Bare Magnetite-Promoted Oxidative Hydroxylation of Arylboronic Acids and Subsequent Conversion into Phenolic Compounds

Abstract

The simple combination of readily available, recoverable, and recyclable magnetite (Fe₃O₄) nanoparticles and an environmentally friendly oxidant (H₂O₂) induced the effective functional group transformation of arylboronic acids into their corresponding phenols under mild conditions. Moreover, subsequent treatment of the reaction intermediate with appropriate electrophiles was accomplished in a one-pot system, leading to the formation of halophenols and phenolic derivatives.

Key words

magnetite - H₂O₂ - ipso-hydroxylation - arylboronic acids - phenols

Publication History

Received: 29 March 2022

Accepted after revision: 06 May 2022

Article published online:
03 June 2022

• References and Notes

• 1a Tyman JH. P. Synthetic and Natural Phenols . Elsevier; New York: 1996
• 1b Rappoport Z. The Chemistry of Phenols . Wiley-VCH; Weinheim: 2003
• 2 Zhu C, Wang R, Falck JR. Org. Lett. 2012; 14: 3494
• 3a Molander GA, Cavalcanti LN. J. Org. Chem. 2011; 76: 623
• 3b Maleczka RE. Jr, Shi F, Holmes D, Smith MR. III. J. Am. Chem. Soc. 2003; 125: 7792
• 3c Travis BR, Ciaramitaro BP, Borhan B. Eur. J. Org. Chem. 2002; 3429
• 3d Webb KS, Levy D. Tetrahedron Lett. 1995; 36: 5117
• 3e Badart MP, Hawkins BC. Synthesis 2021; 53: 1683
• 4a Chatterjee N, Goswami A. Tetrahedron Lett. 2015; 56: 1524
• 4b Pazenok S, Leroux FR. In Frontiers of Organofluorine Chemistry . Ojima I. World Scientific; London: 2020: 695
• 5 Kianmehr E, Yahyaee M, Tabatabai K. Tetrahedron Lett. 2007; 48: 2713
• 6a Guo S, Lu L, Cai H. Synlett 2014; 24: 1712
• 6b Chen DS, Huang JM. Synlett 2013; 24: 499
• 7a Dar BA, Bhatti P, Singh AP, Lazar A, Sharma PR, Sharma M, Singh B. Appl. Catal., A 2013; 466: 60
• 7b Yang D, An B, Wei W, Jiang M, You J, Wang H. Tetrahedron 2014; 70: 3630
• 7c Yang H, Li Y, Jiang M, Wang J, Fu H. Chem. Eur. J. 2011; 17: 5652
• 7d Affrose A, Azath IA, Dhakshinamoorthy A, Pitchumani K. J. Mol. Catal. A: Chem. 2014; 395: 500
• 7e Xu J, Wang X, Shao C, Su D, Cheng G, Hu Y. Org. Lett. 2010; 12: 1964
• 7f Inamoto K, Nozawa K, Yonemoto M, Kondo Y. Chem. Commun. 2011; 47: 11775
• 7g Zheng J, Lin S, Zhu X, Jiang B, Yang Z, Pan Z. Chem. Commun. 2012; 48: 6235
• 7h Gogoi N, Gogoi PK, Borah G, Bora U. Tetrahedron Lett. 2016; 57: 4050
• 7i Silveria DG, Monzon DM, Crisostomo FP, Martin T, Martin VS, Carrillo R. Chem. Commun. 2015; 51: 7027
• 8 Wang ZJ, Li R, Landfester K, Zhang KA. I. Polymer 2017; 126: 291
• 9a Zhong Y, Yuan L, Huang Z, Gu W, Shao Y, Han W. RSC Adv. 2014; 4: 33164
• 9b Kotoučová H, Strnadová I, Kovandová M, Chudoba J, Dvořákovác H, Cibulka R. Org. Biomol. Chem. 2014; 12: 2137
• 10a Laskar K, Paul S, Bora U. Tetrahedron Lett. 2019; 60: 151044
• 10b Gualandi A, Savoini A, Saporetti R, Franchi P, Lucarini M, Cozzi PG. Org. Chem. Front. 2018; 5: 1573
• 10c Silveira-Dorta G, Monzón DM, Crisóstomo FP, Martín T, Martín VS, Carrillo R. Chem. Commun. 2015; 51: 7027
• 10d Matsui K, Ishigami T, Yamaguchi T, Yamaguchi E, Tada N, Miura T, Itoh A. Synlett 2014; 25: 2613

