Copper-Catalyzed Aerobic Oxidations of Organic Molecules: Pathways for Two-Electron Oxidation with a Four-Electron Oxidant and a One-Electron Redox-Active Catalyst

Accounts of Chemical Research

Volumn 48, Issue 6, 2015, Pages 1756-1766

  McCann, Scott D ^a   Stahl, Shannon S ^a  

^a UNIVERSITY OF WISCONSIN MADISON   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 84934941677     PISSN: 00014842     EISSN: 15204898     Source Type: Journal    
DOI: 10.1021/acs.accounts.5b00060     Document Type: Article

References (74)

1. Cavani, F.; Teles, J. H. Sustainability in Catalytic Oxidation: An Alternative Approach or a Structural Evolution? ChemSusChem 2009, 2, 508-534
2. For further discussion, see: Osterberg, P. M.; Niemeier, J. K.; Welch, C. J.; Hawkins, J. M.; Martinelli, J. R.; Johnson, T. E.; Root, T. W.; Stahl, S. S. Experimental Limiting Oxygen Concentrations for Nine Organic Solvents at Temperatures and Pressures Relevant to Aerobic Oxidations in the Pharmaceutical Industry Org. Process Res. Dev. 2014, 10.1021/op500328f
3. Mirica, L. M.; Ottenwaelder, X.; Stack, T. D. P. Structure and Spectroscopy of Copper-Dioxygen Complexes Chem. Rev. 2004, 104, 1013-1045
4. Lewis, E. A.; Tolman, W. B. Reactivity of Dioxygen-Copper Systems Chem. Rev. 2004, 104, 1047-1076
5. Hatcher, L. Q.; Karlin, K. D. Ligand Influences in Copper-Dioxygen Complex-Formation and Substrate Oxidations Adv. Inorg. Chem. 2006, 58, 131-184
6. Itoh, S.; Fukuzumi, S. Monooxygenase Activity of Type 3 Copper Proteins Acc. Chem. Res. 2007, 40, 592-600
7. Rolff, M.; Schottenheim, J.; Decker, H.; Tuczek, F. Copper-O2 Reactivity of Tyrosinase Models towards External Monophenolic Substrates: Molecular Mechanisms and Comparison with the Enzyme Chem. Soc. Rev. 2011, 40, 4077-4098
8. Hoffmann, A.; Citek, C.; Binder, S.; Goos, A.; Rübhausen, M.; Troeppner, O.; Ivanović-Burmazović, I.; Wasinger, E. C.; Stack, T. D. P.; Herres-Pawlis, S. Catalytic Phenol Hydroxylation with Dioxygen: Extension of the Tyrosinase Mechanism beyond the Protein Matrix Angew. Chem., Int. Ed. 2013, 52, 5398-5401
9. Citek, C.; Lyons, C. T.; Wasinger, E. C.; Stack, T. D. P. Self-Assembly of the Oxy-Tyrosinase Core and the Fundamental Components of Phenolic Hydroxylation Nat. Chem. 2012, 4, 317-322
10. Esguerra, K. V. N.; Fall, Y.; Petitjean, L.; Lumb, J.-P. Controlling the Catalytic Aerobic Oxidation of Phenols J. Am. Chem. Soc. 2014, 136, 7662-7668
11. Esguerra, K. V. N.; Fall, Y.; Lumb, J.-P. A Biomimetic Catalytic Aerobic Functionalization of Phenols Angew. Chem., Int. Ed. 2014, 53, 5877-5881
12. Stahl, S. S. Palladium Oxidase Catalysis: Selective Oxidation of Organic Chemicals via Direct Dioxygen-Coupled Catalytic Turnover Angew. Chem., Int. Ed. 2004, 43, 3400-3420
13. Stahl, S. S. Palladium-Catalyzed Oxidation of Organic Chemicals with O2 Science 2005, 309, 1824-1826
14. McDonald, R. I.; Liu, G.; Stahl, S. S. Palladium(II)-Catalyzed Alkene Functionalization via Nucleopalladation: Stereochemical Pathways and Enantioselective Catalytic Applications Chem. Rev. 2011, 111, 2981-3019
15. Campbell, A. N.; Stahl, S. S. Overcoming the Oxidant Problem: Strategies To Use O2 as the Oxidant in Organometallic C-H Oxidation Reactions Catalyzed by Pd (and Cu) Acc. Chem. Res. 2012, 45, 851-863
