6.1.43 Product Subclass 43: Azaborines (Borazines)

Abstract

Azaborines (or borazines) represent an interesting class of heterocycles incorporating a boron–nitrogen structural motif within an aromatic ring system. This creates a system that is isosteric to traditional all-carbon ring systems, as the lone pair on nitrogen can donate into the empty orbital at boron to afford aromatic properties. Reviewed herein are synthetic strategies to access mono- and bicyclic azaborine cores, along with subsequent functionalization strategies, some of which are uniquely applicable due to the inherent dipole imparted on these ring systems.

Key words

azaborines - aromaticity - bicyclic compounds - borazarenes - borazines - boron compounds - cyclization - heterocycles - isosteres

• 1 Bosdet MJD, Piers WE. Can. J. Chem. 2009; 87: 8

• 2 Baranac-Stojanović M. Chem.–Eur. J. 2014; 20: 16 558

• 3 Huang J, Li Y. Front. Chem. (Lausanne, Switz.) 2018; 6: 341

• 4 Giustra ZX, Liu S.-Y. J. Am. Chem. Soc. 2018; 140: 1184

• 5 Campbell PG, Marwitz AJV, Liu S.-Y. Angew. Chem. Int. Ed. 2012; 51: 6074

• 6 Wang X.-Y, Wang J.-Y, Pei J. Chem.–Eur. J. 2015; 21: 3528

• 7 Wang BJ, Groziak MP. Adv. Heterocycl. Chem. 2016; 118: 47

• 8 Morgan MM, Piers WE. Dalton Trans. 2016; 45: 5920

• 9 McConnell CR, Liu S.-Y. Chem. Soc. Rev. 2019; 48: 3436

• 10 Dewar MJS, Marr PA. J. Am. Chem. Soc. 1962; 84: 3782

• 11 White DG. J. Am. Chem. Soc. 1963; 85: 3634

• 12 Davies KM, Dewar MJS, Rona P. J. Am. Chem. Soc. 1967; 89: 6294

• 13 Ashe AJ, Fang X. Org. Lett. 2000; 2: 2089

• 14 Marwitz AJV, Abbey ER, Jenkins JT, Zakharov LN, Liu S.-Y. Org. Lett. 2007; 9: 4905

• 15 Marwitz AJV, Matus MH, Zakharov LN, Dixon DA, Liu S.-Y. Angew. Chem. Int. Ed. 2009; 48: 973

• 16 Abbey ER, Lamm AN, Baggett AW, Zakharov LN, Liu S.-Y. J. Am. Chem. Soc. 2013; 135: 12 908

• 17 Leonori D, Aggarwal VK. Acc. Chem. Res. 2014; 47: 3174

• 18 Ashe AJ, Fang X, Fang X, Kampf JW. Organometallics 2001; 20: 5413

• 19 Pan J, Kampf JW, Ashe AJ. Organometallics 2004; 23: 5626

• 20 Braunschweig H, Celik MA, Dellermann T, Frenking G, Hammond K, Hupp F, Kelch H, Krummenacher I, Lindl F, Mailänder L, Müssig JH, Ruppert A. Chem.–Eur. J. 2017; 23: 8006

• 21 Su X, Baker JJ, Martin CD. Chem. Sci. 2020; 11: 126

• 22 Marwitz AJV, McClintock SP, Zakharov LN, Liu S.-Y. Chem. Commun. (Cambridge) 2010; 46: 779

• 23 McConnell CR, Campbell PG, Fristoe CR, Memmel P, Zakharov LN, Li B, Darrigan C, Chrostowska A, Liu S.-Y. Eur. J. Inorg. Chem. 2017; 2207

• 24 Lamm AN, Garner III EB, Dixon DA, Liu S.-Y. Angew. Chem. Int. Ed. 2011; 50: 8157

