Copper-Catalyzed Chemoselective Nitro Reduction

Abstract

The reduction of nitro compounds into the highly valuable anilines is reported using a Cu catalyst and B₂Pin₂. The reactions proceed under very mild conditions and showcase excellent functional group tolerance. This method is applied to a large panel of nitro derivatives, including biorelevant molecules and important synthetic intermediates, toward the synthesis of active pharmaceutical ingredients (APIs). This novel reaction manifold intends to provide a complementary approach to the existing portfolio of nitro-reduction methods.

Key words

nitro group - aniline - reduction - copper - boryl radicals

Publication History

Received: 05 April 2024

Accepted after revision: 14 May 2024

Accepted Manuscript online:
14 May 2024

Article published online:
28 May 2024

• References

• 1a Lawrence SA. Amines: Synthesis, Properties and Applications . Cambridge University Press; Cambridge: 2004
• 1b McGrath NA, Brichacek M, Njardarson JT. A. J. Chem. Educ. 2010; 87: 1348
• 1c The Chemistry of Anilines . Rappoport Z. John Wiley & Sons; Hoboken: 2007
• 2a Hodgson HH. Chem. Rev. 1947; 40: 251
• 2b Akhtar R, Zahoor AF, Rasool N, Ahmad M, Ali KG. Mol. Diversity 2022; 26: 1837

For selected reviews, see:
• 3a Orlandi M, Brenna D, Harms R, Jost S, Benaglia M. Org. Process Res. Dev. 2018; 22: 430
• 3b Booth G. Nitro Compounds, Aromatic. In Ullmann's Encyclopedia of Industrial Chemistry. Wiley-VCH; New York: 2000
• 3c Kadam HK, Tilve SG. RSC Adv. 2015; 5: 83391
• 4 Porter HK. In Organic Reactions . John Wiley & Sons; Hoboken: 2011: 455
• 5 Wang Z. In Comprehensive Organic Name Reactions and Reagents . Wang Z. Wiley-VCH; Weinheim: 2010: 284

For selected examples, see:
• 6a Epa K, Aakeroÿ CB, Desper J, Rayat S, Chandra KL, Cruz-Cabeza AJ. Chem. Commun. 2013; 49: 7929
• 6b Jeanty M, Blu J, Suzenet F, Guillaumet G. Org. Lett. 2009; 11: 5142
• 6c Zhang L, Fan J, Vu K, Hong K, Le Brazidec JY, Shi J, Biamonte M, Busch DJ, Lough RE, Grecko R, Ran Y, Sensintaffar JL, Kamal A, Lundgren K, Burrows FJ, Mansfield R, Timony GA, Ulm EH, Kasibhatla SR, Boehm MF. J. Med. Chem. 2006; 49: 5352

For selected reviews, see:
• 7a Tafesh A, Weiguny J. Chem. Rev. 1996; 96: 2035
• 7b Blaser H.-U, Steiner H, Studer M. ChemCatChem 2009; 1: 210
• 7c Romero AH. ChemistrySelect 2020; 5: 13054
• 8 Formenti D, Ferretti F, Scharnagl FK, Beller M. Chem. Rev. 2019; 119: 2611

For selected examples, see:
• 9a Giomi D, Ceccarelli J, Salvini A, Brandi A. ChemistrySelect 2020; 5: 10511
• 9b Bhattacharjee A, Hosoya H, Ikeda H, Nishi K, Tsurugi H, Mashima K. Chem. Eur. J. 2018; 24: 11278
• 9c Park KK, Oh CH, Joung WK. Tetrahedron Lett. 1993; 34: 7445
• 9d McLaughlin MA, Barnes DM. Tetrahedron Lett. 2006; 47: 9095

