5 Electrosynthesis in Continuous Flow

A. A. Folgueiras-Amador; T. Wirth

Abstract

Organic electrosynthesis is recognized as a green enabling methodology to perform reactions in an efficient and straightforward way. Electrons are used as the reagent to form anionic and cationic radical species from neutral organic molecules, achieving oxidations and reductions and replacing toxic and dangerous reagents. Within this field, the use of microreactors in continuous flow is particularly compatible with electrochemistry because of the convenient advantages of flow over batch, including: (i) low loading or no supporting electrolyte at all, due to the small distance between electrodes, providing significant advantages in downstream processing; (ii) high electrode surface-to-reactor volume ratio; (iii) short residence time; and (iv) improved mixing effects. In this chapter, the most relevant electrochemical flow reactors and electrochemical transformations performed in continuous flow are presented and discussed.

Schlüsselwörter

flow electrosynthesis - electrochemical microreactors - flow chemistry - electrochemistry - anodic oxidations - cathodic reductions - divided cells - undivided cells

• 1 Frontana-Uribe BA, Little RD, Ibanez JG, Palma A, Vasquez-Medrano R. Green Chem. 2010; 12: 2099

• 2 Schäfer HJ, Harenbrock M, Klocke E, Plate M, Weiper-Idelmann A. Pure Appl. Chem. 2007; 79: 2047

• 3 Steckhan E, Arns T, Heineman WR, Hilt G, Hoormann D, Jörissen J, Kröner L, Lewall B, Pütter H. Chemosphere 2001; 43: 63

• 4 Simonet J, Pilard J.-F, In: Organic Electrochemistry Lund H, Hammerich O. Marcel Dekker New York 2001; 1163

• 5 Utley JHP, Nielsen MF, Wyatt PB, In: Organic Electrochemistry Hammerich O, Speiser B. CRC Press Boca Raton, FL 2016; 1625

• 6 Yoshida J, Kataoka K, Horcajada R, Nagaki A. Chem. Rev. 2008; 108: 2265

• 7 Sperry JB, Wright DL. Chem. Soc. Rev. 2006; 35: 605

• 8 Moeller KD. Tetrahedron 2000; 56: 9527

• 9 Organic Electrochemistry. Hammerich O, Speiser B. CRC Press; Boca Raton, FL 2016

• 10 Fry AJ. Synthetic Organic Electrochemistry. Wiley; New York 1989

• 11 Lund H. J. Electrochem. Soc. 2002; 149: S21

• 12 Utley J. Chem. Soc. Rev. 1997; 26: 157

• 13 Pütter H, In: Organic Electrochemistry Lund H, Hammerich O. Marcel Dekker New York 2001; 1259

• 14 Steckhan E In: Ullmannʼs Encyclopedia of Industrial Chemistry Wiley-VCH Weinheim, Germany 2011; 12. 315-349

• 15 Yoshida J. Electrochem. Soc. Interface 2009; 18: 40

• 16 Ziogas A, Kolb G, OʼConnell M, Attour A, Lapicque F, Matlosz M, Rode S. J. Appl. Electrochem. 2009; 39: 2297

• 17 Horii D, Atobe M, Fuchigami T, Marken F. Electrochem. Commun. 2005; 7: 35

• 18 Attour A, Dirrenberger P, Rode S, Ziogas A, Matlosz M, Lapicque F. Chem. Eng. Sci. 2011; 66: 480

• 19 Watts K, Baker A, Wirth T. J. Flow Chem. 2014; 4: 2

• 20 Folgueiras-Amador AA, Wirth T. J. Flow Chem. 2017; 7: 94 material modified from original article published by Akadémiai Kiadó creativecommons.org/licenses/by-nc/4.0/

• 21 Microreactors in Organic Synthesis and Catalysis. Wirth T. Wiley-VCH; Weinheim, Germany 2008

• 22 Yoshida J. Flash Chemistry: Fast Organic Synthesis in Microsystems. Wiley-VCH; Weinheim, Germany 2008

• 23 Paddon CA, Atobe M, Fuchigami T, He P, Watts P, Haswell SJ, Pritchard GJ, Bull SD, Marken F. J. Appl. Electrochem. 2006; 36: 617

• 24 Küpper M, Hessel V, Löwe H, Stark W, Kinkel J, Michel M, Schmidt-Traub H. Electrochim. Acta 2003; 48: 2889

