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Singlet oxygen-mediated selective C-H bond hydroperoxidation of ethereal hydrocarbons
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Singlet oxygen-mediated selective C-H bond hydroperoxidation of ethereal hydrocarbons

Arunachalam Sagadevan, Kuo Chu Hwang 和 Ming-Der Su
Nature communications, 卷.8(1), 頁碼.1812-8
27/11/2017
PMID: 29180784
Web of Science ID: WOS:000416293600028

摘要

Multidisciplinary Sciences Science & Technology Science & Technology - Other Topics
Singlet O-2 is a key reactive oxygen species responsible for photodynamic therapy and is generally recognized to be chemically reactive towards C=C double bonds. Herein, we report the hydroperoxidation/lactonization of alpha-ethereal C-H bonds by singlet O-2 ((1)Delta(g)) under exceptionally mild conditions, i.e., room temperature and ambient pressure, with modest to high yields (38 similar to 90%) and excellent site selectivity. Singlet O-2 has been known for > 90 years, but was never reported to be able to react with weakly activated C-H bonds in saturated hydrocarbons. Theoretical calculations indicate that singlet O-2 directly inserts into the alpha-ethereal C-H bond in one step with conservation of steric configuration in products. The current discovery of chemical reaction of singlet oxygen with weakly activated solvent C-H bonds, in addition to physical relaxation pathway, provides an important clue to a 35-year-old unresolved mystery regarding huge variations of solvent dependent lifetime of singlet O-2.

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https://doi.org/10.1038/s41467-017-01906-5檢視
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