Promoters used with oxidant H₂O₂, see:
• 11a Urea: Gupta S, Chaudhary P, Srivastava V, Kandasamy J. Tetrahedron Lett. 2016; 57: 2506
• 11b Biosilica: Mahanta A, Adhikari P, Bora U, Thakur AJ. Tetrahedron Lett. 2015; 56: 1780
• 11c H₃BO₃: Gogoi K, Dewan A, Gogoi A, Borah G, Bora U. Heteroat. Chem. 2014; 25: 127
• 11d Al₂O₃: Gogoi A, Bora U. Tetrahedron Lett. 2013; 54: 1821
• 11e Water extract of rice straw ash: Saikia E, Bora SJ, Chetia B. RSC Adv. 2015; 5: 102723
• 11f Poly(N-vinylpyrrolidone) (PVD)/poly(4-vinylpyridine) (PVP): Prakash GK. S, Chacko S, Panja C, Thomas TE, Gurung L, Rasul G, Mathew T, Olah GA. Adv. Synth. Catal. 2009; 351: 1567
• 11g Iodine: Gogoi A, Bora U. Synlett 2012; 23: 1079
• 11h Amberlite IR-120: Mulakayala N, Ismail Ismail, Kumar KM, Rapolu RK, Kandagatla B, Rao P, Oruganti S, Pal M. Tetrahedron Lett. 2012; 53: 6004
• 11i Mont K-10@AgNPs: Begum T, Gogoi A, Gogoi PK, Bora U. Tetrahedron Lett. 2015; 56: 95
• 11j Silica chloride: Wagh RB, Nagarkar JN. Tetrahedron Lett. 2017; 58: 3323
• 12 Sawant SD, Hudwekar AD, Kumar KA. A, Venkateswarlu V, Singh PP, Vishwakarma RA. Tetrahedron Lett. 2014; 55: 811
• 13 Saikia I, Hazarika M, Hussian N, Das MR, Tamuly C. Tetrahedron Lett. 2017; 58: 4255
• 14a Chutia R, Chetia B. J. Chem. Sci. 2019; 131: 48
• 14b Chutia R, Chetia B. J. Coord. Chem. 2020; 73: 1925
• 15 Saha A, Payra S, Dutta D, Banerjee S. ChemPlusChem 2017; 82: 1129
• 16 For a recent review, see: Ke Y, Wang S, Liu G, Li M, White TJ, Long Y. Small 2018; 1802025
• 17a Luo G, Lv X, Wang X, Yan S, Gao X, Xu J, Ma H, Jiao Y, Li F, Chen J. RSC Adv. 2015; 5: 94164
• 17b Wanna WH, Janmanchi D, Thiyagarajan N, Ramu R, Tsai Y.-F, Pao C.-W, Yua S.-F. New J. Chem. 2019; 43: 17819
• 17c Gopinath R, Patel BK. Org. Lett. 2000; 2: 577
• 18 Phukan S, Mahanta A, Rashid MH. Appl. Catal., A 2018; 562: 58
• 19 Karthik M, Suresh P. ACS Sustainable Chem. Eng. 2019; 7: 9028
• 20 Elumalai V, Hansen JH. RSC Adv. 2020; 10: 40582
• 21 Gawande MB, Branco PS, Varma RS. Chem. Soc. Rev. 2013; 42: 3371
• 22 Zarnegar Z, Safari J. Green Chem. Lett. Rev. 2017; 10: 235 ; and references cited therein
• 23a Zhu Y, Wu Q. J. Nanopart. Res. 1999; 1: 393
• 23b Park J, Lee D, Hwang N.-M, Kang M, Kim SC, Hwang Y, Park J.-G, Noh H.-J, Kim J.-Y, Park J.-H, Hyeon T. Angew. Chem. Int. Ed. 2005; 44: 2872
• 23c Thapa D, Palkar VR, Kurup MB, Malik SK. Mater. Lett. 2004; 58: 2692
• 23d Zhuo ZH, Wang J, Liu X, Chan HS. O. J. Mater. Chem. 2001; 11: 1704
• 23e Vollath D, Szabó DV, Tyalor RD, Willis JO. J. Mater. Res. 1997; 12: 2175
• 24a Baharin SN. A, Sarih NM, Mohamad S. Polymers 2016; 8: 117
• 24b Majeed MI, Guo J, Yan W, Tan B. Polymers 2016; 8: 392
• 25 Danqing L, Ming J, Li L, Mohammadnia M. Appl. Organomet. Chem. 2020; 34: e5820
• 26 Roth H.-C, Schwaminger SP, Schindler M, Wagner FE, Berensmeier S. J. Magn. Magn. Mater. 2015; 377: 81
• 27a Whitefield FB, Hill JL, Shaw KJ. J. Agric. Food Chem. 1997; 45: 889
• 27b Wuilloud RG, Selar N, Kannamkumarath SS, Caruso JA. J. Anal. At. Spectrom. 2004; 19: 1442
• 27c Garcia-Capdevila L, Lopez-Calull C, Pompermayer S, Arroyo C, Molins-Pujol AM, Bonal J. J. Chromatogr. B: Anal. Technol. Biomed. Life Sci. 1998; 708: 169
• 28a Greene TW, Wuts PG. M. Protective Groups in Organic Synthesis, 3rd ed. Wiley & Sons; New York: 1999
• 28b Kocienski PJ. Protecting Groups . Georg Thieme; Stuttgart: 2004

