Synlett 2020; 31(03): 272-274
DOI: 10.1055/s-0039-1691534
letter
© Georg Thieme Verlag Stuttgart · New York

Photoinduced Carbon Tetrabromide Initiated Aerobic Oxidation of Substituted Toluenes to Carboxylic Acids

*
Kun Zheng
,
Xiaoyu Yan
,
Guofu Zhang
,
Xinhuan Yan
,
Xiaoqing Li
,
Xiangsheng Xu
This work was supported by the National Key Research and Development Program of China (2017YFC0210900).
Further Information

Publication History

Received: 17 October 2019

Accepted after revision: 28 November 2019

Publication Date:
13 December 2019 (online)


Abstract

A mild and metal-free procedure is reported for the aerobic oxidation of substituted toluenes to carboxylic acids by using CBr4 as initiator under irradiation from a 400 nm blue light-emitting diode.

Supporting Information

 
  • References and Notes

    • 1a Sheldon RA, Kochi JK. Metal-Catalyzed Oxidations of Organic Compounds: Mechanistic Principles and Synthetic Methodology Including Biochemical Processes. Academic Press; New York: 1981
    • 1b Simandi L. Catalytic Activation of Dioxygen by Metal Complexes. Kluwer Academic; Boston: 1992
    • 1c Henry PM. Palladium Catalyzed Oxidation of Hydrocarbons. Reidel; Dordrecht: 1980
    • 2a Nguyen TT, Grigorjeva L, Daugulis O. Angew. Chem. Int. Ed. 2018; 57: 1688
    • 2b Li Q, Meng L, Zhou S, Deng X, Wang N, Ji Y, Peng Y, Xing J, Yao G. Eur. J. Med. Chem. 2019; 180: 509
    • 2c Oliveira C, Bagetta D, Cagide F, Teixeira J, Amorim R, Silva T, Garrido J, Remiao F, Uriarte E, Oliveira PJ, Alcaro S, Ortuso F, Borges F. Eur. J. Med. Chem. 2019; 174: 116
    • 2d Zhang Z, Hao K, Li H, Lu R, Liu C, Zhou M, Li B, Meng Z, Hu Q, Jiang C. Eur. J. Med. Chem. 2019; 181: 111564
    • 3a Miki J, Osada Y, Tachibana Y, Shikada T. Catal. Lett. 1995; 30: 263
    • 3b Yoshino Y, Hayashi Y, Iwahama T, Sakaguchi S, Ishii Y. J. Org. Chem. 1997; 62: 6810
    • 3c Yamazaki S. Org. Lett. 1999; 1: 2129
    • 3d Rogovin M, Neumann R. J. Mol. Catal. A: Chem. 1999; 138: 315
    • 3e Bandyopadhyay R, Biswas S, Bhattacharyya R, Guha S, Mukherjee AK. Chem. Commun. 1999; 1627
    • 3f Das BK, Clark JH. Chem. Commun. 2000; 605
    • 3g Fraga-Dubreuil J, Garcia-Verdugo E, Hamley PA, Vaquero EM, Dudd LM, Pearson I, Housley D, Partenheimer W, Thomas WB, Whiston K, Poliakoff M. Green Chem. 2007; 9: 1238
    • 3h Wang J.-Q, He L.-N. New J. Chem. 2009; 33: 1637
    • 3i Nakamura R, Obora Y, Ishii Y. Adv. Synth. Catal. 2009; 351: 1677
    • 3j Cui L.-Q, Liu K, Zhang C. Org. Biomol. Chem. 2011; 9: 2258
    • 3k Hu Y, Zhou L, Lu W. Synthesis 2017; 49: 4007
    • 4a Ishii Y, Nakayama K, Takeno M, Sakaguchi S, Iwahama T, Nishiyama Y. J. Org. Chem. 1995; 60: 3934
    • 4b Paul S, Nanda P, Gupta R. Synlett 2004; 531
    • 4c Lu T, Mao Y, Yao K, Xu J, Lu M. Catal. Commun. 2012; 27: 124
    • 4d Liu G, Tang R, Wang Z. Catal. Lett. 2014; 144: 717
    • 4e Ozen R. Asian J. Chem. 2014; 26: 941
    • 4f Heidari M, Sedrpoushan A, Mohannazadeh F. Org. Process Res. Dev. 2017; 21: 641
  • 6 Sugai T, Itoh A. Tetrahedron Lett. 2007; 48: 9096
  • 7 Arylcarboxylic Acids 1a–v; General Procedure CAUTION: The reaction is inherently explosive in nature because significant concentrations of peroxide and hydroperoxide intermediates are generated. Appropriate precautions should be adopted. The reaction should not be scaled up. A solution of the appropriate substrate 1 (0.5 mmol) and CBr4 (0.05 mol) in anhyd MeCN (10 mL) was stirred in a round-bottom flask fitted with an O2 balloon, and irradiated externally with a 60 W 400 nm LED at rt. When the reaction was complete (TLC), the solvent was evaporated under reduced pressure. The residue was purified by column chromatography (silica gel). Benzoic Acid (2a) White solid; yield: 58.6 mg (96%); mp: 120–121 °C; Rf = 0.73 (50% EtOAc–PE). 1H NMR (500 MHz, CDCl3): δ = 8.34–8.02 (m, 2 H), 7.71–7.54 (m, 1 H), 7.48 (t, J = 7.9 Hz, 2 H).
  • 8 King JW, Quinney PR. J. Chromatogr. 1970; 49: 161
    • 9a Tripathi S, Singh SN, Yadav LD. S. RSC Adv. 2016; 6: 14547
    • 9b Sandhiya L, Zipse H. Chem. Eur. J. 2015; 21: 14060
  • 10 Sankar M, Nowicka E, Carter E, Murphy DM, Knight DW. Bethell D, Hutchings GJ. Nat. Commun. 2014; 5: doi: 10.1038/ncomms 4332