) were added in a 10 mL sealed tube with a Teflon-lined cap. The vessel was heated in an oil bath at 60 °C for 20 h followed by cooling. The contents were subjected to flash chromatography to give the corresponding product (75%) as a pale yellow oil. The purified material was dried under an oil-pump vacuum. 2-(2-Methoxyphenyl)-2-oxo-1-phenylhydrazin-2-ium-1-ide (3aa) Pale yellow oil. 1H NMR (400 MHz, CDCl3): δ = 8.16–8.14 (m, 2 H), 7.57–7.55 (m, 1 H), 7.48–7.44 (m, 2 H), 7.42–7.36 (m, 2 H), 7.04–7.00 (m, 2 H), 3.87 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 151.52, 143.97, 139.67, 130.95, 129.68, 128.55, 125.21, 124.24, 120.34, 112.79, 56.10. ESI-HRMS: m/z [M + Na]+ calcd for C13H12N2O2Na+: 251.0796; found: 251.0787.
  • 22 Balch AL, Petridis D. Inorg. Chem. 1969; 8: 2247
  • 23 Yoneyama T, Crabtree RH. J. Mol. Catal. A: Chem. 1996; 108: 35
    • 24a Powers DC, Ritter T. Nat. Chem. 2009; 1: 302
    • 24b Powers DC, Geibel MA. L, Klein JE. M. N, Ritter T. J. Am. Chem. Soc. 2009; 131: 17050