16. Copper-Oxygen Chemistry; Karlin, K. D; Itoh, S.; Rokita, S., Eds.; John Wiley & Sons: Hoboken, NJ, 2011.
17. Gamez, P.; Aubel, P. G.; Driessen, W. L.; Reedijk, J. Homogeneous Bio-Inspired Copper-Catalyzed Oxidation Reactions Chem. Soc. Rev. 2001, 30, 376-385
18. Punniyamurthy, T.; Rout, L. Recent Advances in Copper-Catalyzed Oxidation of Organic Compounds Coord. Chem. Rev. 2008, 252, 134-154
19. Wendlandt, A. E.; Suess, A. M.; Stahl, S. S. Copper-Catalyzed Aerobic Oxidative C-H Functionalizations: Trends and Mechanistic Insights Angew. Chem., Int. Ed. 2011, 50, 11062-11087
20. Shi, Z.; Zhang, C.; Tang, C.; Jiao, N. Recent Advances in Transition-Metal Catalyzed Reactions Using Molecular Oxygen as the Oxidant Chem. Soc. Rev. 2012, 41, 3381-3430
21. Allen, S. E.; Walvoord, R. R.; Padilla-Salinas, R.; Kozlowski, M. C. Aerobic Copper-Catalyzed Organic Reactions Chem. Rev. 2013, 113, 6234-6458
22. Zhang, C.; Tang, C.; Jiao, N. Recent Advances in Copper-Catalyzed Dehydrogenative Functionalization via Single Electron Transfer (SET) Process Chem. Soc. Rev. 2012, 41, 3464-3484
23. Girard, S. A.; Knauber, T.; Li, C.-J. The Cross-Dehydrogenative Coupling of Csp3-H Bonds: A Versatile Strategy for C-C Bond Formations Angew. Chem., Int. Ed. 2014, 53, 74-100
24. Ryland, B. L.; Stahl, S. S. Practical Aerobic Oxidations of Alcohols and Amines with Homogeneous Copper/TEMPO and Related Catalyst Systems Angew. Chem., Int. Ed. 2014, 53, 8824-8838
25. Cao, Q.; Dornan, L. M.; Rogan, L.; Hughes, N. L.; Muldoon, M. J. Aerobic Oxidation Catalysis with Stable Radicals Chem. Commun. 2014, 50, 4524-4543
26. Hickman, A. J.; Sanford, M. S. High-Valent Organometallic Copper and Palladium in Catalysis Nature 2012, 484, 177-185
27. Yang, L.; Lu, Z.; Stahl, S. S. Regioselective Copper-Catalyzed Chlorination and Bromination of Arenes with O2 as the Oxidant Chem. Commun. 2009, 6460-6462
28. Chen, X.; Hao, X.-S.; Goodhue, C. E.; Yu, J.-Q. Cu(II)-Catalyzed Functionalizations of Aryl C-H Bonds Using O2 as an Oxidant J. Am. Chem. Soc. 2006, 128, 6790-6791
29. Uemura, T.; Imoto, S.; Chatani, N. Amination of the Ortho C-H Bonds by the Cu(OAc)2-Mediated Reaction of 2-Phenylpyridines with Anilines Chem. Lett. 2006, 35, 842-843
30. Menini, L.; Gusevskaya, E. V. Novel Highly Selective Catalytic Oxychlorination of Phenols Chem. Commun. 2006, 209-211
31. Qiao, J. X.; Lam, P. Y. S. Copper-Promoted Carbon-Heteroatom Bond Cross-Coupling with Boronic Acids and Derivatives Synthesis 2011, 829-856
32. Neuville, L. Alternative and Emerging Reagents for the Arylation of Heteronucleophiles. In Copper-Mediated Cross-Coupling Reactions; Evano, G.; Blanchard, N., Eds.; John Wiley & Sons: Hoboken, NJ, 2011; pp 113-185.
