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Synthesis 2025; 57(07): 1280-1294
DOI: 10.1055/a-2403-0760
DOI: 10.1055/a-2403-0760
short review
Enzymatic and Bio-Inspired Enantioselective Oxidation of Non-Activated C(sp 3)–H Bonds
Economic support from Spain, Ministry of Science (MINECO, PRE2019-090149 to AP, PGC2018-101737-B-I00 to M.C.), Generalitat de Catalunya (ICREA Academia to M.C., 2017 SGR-00264 and 2017 SGR-1707).
Abstract
The enantioselective oxidation of C–H bonds relies on two different approaches: the use of enzymes or bio-inspired transition metal catalysts. Both are powerful tools, as they transform ubiquitous C(sp3)–H bonds into valuable oxygenated building blocks. However, the reaction remains a challenge in synthetic chemistry, continuously demanding efficient catalytic systems to improve substrate scopes. Optimization of site- and enantioselectivities in bio-catalytic systems is underpinned by protein engineering, while ligand design and medium effects play crucial roles in bio-inspired synthetic complexes. In this Short Review, recent advances in the field are described, focusing on reactions that target strong, non-activated C–H bonds.
1 Introduction
1.1 Enantioselective Catalytic C–H Oxidation in Nature and Bio-Inspired Systems
1.2 Biological C–H Oxidation Mechanism and Challenges for the Implementation of Chirality with Synthetic Catalysts
1.3 Bio-Catalytic C–H Oxidation Systems: From Microorganism to Engineered Enzymes
1.4 Mimicking Nature: The Bio-Inspired C–H Oxidation Approach
1.5 Origin of Enantioselectivity
2 Enantioselective C–H Oxidation of Non-Activated C–H Bonds
2.1 Hydroxylation at Non-Activated C–H Bonds by Bio-Catalytic Systems
2.2 Enantioselective C–H Lactonization with Enzymatic Systems
2.3 Oxidation at Non-Activated C–H Bonds by Synthetic Catalysts
2.4 Enantioselective Lactonization with Small-Molecule Catalysts
3 Conclusions
Key words
cytochrome P450 - enantioselectivity - oxidation - bio-inspired catalysts - C–H bond functionalization - hydrogen atom transfer - H2O2 - oxygenases - aliphatic C–H hydroxylationPublication History
Received: 16 July 2024
Accepted after revision: 26 August 2024
Accepted Manuscript online:
26 August 2024
Article published online:
07 October 2024
© 2024. Thieme. All rights reserved
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