Cobalt-Catalyzed C–H Bond Functionalization: a Personal Account

Abstract

The development of green and sustainable synthetic methods is of great interest worldwide. Today the direct activation and functionalization of relatively inert C–H bonds is one of the top fields in organic chemistry, and this strategy already represents a sustainable and more environmentally friendly approach due to its atom and step economy compared to alternative C–C and C–Het bond-forming processes. Much progress has been made in developing C–H bond functionalization methods using noble-metal catalysts. Cobalt has recently emerged as an attractive alternative because it is less toxic, cheaper, and more abundant than noble metals. This Account summarizes the cobalt-catalyzed C–H bond-functionalization methods that have been developed during the corresponding author’s research career.

1 Introduction and Background

2 C–H Bond Functionalization of 8-Aminoquinoline Benzamides

3 Mechanistic Investigations of Cobalt-Catalyzed, Aminoquinoline-Directed C–H Bond Functionalization of Benzamides

4 C(sp²)–H Bond Functionalization of 8-Aminoquinoline Phosphinamides

5 C(sp²)–H Bond Carbonylation of 8-Aminoquinoline Sulfonamides

6 C(sp²)–H Bond Functionalization of Benzoic Acids

7 C(sp²)–H Bond Functionalization of Phenylglycine Derivatives

8 C(sp²)–H Bond Functionalization of Phenylalanine Derivatives

9 Conclusion

Key words

amino acid - annulations - carbonylation - C–H bond activation - cobalt catalysis - imination - intramolecular amidation

Publication History

Received: 14 February 2025

Accepted after revision: 21 March 2025

Article published online:
29 April 2025

• References


For selected reviews, see:
• 1a Lyons TW, Sanford MS. Chem. Rev. 2010; 110: 1147
• 1b Ackermann L. Chem. Rev. 2011; 111: 1315
• 1c Baudoin O. Chem. Soc. Rev. 2011; 40: 4902
• 1d He J, Wasa M, Chan KS. L, Shao Q, Yu J.-Q. Chem. Rev. 2017; 117: 8754
• 1e Hartwig JF. J. Am. Chem. Soc. 2016; 138: 2

For selected reviews, see:
• 2a Baudoin O. Angew. Chem. Int. Ed. 2020; 59: 17798
• 2b Abrams DJ, Provencher PA, Sorensen EJ. Chem. Soc. Rev. 2018; 47: 8925
• 2c Guillemard L, Kaplaneris N, Ackermann L, Johansson MJ. Nat. Rev. Chem. 2021; 5: 522
• 2d Jana R, Begam HM, Dinda E. Chem. Commun. 2021; 57: 10842

For selected reviews, see:
• 3a Gandeepan P, Müller T, Zell D, Cera G, Warratz S, Ackermann L. Chem. Rev. 2019; 119: 2192
• 3b Mo J, Messinis AM, Li J, Warratz S, Ackermann L. Acc. Chem. Res. 2024; 57: 10
• 3c Khake SM, Chatani N. Chem 2020; 6: 1056
• 3d Shang R, Ilies L, Nakamura E. Chem. Rev. 2017; 117: 9086
• 3e Guo X.-X, Gu D.-W, Wu Z, Zhang W. Chem. Rev. 2015; 115: 1622
• 3f Liu W, Ackermann L. ACS Catal. 2016; 6: 3743

For selected reviews on cobalt-catalyzed C–H bond functionalization, see:
• 4a Lukasevics L, Cizikovs A, Grigorjeva L. Chem. Commun. 2021; 57: 10827
• 4b Mei R, Dhawa U, Samanta RC, Ma W, Wencel-Delord J, Ackermann L. ChemSusChem 2020; 13: 3306
• 4c Baccalini A, Vergura S, Dolui P, Zanoni G, Maiti D. Org. Biomol. Chem. 2019; 17: 10119
• 4d Gao K, Yoshikai N. Acc. Chem. Rev. 2014; 47: 1208
• 4e Yoshino T, Matsunaga S. Adv. Synth. Catal. 2017; 359: 1245
• 4f Lukasevics L, Grigorjeva L. Org. Biomol. Chem. 2020; 18: 7460
• 5 Gao K, Lee P.-S, Fujita T, Yoshikai N. J. Am. Chem. Soc. 2010; 132: 12249
• 6 Yoshino T, Ikemoto H, Matsunaga S, Kanai M. Angew. Chem. Int. Ed. 2013; 52: 2207
• 7 Grigorjeva L, Daugulis O. Angew. Chem. Int. Ed. 2014; 53: 10209
• 8 Grigorjeva L, Daugulis O. Org. Lett. 2014; 16: 4684
• 9 Grigorjeva L, Daugulis O. Org. Lett. 2014; 16: 4688
• 10 Grigorjeva L, Daugulis O. Org. Lett. 2015; 17: 1204
• 11a For methodology development, see the Supporting Information of ref. 11b.
• 11b Lukasevics L, Oh GN, Wang X, Grigorjeva L, Daugulis O. J. Am. Chem. Soc. 2025; 147: 2476
• 12a Cizikovs A, Grigorjeva L. Inorganics 2023; 11: 194
• 12b Lukasevics L, Grigorjeva L. Mechanistic Studies on Cobalt-Catalyzed, Bidentate Chelation-Assisted C–H Bond Functionalization. In Handbook of C–H Functionalization. Maiti D. Wiley-VCH; Weinheim: 2022
• 13 Nguyen TT, Grigorjeva L, Daugulis O. ACS Catal. 2016; 6: 551
• 14 Nguyen TT, Grigorjeva L, Daugulis O. Chem. Commun. 2017; 53: 5136
• 15 Nguyen TT, Grigorjeva L, Daugulis O. Angew. Chem. Int. Ed. 2018; 57: 1688
• 16a Weiner B, Szymański W, Janssen DB, Minnaard AJ, Feringa BL. Chem. Soc. Rev. 2010; 39: 1656
• 16b Saladino R, Botta G, Crucianelli M. Mini-Rev. Med. Chem. 2012; 12: 277
• 17 Zagorska PA, Grigorjeva L, Bolsakova J. Chem. Heterocycl. Compd. 2021; 57: 159
• 18 Bolsakova J, Lukasevics L, Grigorjeva L. J. Org. Chem. 2020; 85: 4482
• 19 Lukasevics L, Cizikovs A, Grigorjeva L. Org. Lett. 2020; 22: 2720
• 20 Cizikovs A, Lukasevics L, Grigorjeva L. Tetrahedron 2021; 93: 132307
• 21 Lukasevics L, Cizikovs A, Grigorjeva L. Org. Lett. 2021; 23: 2748
• 22 Lukasevics L, Cizikovs A, Grigorjeva L. Chem. Commun. 2022; 58: 9754
• 23 Cizikovs A, Zagorska PA, Grigorjeva L. Org. Lett. 2024; 26: 9536
• 24 Cizikovs A, Basens EE, Zagorska PA, Kinens A, Grigorjeva L. ACS Catal. 2024; 14: 1690