33. Siemsen, P.; Livingston, R. C.; Diederich, F. Acetylenic Coupling: A Powerful Tool in Molecular Construction Angew. Chem., Int. Ed. 2000, 39, 2632-2657
34. Bai, R.; Zhang, G.; Yi, H.; Huang, Z.; Qi, X.; Liu, C.; Miller, J. T.; Kropf, A. J.; Bunel, E. E.; Lan, Y.; Lei, A. Cu(II)-Cu(I) Synergistic Cooperation To Lead the Alkyne C-H Activation J. Am. Chem. Soc. 2014, 136, 16760-16763
35. Hamada, T.; Ye, X.; Stahl, S. S. Copper-Catalyzed Aerobic Oxidative Amidation of Terminal Alkynes: Efficient Synthesis of Ynamides J. Am. Chem. Soc. 2008, 130, 833-835
36. Gao, Y.; Wang, G.; Chen, L.; Xu, P.; Zhao, Y.; Zhou, Y.; Han, L.-B. Copper-Catalyzed Aerobic Oxidative Coupling of Terminal Alkynes with H -Phosphonates Leading to Alkynylphosphonates J. Am. Chem. Soc. 2009, 131, 7956-7957
37. Wie, Y.; Zhao, H.; Kan, J.; Su, W.; Hong, M. Copper-Catalyzed Direct Alkynylation of Electron-Deficient Polyfluoroarenes with Terminal Alkynes Using O2 as an Oxidant J. Am. Chem. Soc. 2010, 132, 2522-2523
38. Chu, L.; Qing, F.-L. Copper-Mediated Aerobic Oxidative Trifluoromethylation of Terminal Alkynes with Me3SiCF3 J. Am. Chem. Soc. 2010, 132, 7262-7263
39. Wendlandt, A. E.; Stahl, S. S. Copper(II)-Mediated Oxidative Cyclization of Enamides to Oxazoles Org. Biomol. Chem. 2012, 10, 3866-3870
40. Ueda, S.; Nagasawa, H. Synthesis of 2-Arylbenzoxazoles by Copper-Catalyzed Intramolecular Oxidative C-O Coupling of Benzanilides Angew. Chem., Int. Ed. 2008, 47, 6411-6413
41. Brasche, G.; Buchwald, S. L. C-H Functionalization/C-N Bond Formation: Copper-Catalyzed Synthesis of Benzimidazoles from Amidines Angew. Chem., Int. Ed. 2008, 47, 1932-1934
42. King, A. E.; Brunold, T. C.; Stahl, S. S. Mechanistic Study of Copper-Catalyzed Aerobic Oxidative Coupling of Arylboronic Esters and Methanol: Insights into an Organometallic Oxidase Reaction J. Am. Chem. Soc. 2009, 131, 5044-5045
43. King, A. E.; Ryland, B. L.; Brunold, T. C.; Stahl, S. S. Kinetic and Spectroscopic Studies of Aerobic Copper(II)-Catalyzed Methoxylation of Arylboronic Esters and Insights into Aryl Transmetalation to Copper(II) Organometallics 2012, 31, 7948-7957
44. Ribas, X.; Jackson, D. A.; Donnadieu, B.; Mahía, J.; Parella, T.; Xifra, R.; Hedman, B.; Hodgson, K. O.; Llobet, A.; Stack, T. D. P. Aryl C-H Activation by CuII To Form an Organometallic Aryl-CuIII Species: A Novel Twist on Copper Disproportionation Angew. Chem., Int. Ed. 2002, 41, 2991-2994
45. For recent reviews of high-valent organocopper species, see ref 7c, ref 10, and the following: Casitas, A.; Ribas, X. The Role of Organometallic Copper(III) Complexes in Homogeneous Catalysis Chem. Sci. 2013, 4, 2301-2318
