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Synthesis 2018; 50(24): 4715-4745
DOI: 10.1055/s-0037-1610297
review
© Georg Thieme Verlag Stuttgart · New York

Advances in Catalytic Aerobic Oxidations by Activation of Dioxygen-Monooxygenase Enzymes and Biomimetics

Marina Petsi
,
Alexandros L. Zografos  *
Aristotle University of Thessaloniki, Department of Chemistry, Laboratory of Organic Chemistry, Main Campus, Thessaloniki, 54124, Greece   Email: alzograf@chem.auth.gr
› Author AffiliationsThis work was supported by the project ‘OPENSCREEN-GR’ (MIS 5002691) which is implemented under the Action ‘Reinforcement of the Research and Innovation Infrastructure’, funded by the Operational Program ‘Competitiveness, Entrepreneurship and Innovation’ (NSRF 2014-2020) and co-financed by Greece and the European Union (European Regional Development Fund). Part of the project was inspired by helpful discussions within CH-Activation in Organic Synthesis COST Action CA15106.
Further Information

Publication History

Received: 23 July 2018

Accepted after revision: 03 September 2018

Publication Date:
15 October 2018 (online)

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Abstract

Monooxygenases are not only some of the most versatile machineries in our lives, but also some of the most explored enzymes in modern organic synthesis. They provide knowledge and inspiration on how the most abandoned oxidant, dioxygen, can be activated and utilized to deliver selective oxidations. This review presents an outline in the mechanisms that Nature uses to succeed in these processes and recent indicative examples on how chemists use this knowledge to develop selective oxidation protocols based on dioxygen as the terminal oxidant.

1 Introduction

2 Monooxygenases

2.1 Metal-Based Monooxygenases

2.1.1 Cytochromes

2.1.2 Copper-Dependent Monooxygenases

2.1.3 Heme-Independent Iron Monooxygenases

2.1.4 Pterin-Dependent Monooxygenases

2.2 Metal-Free Monooxygenases

2.2.1 Flavin-Dependent Monooxygenases

2.2.2 Systems without Cofactors

3 Biomimetic Aerobic Oxidations

3.1 Aerobic Oxidations Based on Metal Catalysts

3.1.1 Epoxidations and Allylic Oxidations

3.1.2 Oxidations of Unactivated Carbon Atoms and Benzylic Oxidations

3.1.3 Oxidations of Aryl Groups

3.1.4 Heteroatom Oxidations

3.2 Aerobic Oxidations Based on Organocatalysts

3.2.1 Baeyer–Villiger Oxidations

3.2.2 Oxidations of Aryl Groups

3.2.3 Heteroatom Oxidations

4 Conclusion

Key words

high-valent metal complexes - flavins - biomimetics - C–H oxidations - sustainable oxidations - green oxidations