Selected examples, see:
• 29a Lourenco NM. T, Afonso CA. M. Tetrahedron 2003; 59: 789
• 29b Godfrey JD, Mueller RH, Sedergran TC, Soundararajan N, Colandrea VJ. Tetrahedron Lett. 1994; 35: 6405
• 29c Zhang M, Flynn DL, Hanson PR. J. Org. Chem. 2007; 72: 3194
• 29d Shah ST. A, Khan KM, Hussain H, Anwar MU, Fecker M, Voelter W. Tetrahedron 2005; 61: 6652
• 29e Shah ST. A, Khan KM, Heinrich AM, Choudhary MI, Voelter W. Tetrahedron Lett. 2002; 43: 8603
• 29f Brown Ripin DH, Vetelino M. Synlett 2003; 2353
• 29g Bu XL, Jing HW, Wang L, Chang T, Jin LL, Liang YM. J. Mol. Catal. A: Chem. 2006; 259: 121
• 29h Gathirwa JW, Maki T. Tetrahedron 2012; 68: 370
• 30 Brittain WD. G, Cobb SL. Org. Biomol. Chem. 2019; 17: 2110
• 31 Hao C, Shen Y, Wang Z, Wang X, Feng F, Ge C, Zhao Y, Wang K. ACS Sustainable Chem. Eng. 2016; 4: 1069
• 32 A representative procedure for the ipso-hydroxylation: A flask containing a Fe₃O₄@magnetic bar was charged with phenylboronic acid (3.0 mmol), and H₂O₂ (aq. 30 wt%, 0.3 mL). Then, the mixture was stirred at room temperature in open air for 5 min. The resulting mixture was then extracted with ethyl acetate (3 × 10 mL). The combined organic layers were washed with water, then dried with anhydrous Na₂SO₄, and evaporated under reduced pressure. The crude mixture was purified by column chromatography on silica gel (hexanes/ethyl acetate) to give phenol (2a) in 99% isolate yield as a colorless oily liquid. ¹H NMR (400 MHz, CDCl₃): δ = 7.28 (t, J = 8.4 Hz, 2 H), 6.99–6.95 (m, 1 H), 6.89–6.85 (m, 2 H), 4.80 (br s, 1 H) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 155.4, 129.7, 120.9, 115.3 ppm.