• 25 Rudebusch GE, Zakharov LN, Liu S.-Y. Angew. Chem. Int. Ed. 2013; 52: 9316

• 26 Zhao P, Nettleton DO, Karki RG, Zécri FJ, Liu S.-Y. ChemMedChem 2017; 12: 358

• 27 Brown AN, Zakharov LN, Mikulas T, Dixon DA, Liu S.-Y. Org. Lett. 2014; 16: 3340

• 28 Pan J, Kampf JW, Ashe AJ. Org. Lett. 2007; 9: 679

• 29 Baranac-Stojanović M. J. Org. Chem. 2019; 84: 13 582

• 30 Zhang Y, Sun F, Dan W, Fang X. J. Org. Chem. 2017; 82: 12 877

• 31 Zhang Y, Dan W, Fang X. Organometallics 2017; 36: 1677

• 32 Brown AN, Li B, Liu S.-Y. Tetrahedron 2019; 75: 580

• 33 Brown AN, Li B, Liu S.-Y. J. Am. Chem. Soc. 2015; 137: 8932

• 34 Baggett AW, Vasiliu M, Li B, Dixon DA, Liu S.-Y. J. Am. Chem. Soc. 2015; 137: 5536

• 35 McConnell CR, Haeffner F, Baggett AW, Liu S.-Y. J. Am. Chem. Soc. 2019; 141: 9072

• 36 Baggett AW, Liu S.-Y. J. Am. Chem. Soc. 2017; 139: 15 259

• 37 Burford RJ, Li B, Vasiliu M, Dixon DA, Liu S.-Y. Angew. Chem. Int. Ed. 2015; 54: 7823

• 38 Boger DL. Chem. Rev. 1986; 86: 781

• 39 García-Rodeja Y, Fernández I. J. Org. Chem. 2016; 81: 6554

• 40 Edel K, Yang X, Ishibashi JSA, Lamm AN, Maichle-Mössmer C, Giustra ZX, Liu S.-Y, Bettinger HF. Angew. Chem. Int. Ed. 2018; 57: 5296

• 41 Giustra ZX, Yang X, Chen M, Bettinger HF, Liu S.-Y. Angew. Chem. Int. Ed. 2019; 58: 18 918

• 42 Baggett AW, Guo F, Li B, Liu S.-Y, Jäkle F. Angew. Chem. Int. Ed. 2015; 54: 11 191

• 43 Wan W.-M, Baggett AW, Cheng F, Lin H, Liu S.-Y, Jäkle F. Chem. Commun. (Cambridge) 2016; 52: 13 616

• 44 Xu S, Mikulas TC, Zakharov LN, Dixon DA, Liu S.-Y. Angew. Chem. Int. Ed. 2013; 52: 7527

• 45 Xu S, Zakharov LN, Liu S.-Y. J. Am. Chem. Soc. 2011; 133: 20 152

• 46 Li J, Daniliuc CG, Mück-Lichtenfeld C, Kehr G, Erker G. Angew. Chem. Int. Ed. 2019; 58: 15 377

• 47 Braunschweig H, Damme A, Jimenez-Halla JOC, Pfaffinger B, Radacki K, Wolf J. Angew. Chem. Int. Ed. 2012; 51: 10 034

• 48 Liu X, Zhang Y, Li B, Zakharov LN, Vasiliu M, Dixon DA, Liu S.-Y. Angew. Chem. Int. Ed. 2016; 55: 8333

• 49 Liu X, Wu P, Li J, Cui C. J. Org. Chem. 2015; 80: 3737

• 50 Choi JH, Lim HJ. Org. Biomol. Chem. 2015; 13: 5131

• 51 de Lescure LR, Jesse T, Groziak MP, Powers XB, Olmstead MM. J. Heterocycl. Chem. 2019; 56: 2960

• 52 Dewar MJS, Dietz R. J. Chem. Soc. 1959; 2728

• 53 Paetzold P, Stanescu C, Stubenrauch JR, Bienmüller M, Englert U. Z. Anorg. Allg. Chem. 2004; 630: 2632

