Pyridine-Mediated B–B Bond Activation of (RO)₂B–B(OR)₂ for Generating Borylpyridine Anions and Pyridine-Stabilized Boryl Radicals as Useful Boryl Reagents in Organic Synthesis

Abstract

Significant developments have been achieved in recent years toward the utilization of (RO)₂B–B(OR)₂ for exploring transition-metal-free organic transformations in organic synthesis. Among the various combinations of Lewis bases with diborons developed so far, pyridine derivatives are simple, commercially available, and cheap compounds to expand the synthetic utility of diborons by generating borylpyridine anions and pyridine-stabilized boryl radicals via B–B bond cleavage. These borylpyridine species mediate a series of transformations in both a catalytic and stoichiometric manner for C–X activation (X = halogen, CO₂H, NR₂) and concomitant C-borylation, hydroboryl­ation, C–C bond formation, and reduction reactions.

1 Introduction

2 Reaction Pathway for B–B Bond Cleavage of Diborons with Electron-Deficient Pyridines

3 Pyridine-Mediated B–B Bond Activation of (RO)₂B–B(OR)₂ for Application in Organic Synthesis

3.1 Dehalogenative C-Borylation

3.2 Desulfonative C-Borylation

3.3 Decarboxylative C-Borylation

3.4 Deaminative C-Borylation

3.5 Hydroborylation

3.6 C–C Bond Formation

3.7 Pyridine Functionalization

3.8 Deoxygenation and N-Borylation Reactions

4 Conclusions

Key words

diboron - pyridine - B–B bond cleavage - borylation - single-electron transfer - radical reaction

Publication History

Received: 03 March 2021

Accepted after revision: 20 April 2021

Accepted Manuscript online:
20 April 2021

Article published online:
25 May 2021

• References

• 1 Neeve EC, Geier SJ, Mkhalid IA. I, Westcott SA, Marder TB. Chem. Rev. 2016; 116: 9091

Recent reviews:
• 2a Dembitsky VM, Ali HA, Srebnik M. Adv. Organomet. Chem. 2004; 51: 193
• 2b Ishiyama T, Miyaura N. Chem. Rec. 2004; 3: 271
• 2c Miyaura N. Bull. Chem. Soc. Jpn. 2008; 81: 1535
• 2d Yoshida H. ACS Catal. 2016; 6: 1799
• 2e Kubota K, Iwamoto H, Ito H. Org. Biomol. Chem. 2017; 15: 285
• 2f Hemming D, Fritzemeier R, Westcott SA, Santos WL, Steel PG. Chem. Soc. Rev. 2018; 47: 7477
• 2g He Z, Hu Y, Xia C, Liu C. Org. Biomol. Chem. 2019; 17: 6099

Related reviews:
• 3a Gulyás H, Bonet A, Pubill-Ulldemolins C, Solé C, Fernández E. Pure Appl. Chem. 2012; 84: 2219
• 3b Cid J, Gulyás H, Carbó JJ, Fernández E. Chem. Soc. Rev. 2012; 41: 3558
• 3c Dewhurst RD, Neeve EC, Braunschweig H, Marder TB. Chem. Commun. 2015; 51: 9594
• 3d Cuenca AB, Shishido R, Ito H, Fernández E. Chem. Soc. Rev. 2017; 46: 415
• 3e Wen Y, Deng C, Xie J, Kang X. Molecules 2019; 24: 101
• 4a Urry G, Kerrigan J, Parsons TD, Schlesinger HI. J. Am. Chem. Soc. 1954; 76: 5299
• 4b Ceron P, Finch A, Frey J, Kerrigan J, Parsons T, Urry G, Schlesinger HI. J. Am. Chem. Soc. 1959; 81: 6369
• 4c Morrison JA. Chem. Rev. 1991; 91: 35