46. Huffman, L. M.; Stahl, S. S. Carbon-Nitrogen Bond Formation Involving Well-Defined Aryl-Copper(III) Complexes J. Am. Chem. Soc. 2008, 130, 9196-9197
47. Huffman, L. M.; Stahl, S. S. Mechanistic Analysis of trans C-N Reductive Elimination from a Square-Planar Macrocyclic Aryl-Copper(III) Complex Dalton Trans. 2011, 40, 8959-8963
48. Huffman, L. M.; Casitas, A.; Font, M.; Canta, M.; Costas, M.; Ribas, X.; Stahl, S. S. Observation and Mechanistic Study of Facile C-O Bond Formation between a Well-Defined Aryl-Copper(III) Complex and Oxygen Nucleophiles Chem.-Eur. J. 2011, 17, 10643-10650
49. Furuta, H.; Maeda, H.; Osuka, A. Doubly N-Confused Porphyrin: A New Complexing Agent Capable of Stabilizing Higher Oxidation States J. Am. Chem. Soc. 2000, 122, 803-807
50. Wang, Z.-L.; Zhao, L.; Wang, M.-X. Regiospecific Functionalization of Azacalixaromatics through Copper-Mediated Aryl C-H Activation and C-O Bond Formation Org. Lett. 2011, 13, 6560-6563
51. Zhang, H.; Yao, B.; Zhao, L.; Wang, D.-X.; Xu, B.-Q.; Wang, M.-X. Direct Synthesis of High-Valent Aryl-Cu(II) and Aryl-Cu(III) Compounds: Mechanistic Insight into Arene C-H Bond Metalation J. Am. Chem. Soc. 2014, 136, 6326-6332
52. King, A. E.; Huffman, L. M.; Casitas, A.; Costas, M.; Ribas, X.; Stahl, S. S. Copper-Catalyzed Aerobic Oxidative Functionalization of an Arene C-H Bond: Experimental Evidence for an Aryl-Copper(III) Intermediate J. Am. Chem. Soc. 2010, 132, 12068-12073
53. Casitas, A.; King, A. E.; Parella, T.; Costas, M.; Stahl, S. S.; Ribas, X. Direct Observation of CuI/CuIII Redox Steps Relevant to Ullmann-Type Coupling Reactions Chem. Sci. 2010, 1, 326-330
54. Suess, A. M.; Ertem, M. Z.; Cramer, C. J.; Stahl, S. S. Divergence between Organometallic and Single-Electron-Transfer Mechanisms in Copper(II)-Mediated Aerobic C-H Oxidation J. Am. Chem. Soc. 2013, 135, 9797-9804
55. Daugulis, O.; Do, H.-Q.; Shabashov, D. Palladium- and Copper-Catalyzed Arylation of Carbon-Hydrogen Bonds Acc. Chem. Res. 2009, 42, 1074-1086
56. Rouquet, G.; Chatani, N. Catalytic Functionalization of C(sp2)-H and C(sp3)-H Bonds by Using Bidentate Directing Groups Angew. Chem., Int. Ed. 2013, 52, 11726-11743
57. Roane, J.; Daugulis, O. Copper-Catalyzed Etherification of Arene C-H Bonds Org. Lett. 2013, 15, 5842-5845
58. Wang, Z.; Ni, J.; Kuninobu, Y.; Kanai, M. Copper-Catalyzed Intramolecular C(sp3)-H and C(sp2)-H Amidation by Oxidative Cyclization Angew. Chem., Int. Ed. 2014, 53, 3496-3499
59. Ye, X.; Johnson, M. D.; Diao, T.; Yates, M. H.; Stahl, S. S. Development of Safe and Scalable Continuous-Flow Methods for Palladium-Catalyzed Aerobic Oxidation Reactions Green Chem. 2010, 12, 1180-1186