For selected examples, see:
• 10a Lu H, Geng Z, Li J, Zou D, Wu Y, Wu Y. Org. Lett. 2016; 18: 2774
• 10b Hosoya H, Castro LC, Sultan I, Nakajima Y, Ohmura T, Sato K, Tsurugi H, Suginome M, Mashima K. Org. Lett. 2019; 21: 9812
• 10c Chen D, Zhou Y, Zhou H, Liu S, Liu Q, Zhang K, Uozumi Y. Synlett 2018; 29: 1765
• 10d Jang M, Lim T, Park BY, Han MS. J. Org. Chem. 2022; 87: 910
• 10e Yin L, Huang G, Lin X, Song X, Chen Y, Yan T, Li M, Dang L. Org. Chem. Front. 2023; 10: 4623
• 10f Yao W, Wang J, Lou Y, Wu H, Qi X, Yang J, Zhong A. Org. Chem. Front. 2021; 8: 4554
• 10g Chen C, Lu C, Zhao B. J. Org. Chem. 2023; 88: 16391
• 10h Wang B, Ma J, Ren H, Lu S, Xu J, Liang Y, Lu C, Yan H. Chin. Chem. Lett. 2022; 33: 2420
• 10i Corkovic A, Chiarella T, Williams FJ. Org. Lett. 2023; 25: 8787

For selected examples, see:
• 11a Zhong M, Pannecoucke X, Jubault P, Poisson T. Chem. Eur. J. 2021; 27: 11818
• 11b Zhong M, Gagné Y, Hope TO, Pannecoucke X, Frenette M, Jubault P, Poisson T. Angew. Chem. Int. Ed. 2021; 60: 14498
• 11c Brégent T, Bouillon J.-P, Poisson T. Org. Lett. 2020; 22: 7688
• 11d Ivanova MV, Bayle A, Besset T, Pannecoucke X, Poisson T. Chem. Eur. J. 2017; 23: 17318
• 11e Bayle A, Cocaud C, Nicolas C, Martin OR, Poisson T, Pannecoucke X. Eur. J. Org. Chem. 2015; 3787
• 12a Aelterman M, Jubault P, Poisson T. Eur. J. Org. Chem. 2023; e202300063
• 12b Aelterman M, Biremond T, Jubault P, Poisson T. Chem. Eur. J. 2022; 28: e2022002194
• 12c Brégent T, Bouillon J.-P, Poisson T. Chem. Eur. J. 2021; 27: 13966
• 12d Aelterman M, Sayes M, Jubault P, Poisson T. Chem. Eur. J. 2021; 27: 8277
• 13 The deoxygenation step might occur in the presence of other boron derivatives.
• 14a Ming W, Liu X, Friedrich A, Krebs J, Marder TB. Org. Lett. 2020; 22: 365
• 14b Mao L, Szabo KJ, Marder TB. Org. Lett. 2017; 19: 1204
• 15 Li W, Artz J, Broicher C, Junge K, Hartmann H, Besmehn A, Palkovits R, Beller M. Catal. Sci. Technol. 2019; 9: 157
• 16 Sun H.-b, Ai Y, Li D, Tang Z, Shao Z, Liang Q. Chem. Eng. J. 2017; 314: 328
• 17 Zhao X, Wu M, Liu Y, Cao S. Org. Lett. 2018; 20: 5564
• 18 Xu Z.-B, Lu G.-P, Cai C. Catal. Commun. 2017; 99: 57
• 19 Legnani L, Prina Cerai G, Morandi B. ACS Catal. 2016; 6: 8162
• 20 Chen Y, Kamlet AS, Steinman JB, Liu DR. Nat. Chem. 2011; 3: 146
• 21 Sorribes I, Liu L, Corma A. ACS Catal. 2017; 7: 2698
• 22 Sharma U, Kumar N, Kumar Verna P, Kumar V, Singh B. Green Chem. 2012; 14: 2289
• 23 Ham WS, Hillenbrand J, Jacq J, Genicot C, Ritter T. Angew. Chem. Int. Ed. 2019; 58: 532
• 24 Cantillo D, Moghaddam MM, Kappe O. J. Org. Chem. 2013; 78: 4530
• 25 Rousseaux S, Liégault B, Fagnou K. Chem. Sci. 2012; 3: 244
• 26 Ida Y, Matsubara A, Nemoto T, Saito M, Hirayama S, Fujii H, Nagase H. Bioorg. Med. Chem. 2012; 20: 5810
• 27 Kasparian AJ, Savarin C, Allgeier AM, Walker SD. J. Org. Chem. 2011; 76: 9841
• 28 Loos P, Alex H, Hassfeld J, Lovis K, Platzek J, Steinfeld N, Hubner S. Org. Process. Res. Dev. 2016; 20: 452
• 29 Jagadeesh RV, Banerjee D, Arockiam PB, Junge H, Junge K, Pohl M.-M, Radnik J, Bruckner A, Beller M. Green Chem. 2015; 17: 898