Early examples:
• 5a Lee K.-s, Zhugralin AR, Hoveyda AH. J. Am. Chem. Soc. 2009; 131: 7253
• 5b Bonet A, Gulyás H, Fernández E. Angew. Chem. Int. Ed. 2010; 49: 5130
• 5c Bonet A, Pubill-Ulldemolins C, Bo C, Gulyás G, Fernández E. Angew. Chem. Int. Ed. 2011; 50: 7158
• 5d Pubill-Ulldemolins C, Bonet A, Bo C, Gulyás H, Fernández E. Chem. Eur. J. 2012; 18: 1121
• 6 A representative early example: Wang G, Zhang H, Zhao J, Li W, Cao J, Zhu C, Li S. Angew. Chem. Int. Ed. 2016; 55: 5985
• 7a Oshima K, Ohmura T, Suginome M. Chem. Commun. 2012; 48: 8571
• 7b Ohmura T, Morimasa Y, Suginome M. J. Am. Chem. Soc. 2015; 137: 2852
• 7c Qi JQ, Jiao L. J. Org. Chem. 2020; 85: 13877
• 8 Hu J, Wang G, Li S, Shi Z. Angew. Chem. Int. Ed. 2018; 57: 15227
• 9 Zhang L, Jiao L. J. Am. Chem. Soc. 2017; 139: 607
• 10 Zhang L, Jiao L. Chem. Sci. 2018; 9: 2711
• 11 Pinet S, Liautard V, Debiais M, Pucheault M. Synthesis 2017; 49: 4759
• 12 Zhang L, Jiao L. J. Am. Chem. Soc. 2019; 141: 9124
• 13 Zhang L, Wu Z.-Q, Jiao L. Angew. Chem. Int. Ed. 2020; 59: 2095
• 14a Cheng Y, Mück-Lichtenfeld C, Studer A. J. Am. Chem. Soc. 2018; 140: 6221
• 14b Cheng Y, Mück-Lichtenfeld C, Studer A. Angew. Chem. Int. Ed. 2018; 57: 16832
• 15 Maekawa Y, Ariki ZT, Nambo M, Crudden CM. Org. Biomol. Chem. 2019; 17: 7300
• 16 Schoenebeck F, Murphy JA, Zhou S, Uenoyama Y, Miclo Y, Tuttle T. J. Am. Chem. Soc. 2007; 129: 13368
• 17 Candish L, Teders M, Glorius F. J. Am. Chem. Soc. 2017; 139: 7440
• 18 Wang G.-Z, Shang R, Fu Y. Org. Lett. 2017; 19: 4291
• 19 Yuanhong M, Pang Y, Chabbra S, Reijerse EJ, Schnegg A, Niski J, Leutzsch M, Cornella J. Chem. Eur. J. 2020; 26: 3738
• 20 Recent review: Obligacion JV, Chirik PJ. Nat. Rev. Chem. 2018; 2: 15
• 21 Yang K, Song Q. Green Chem. 2016; 18: 932
• 22 Xu R, Lu G.-p, Cai C. New J. Chem. 2018; 42: 16456
• 23 Yang H, Zhang L, Zhou F.-Y, Jiao L. Chem. Sci. 2020; 11: 742
• 24 Cao J, Wang G, Gao L, Cheng X, Li S. Chem. Sci. 2018; 9: 3664
• 25 Jo J, Kim S, Choi JH, Chung WJ. Chem. Commun. 2021; 57: 1360
• 26 Gao L, Wang G, Cao J, Yuan D, Xu C, Guo X, Li S. Chem. Commun. 2018; 54: 11534
• 27 Guo A, Han J.-B, Tang X.-Y. Org. Lett. 2018; 20: 2351
• 28a Rablen PR, Hartwig JF. J. Am. Chem. Soc. 1996; 118: 4648
• 28b Rablen PR. J. Am. Chem. Soc. 1997; 119: 8350
• 29 Ueno R, Ikeda Y, Shirakawa E. Eur. J. Org. Chem. 2017; 2017: 4188
• 30 Wang J, Li J, Huang J, Zhu Q. J. Org. Chem. 2016; 81: 3017
• 31 Kondo O, Benson SW. Int. J. Chem. Kinet. 1984; 16: 949
• 32 Burkey TJ, Majewski M, Griller D. J. Am. Chem. Soc. 1986; 108: 2218
• 33 Feng S, Li T, Du C, Chen P, Song D, Li J, Xie X, She X. Chem. Commun. 2017; 53: 4585
• 34 Kokatla HP, Thomson PF, Bae S, Doddi VR, Lakshman MK. J. Org. Chem. 2011; 76: 7842
• 35 Wang G, Cao J, Gao L, Chen W, Huang W, Cheng X, Li S. J. Am. Chem. Soc. 2017; 139: 3904
• 36 Cao J, Wang G, Gao L, Chen H, Liu X, Cheng X, Li S. Chem. Sci. 2019; 10: 2767
• 37 Koniarczyk JL, Greenwood JW, Alegre-Requena JV, Paton RS, McNally A. Angew. Chem. Int. Ed. 2019; 58: 14882
• 38 Chen D, Xu G, Zhou Q, Chung LW, Tang W. J. Am. Chem. Soc. 2017; 139: 9767
• 39 Wilckens K, Lentz D, Czekelius C. Organometallics 2011; 30: 1287
• 40 Zhou Q, Tang W, Chung LW. J. Organomet. Chem. 2018; 864: 97
• 41 Hosoya H, Misal Castro LC, Sultan I, Nakajima Y, Ohmura T, Sato K, Tsurugi H, Suginome M, Mashima K. Org. Lett. 2019; 21: 9812
• 42 Misal Castro LC, Sultan I, Nishii K, Tsurugi H, Mashima K. J. Org. Chem. 2021; 86: 3287
• 43 Heravi MM, Rohani S, Zadsirjan V, Zahedi N. RSC Adv. 2017; 7: 52852