• 25 Jörissen J, Speiser B, In: Organic Electrochemistry Hammerich O, Speiser B. CRC Press Boca Raton, FL 2016; 263

• 26 Green RA, Brown RCD, Pletcher D. J. Flow Chem. 2015; 5: 31

• 27 Lund H, In: Organic Electrochemistry Lund H, Hammerich O. Marcel Dekker New York 2001; 223

• 28 Suga S, Suzuki S, Yamamoto A, Yoshida J. J. Am. Chem. Soc. 2000; 122: 10244

• 29 Yoshida J, Suga S, Suzuki S, Kinomura N, Yamamoto A, Fujiwara K. J. Am. Chem. Soc. 1999; 121: 9546

• 30 Suga S, Okajima M, Fujiwara K, Yoshida J. QSAR Comb. Sci. 2005; 24: 728

• 31 Suga S, Okajima M, Fujiwara K, Yoshida J. J. Am. Chem. Soc. 2001; 123: 7941

• 32 Gütz C, Bänziger M, Bucher C, Galvão TR, Waldvogel SR. Org. Process Res. Dev. 2015; 19: 1428

• 33 Gütz C, Selt M, Bänziger M, Bucher C, Römelt C, Hecken N, Gallou F, Galvão TR, Waldvogel SR. Chem.–Eur. J. 2015; 21: 13878

• 34 Wirth T. Angew. Chem. Int. Ed. 2005; 44: 3656

• 35 Hypervalent Iodine Chemistry. Wirth T. 373. Springer; Heidelberg, Germany 2016

• 36 Singh FV, Wirth T, In: Science of Synthesis: Catalytic Oxidation in Organic Synthesis Muñiz K. Thieme Stuttgart 2017; 1. Section 2.2, 29

• 37 Watts K, Gattrell W, Wirth T. Beilstein J. Org. Chem. 2011; 7: 1108

• 38 Hoffelner H, Lorch HW, Wendt H. J. Electroanal. Chem. 1975; 66: 183

• 39 Horcajada R, Okajima M, Suga S, Yoshida J. Chem. Commun. (Cambridge) 2005; 1303

• 40 Moeller KD. Top. Curr. Chem. 1997; 185: 50

• 41 Schäfer HJ, In: Organic Electrochemistry Lund H, Hammerich O. Marcel Dekker New York 2001; 883

• 42 Torii S, Tanaka H, In: Organic Electrochemistry Lund H, Hammerich O. Marcel Dekker New York 2001; 499

• 43 Uneyama K. Tetrahedron 1991; 47: 555

• 44 Arai K, Watts K, Wirth T. ChemistryOpen 2014; 3: 23

• 45 Chen Y, Yekta S, Yudin AK. Chem. Rev. 2003; 103: 3155

• 46 Kozlowski MC, Morgan BJ, Linton EC. Chem. Soc. Rev. 2009; 38: 3193

• 47 Mohler ML, Kang GS, Hong SS, Patil R, Kirichenko OV, Li W, Rakov IM, Geisert EE, Miller DD. J. Med. Chem. 2006; 49: 5845

• 48 Xie J, Pierce JG, James RC, Okano A, Boger DL. J. Am. Chem. Soc. 2011; 133: 13946

• 49 Inagi S, Hayashi S, Hosaka K, Fuchigami T. Macromolecules 2009; 42: 3881

• 50 Tange M, Okazaki T, Iijima S. ACS Appl. Mater. Interfaces 2012; 4: 6458

• 51 Eberson L, Hartshorn MP, Persson O. J. Chem. Soc., Perkin Trans. 2 1995; 1735

• 52 Eberson L, Hartshorn MP, Persson O. Angew. Chem. Int. Ed. 1995; 34: 2268

• 53 Shuklov IA, Dubrovina NV, Börner A. Synthesis 2007; 2925

• 54 Kirste A, Elsler B, Schnakenburg G, Waldvogel SR. J. Am. Chem. Soc. 2012; 134: 3571

• 55 Kirste A, Schnakenburg G, Stecker F, Fischer A, Waldvogel SR. Angew. Chem. Int. Ed. 2010; 49: 971