• 54 Wisniewski SR, Guenther CL, Argintaru OA, Molander GA. J. Org. Chem. 2014; 79: 365

• 55 Davies GHM, Zhou Z.-Z, Jouffroy M, Molander GA. J. Org. Chem. 2017; 82: 549

• 56 Molander GA, Wisniewski SR, Amani J. Org. Lett. 2014; 16: 5636

• 57 Paetzold PI, Stohr G, Maisch H, Lenz H. Chem. Ber. 1968; 101: 2881

• 58 Zhuang F.-D, Han J.-M, Tang S, Yang J.-H, Chen Q.-R, Wang J.-Y, Pei J. Organometallics 2017; 36: 2479

• 59 Tsuchiya S, Saito H, Nogi K, Yorimitsu H. Org. Lett. 2019; 21: 3855

• 60 Sargent LJ. J. Org. Chem. 1961; 26: 1754

• 61 Dewar MJS, Hashmall J, Kubba VP. J. Org. Chem. 1964; 29: 1755

• 62 Kwong RC, Ma B, Tsai J.-Y, Beers S, Barron E, Kottas G, Dyatkin AB. WO 2010 135 519, 2010

• 63 Wang X, Davies GHM, Koschitzky A, Wisniewski SR, Kelly CB, Molander GA. Org. Lett. 2019; 21: 2880

• 64 Dewar MJS, Dietz R. J. Org. Chem. 1961; 26: 3253

• 65 Molander GA, Wisniewski SR. J. Org. Chem. 2014; 79: 6663

• 66 Molander GA, Wisniewski SR. J. Org. Chem. 2014; 79: 8339

• 67 Molander GA, Wisniewski SR, Etemadi-Davan E. J. Org. Chem. 2014; 79: 11 199

• 68 Davies GHM, Jouffroy M, Sherafat F, Saeednia B, Howshall C, Molander GA. J. Org. Chem. 2017; 82: 8072

• 69 Compton JS, Saeednia B, Kelly CB, Molander GA. J. Org. Chem. 2018; 83: 9484

• 70 Molander GA, Wisniewski SR, Traister KM. Org. Lett. 2014; 16: 3692

• 71 Jouffroy M, Davies GHM, Molander GA. Org. Lett. 2016; 18: 1606

• 72 Molander GA, Amani J, Wisniewski SR. Org. Lett. 2014; 16: 6024

• 73 Xu S, Haeffner F, Li B, Zakharov LN, Liu S.-Y. Angew. Chem. Int. Ed. 2014; 53: 6795

• 74 Chinnapattu M, Sathiyanarayanan KI, Iyer PS. RSC Adv. 2015; 5: 37 716

• 75 Xu S, Zhang Y, Li B, Liu S.-Y. J. Am. Chem. Soc. 2016; 138: 14 566

• 76 Liu Z, Ishibashi JSA, Darrigan C, Dargelos A, Chrostowska A, Li B, Vasiliu M, Dixon DA, Liu S.-Y. J. Am. Chem. Soc. 2017; 139: 6082

• 77 Dewar MJS, Gleicher GJ, Robinson BP. J. Am. Chem. Soc. 1964; 86: 5698

• 78 Dewar MJS, Jones R. J. Am. Chem. Soc. 1968; 90: 2137

• 79 Fang X, Yang H, Kampf JW, Banaszak Holl MM, Ashe AJ. Organometallics 2006; 25: 513

• 80 Sun F, Lv L, Huang M, Zhou Z, Fang X. Org. Lett. 2014; 16: 5024

• 81 Rohr AD, Kampf JW, Ashe AJ. Organometallics 2014; 33: 1318

• 82 Abengózar A, Fernández-González MA, Sucunza D, Frutos LM, Salgado A, García-García P, Vaquero JJ. Org. Lett. 2018; 20: 4902

• 83 Sun F, Huang M, Zhou Z, Fang X. RSC Adv. 2015; 5: 75 607