60. Semmelhack, M. F.; Schmid, C. R.; Cortés, D. A.; Chou, C. S. Oxidation of Alcohols to Aldehydes with Oxygen and Cupric Ion, Mediated by Nitrosonium Ion J. Am. Chem. Soc. 1984, 106, 3374-3376
61. Gamez, P.; Arends, I. W. C. E.; Sheldon, R. A.; Reedijk, J. Room Temperature Aerobic Copper-Catalysed Selective Oxidation of Primary Alcohols to Aldehydes Adv. Synth. Catal. 2004, 346, 805-811
62. Kumpulainen, E. T. T.; Koskinen, A. M. P. Catalytic Activity Dependency on Catalyst Components in Aerobic Copper-TEMPO Oxidation Chem.-Eur. J. 2009, 15, 10901-10911
63. Hoover, J. M.; Stahl, S. S. Highly Practical Copper(I)/TEMPO Catalyst System for Chemoselective Aerobic Oxidation of Primary Alcohols J. Am. Chem. Soc. 2011, 133, 16901-16910
64. Hoover, J. M.; Steves, J. E.; Stahl, S. S. Copper(I)/TEMPO-Catalyzed Aerobic Oxidation of Primary Alcohols to Aldehydes with Ambient Air Nat. Protoc. 2012, 7, 1161-1166
65. Hoover, J. M.; Ryland, B. L.; Stahl, S. S. Mechanism of Copper(I)/TEMPO-Catalyzed Aerobic Alcohol Oxidation J. Am. Chem. Soc. 2013, 135, 2357-2367
66. Hoover, J. M.; Ryland, B. L.; Stahl, S. S. Copper/TEMPO-Catalyzed Aerobic Alcohol Oxidation: Mechanistic Assessment of Different Catalyst Systems ACS Catal. 2013, 3, 2599-2605
67. Dijksman, A.; Arends, I. W. C. E.; Sheldon, R. A. Cu(II)-Nitroxyl Radicals as Catalytic Galactose Oxidase Mimics Org. Biomol. Chem. 2003, 1, 3232-3237
68. Belanzoni, P.; Michel, C.; Baerends, E. J. Cu(bipy)2+/TEMPO-Catalyzed Oxidation of Alcohols: Radical or Nonradical Mechanism? Inorg. Chem. 2011, 50, 11896-11904
69. Steves, J. E.; Stahl, S. S. Copper(I)/ABNO-Catalyzed Aerobic Alcohol Oxidation: Alleviating Steric and Electronic Constraints of Cu/TEMPO Catalyst Systems J. Am. Chem. Soc. 2013, 135, 15742-15745
70. Sasano, Y.; Nagasawa, S.; Yamazaki, M.; Shibuya, M.; Park, J.; Iwabuchi, Y. Highly Chemoselective Aerobic Oxidation of Amino Alcohols into Amino Carbonyl Compounds Angew. Chem., Int. Ed. 2014, 53, 3236-3240
71. Rogan, L.; Hughes, N. L.; Cao, Q.; Dornan, L. M.; Muldoon, M. J. Copper(I)/ketoABNO Catalysed Aerobic Alcohol Oxidation Catal. Sci. Technol. 2014, 4, 1720-1725
72. Ryland, B. L.; McCann, S. D.; Brunold, T. C.; Stahl, S. S. Mechanism of Alcohol Oxidation Mediated by Copper(II) and Nitroxyl Radicals J. Am. Chem. Soc. 2014, 136, 12166-12173
73. Xie, X.; Stahl, S. S. Efficient and Selective Cu/Nitroxyl-Catalyzed Methods for Aerobic Oxidative Lactonization of Diols J. Am. Chem. Soc. 2015, 137, 3767-3770
74. Kim, J.; Stahl, S. S. Cu/Nitroxyl-Catalyzed Aerobic Oxidation of Primary Amines into Nitriles at Room Temperature ACS Catal. 2013, 3, 1652-1656