• 56 Kirste A, Schnakenburg G, Waldvogel SR. Org. Lett. 2011; 13: 3126

• 57 Kirste A, Hayashi S, Schnakenburg G, Malkowsky IM, Stecker F, Fischer A, Fuchigami T, Waldvogel SR. Chem.–Eur. J. 2011; 17: 14164

• 58 Riehl B, Dyballa KM, Franke R, Waldvogel SR. Synthesis 2017; 49: 252

• 59 Schulz L, Enders M, Elsler B, Schollmeyer D, Dyballa KM, Franke R, Waldvogel SR. Angew. Chem. Int. Ed. 2017; 56: 4877

• 60 Lips S, Wiebe A, Elsler B, Schollmeyer D, Dyballa KM, Franke R, Waldvogel SR. Angew. Chem. Int. Ed. 2016; 55: 10872

• 61 Wiebe A, Schollmeyer D, Dyballa KM, Franke R, Waldvogel SR. Angew. Chem. Int. Ed. 2016; 55: 11801

• 62 Elsler B, Wiebe A, Schollmeyer D, Dyballa KM, Franke R, Waldvogel SR. Chem.–Eur. J. 2015; 21: 12321

• 63 Kashiwagi T, Elsler B, Waldvogel SR, Fuchigami T, Atobe M. J. Electrochem. Soc. 2013; 160: G3058

• 64 Yoshida J, Sugawara M, Tatsumi M, Kise N. J. Org. Chem. 1998; 63: 5950

• 65 Horii D, Fuchigami T, Atobe M. J. Am. Chem. Soc. 2007; 129: 11692

• 66 Kuleshova J, Hill-Cousins JT, Birkin PR, Brown RCD, Pletcher D, Underwood TJ. Electrochim. Acta 2011; 56: 4322

• 67 Kuleshova J, Hill-Cousins JT, Birkin PR, Brown RCD, Pletcher D, Underwood TJ. Electrochim. Acta 2012; 69: 197

• 68 Green RA, Brown RCD, Pletcher D, Harji B. Org. Process Res. Dev. 2015; 19: 1424 material modified from original article published by the American Chemical Society creativecommons.org/licenses/by/3.0/

• 69 Green RA, Brown RCD, Pletcher D, Harji B. Electrochem. Commun. 2016; 73: 63 material modified from original article published by Elsevier creativecommons.org/licenses/by/4.0/

• 70 Roth GP, Stalder R, Long TR, Sauer DR, Djuric SW. J. Flow Chem. 2013; 3: 34

• 71 Osman FH, El-Samahy FA. Chem. Rev. 2002; 102: 629

• 72 Nematollahi D, Tammari E. J. Org. Chem. 2005; 70: 7769

• 73 Jung ME, Perez F. Org. Lett. 2009; 11: 2165

• 74 Fakhari AR, Nematollahi D, Shamsipur M, Makarem S, Davarani SSH, Alizadeh A, Khavasi HR. Tetrahedron 2007; 63: 3894

• 75 Wanzlick HW, Lehmann-Horchler M, Mohrmann S, Gritzky R, Heidepriem H, Pankow B. Angew. Chem. Int. Ed. Engl. 1964; 3: 401

• 76 Amemiya F, Horii D, Fuchigami T, Atobe M. J. Electrochem. Soc. 2008; 155: E162

• 77 Kashiwagi T, Amemiya F, Fuchigami T, Atobe M. J. Flow Chem. 2013; 3: 17

• 78 Meunier B, Visser SP, Shaik S. Chem. Rev. 2004; 104: 3947

• 79 Stalder R, Roth GP. ACS Med. Chem. Lett. 2013; 4: 1119

• 80 Waldon DJ, Teffera Y, Colletti AE, Liu J, Zurcher D, Copeland KW, Zhao Z. Chem. Res. Toxicol. 2010; 23: 1947

• 81 Speck K, Magauer T. Beilstein J. Org. Chem. 2013; 9: 2048

• 82 Tang W, Stearns RA, Bandiera SM, Zhang Y, Raab C, Braun MP, Dean DC, Pang J, Leung KH, Doss GA, Strauss JR, Kwei GY, Rushmore TH, Chiu S.-HL, Baillie TA. Drug Metab. Dispos. 1999; 27: 365

