Oxidase catalysis via aerobically generated hypervalent iodine intermediates
The development of sustainable oxidation chemistry demands strategies to harness O 2 as a terminal oxidant. Oxidase catalysis, in which O 2 serves as a chemical oxidant without necessitating incorporation of oxygen into reaction products, would allow diverse substrate functionalization chemistry to...
Gespeichert in:
Veröffentlicht in: | Nature chemistry 2018-02, Vol.10 (2), p.200-204 |
---|---|
Hauptverfasser: | , , |
Format: | Artikel |
Sprache: | eng |
Schlagworte: | |
Online-Zugang: | Volltext |
Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
Zusammenfassung: | The development of sustainable oxidation chemistry demands strategies to harness O
2
as a terminal oxidant. Oxidase catalysis, in which O
2
serves as a chemical oxidant without necessitating incorporation of oxygen into reaction products, would allow diverse substrate functionalization chemistry to be coupled to O
2
reduction. Direct O
2
utilization suffers from intrinsic challenges imposed by the triplet ground state of O
2
and the disparate electron inventories of four-electron O
2
reduction and two-electron substrate oxidation. Here, we generate hypervalent iodine reagents—a broadly useful class of selective two-electron oxidants—from O
2
. This is achieved by intercepting reactive intermediates of aldehyde autoxidation to aerobically generate hypervalent iodine reagents for a broad array of substrate oxidation reactions. The use of aryl iodides as mediators of aerobic oxidation underpins an oxidase catalysis platform that couples substrate oxidation directly to O
2
reduction. We anticipate that aerobically generated hypervalent iodine reagents will expand the scope of aerobic oxidation chemistry in chemical synthesis.
Oxidation chemistry is critical to introducing molecular complexity during chemical synthesis. Development of sustainable oxidation chemistry demands strategies to harness O
2
as a terminal oxidant. Access to hypervalent iodine compounds — a class of broadly useful chemical oxidants — from O
2
increases the scope of aerobic oxidation chemistry that can be achieved. |
---|---|
ISSN: | 1755-4330 1755-4349 |
DOI: | 10.1038/nchem.2873 |