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Generation of N-Centered Radicals via a Photocatalytic Energy Transfer: Remote Double Functionalization of Arenes Facilitated by Singlet Oxygen

Title
Generation of N-Centered Radicals via a Photocatalytic Energy Transfer: Remote Double Functionalization of Arenes Facilitated by Singlet Oxygen
Authors
Soni, Vineet KumarHwang, Ho SeongMoon, Yu KyungPark, Sung-WooYou, YoungminCho, Eun Jin
Ewha Authors
유영민
SCOPUS Author ID
유영민scopus
Issue Date
2019
Journal Title
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
ISSN
0002-7863JCR Link
Citation
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY vol. 141, no. 26, pp. 10538 - 10545
Publisher
AMER CHEMICAL SOC
Indexed
SCI; SCIE; SCOPUS WOS
Document Type
Article
Abstract
An unprecedented approach to the generation of an N-centered radical via a photocatalytic energy-transfer process from readily available heterocyclic precursors is reported, which is distinctive of the previous electron transfer approaches. In combination with singlet oxygen, the in-situ-generated nitrogen radical from the oxadiazoline substrate in the presence of fac-Ir(ppy)(3) undergoes a selective ipso addition to arenes to furnish remotely double-functionalized Spiro-azalactam products. The mechanistic studies provide compelling evidence that the catalytic cycle selects the energy-transfer pathway. A concurrent activation of molecular oxygen to generate singlet oxygen by energy transfer is also rationalized. Furthermore, the occurrence of the electron transfer phenomenon is excluded on the basis of the negative driving forces for one-electron transfer between oxadiazoline and the excited state of fac-Ir(ppy)(3) with a consideration of their redox potentials. The necessity of singlet oxygen as well as the photoactivated oxadiazoline substrate is clearly supported by a series of controlled experiments. Density functional studies have also been carried out to support these observations. The scope of substrates is explored by synthesizing diversely functionalized cyclohexadienone moieties in view of their utility in complex organic syntheses and as potential targets in pharmacology.
DOI
10.1021/jacs.9b05572
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엘텍공과대학 > 화학신소재공학전공 > Journal papers
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