• 83 El-Masri HA, Portier CJ. Drug Metab. Dispos. 1998; 26: 585

• 84 McKellar QA, Coop RL, Jackson F. Int. J. Parasitol. 1995; 25: 1207

• 85 Curry SH. Anal. Chem. 1968; 40: 1251

• 86 Permentier HP, Bruins AP, Bischoff R. Mini-Rev. Med. Chem. 2008; 8: 46

• 87 Karst U. Angew. Chem. Int. Ed. 2004; 43: 2476

• 88 Jones AM, Banks CE. Beilstein J. Org. Chem. 2014; 10: 3056

• 89 Shono T, Matsumura Y, Tsubata K. Org. Synth. 1985; 63: 206

• 90 Gravel E, Poupon E. Nat. Prod. Rep. 2010; 27: 32

• 91 Kabeshov MA, Musio B, Murray PRD, Browne DL, Ley SV. Org. Lett. 2014; 16: 4618

• 92 Üstünes L, Özer A, Laekeman GM, Corthout J, Pieters LAC, Baeten W, Herman AG, Claeys M, Vlietinck AJ. J. Nat. Prod. 1991; 54: 959

• 93 Mahatthananchai J, Bode JW. Acc. Chem. Res. 2014; 47: 696

• 94 Grossmann A, Enders D. Angew. Chem. Int. Ed. 2012; 51: 314

• 95 Biju AT, Kuhl N, Glorius F. Acc. Chem. Res. 2011; 44: 1182

• 96 Nair V, Vellalath S, Babu BP. Chem. Soc. Rev. 2008; 37: 2691

• 97 Green RA, Pletcher D, Leach SG, Brown RCD. Org. Lett. 2015; 17: 3290

• 98 Pattabiraman VR, Bode JW. Nature (London) 2011; 480: 471

• 99 Green RA, Pletcher D, Leach SG, Brown RCD. Org. Lett. 2016; 18: 1198

• 100 He P, Watts P, Marken F, Haswell SJ. Angew. Chem. Int. Ed. 2006; 45: 4146

• 101 He P, Watts P, Marken F, Haswell SJ. Lab Chip 2007; 7: 141

• 102 Porter NA, Scott DM, Rosenstein IJ, Giese B, Veit A, Zeitz HG. J. Am. Chem. Soc. 1991; 113: 1791

• 103 Devlin JP, Ollis WD, Thorpe JE, Wood RJ, Broughton BJ, Warren PJ, Wooldridge KRH, Wright DE. J. Chem. Soc., Perkin Trans. 1 1975; 830

• 104 Sabitha G, Srividya R, Yadav JS. Tetrahedron 1999; 55: 4015

• 105 Kantchev EAB, OʼBrien CJ, Organ MG. Angew. Chem. Int. Ed. 2007; 46: 2768

• 106 Hopkinson MN, Richter C, Schedler M, Glorius F. Nature (London) 2014; 510: 485

• 107 Mercs L, Albrecht M. Chem. Soc. Rev. 2010; 39: 1903

• 108 Monteiro DCF, Phillips RM, Crossley BD, Fielden J, Willans CE. Dalton Trans. 2012; 41: 3720

• 109 Chapman MR, Shafi YM, Kapur N, Nguyen BN, Willans CE. Chem. Commun. (Cambridge) 2015; 51: 1282

• 110 Pintauro PN, Johnson DK, Park K, Baizer MM, Nobe K. J. Appl. Electrochem. 1984; 14: 209

• 111 Simonet J, Pilard J.-F, In: Organic Electrochemistry Lund H, Hammerich O. Marcel Dekker New York 2001; 1171

• 112 Steckhan E. Top. Curr. Chem. 1987; 142: 1

• 113 Steckhan E. Angew. Chem. Int. Ed. 1986; 25: 683

• 114 Hill-Cousins JT, Kuleshova J, Green RA, Birkin PR, Pletcher D, Underwood TJ, Leach SG, Brown RCD. ChemSusChem 2012; 5: 326

• 115 Ciriminna R, Pagliaro M. Org. Process Res. Dev. 2010; 14: 245

• 116 Tebben L, Studer A. Angew. Chem. Int. Ed. 2011; 50: 5034

• 117 Alfonsi K, Colberg J, Dunn PJ, Fevig T, Jennings S, Johnson TA, Kleine HP, Knight C, Nagy MA, Perry DA, Stefaniak M. Green Chem. 2008; 10: 31

• 118 Bogdan A, McQuade DT. Beilstein J. Org. Chem. 2009; 5: 17