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Article: Chiral Iron Porphyrins Catalyze Enantioselective Intramolecular C(sp3)−H Bond Amination Upon Visible-Light Irradiation

TitleChiral Iron Porphyrins Catalyze Enantioselective Intramolecular C(sp3)−H Bond Amination Upon Visible-Light Irradiation
Authors
KeywordsAmination
Asymmetric Catalysis
Iron
Photocatalysis
Porphyrins
Issue Date16-Feb-2023
PublisherWiley
Citation
Angewandte Chemie International Edition, 2023, v. 62, n. 19 How to Cite?
Abstract

Iron-catalyzed asymmetric amination of C(sp(3))-H bonds is appealing for synthetic applications due to the biocompatibility and high earth abundance of iron, but examples of such reactions are sparse. Herein we describe chiral iron complexes of meso- and beta-substituted-porphyrins that can catalyze asymmetric intramolecular C(sp(3))-H amination of aryl and arylsulfonyl azides to afford chiral indolines (29 examples) and benzofused cyclic sulfonamides (17 examples), respectively, with up to 93 % ee (yield: up to 99 %) using 410 nm light under mild conditions. Mechanistic studies, including DFT calculations, for the reactions of arylsulfonyl azides reveal that the Fe(NSO2Ar) intermediate generated in situ under photochemical conditions reacts with the C(sp(3))-H bond through a stepwise hydrogen atom transfer/radical rebound mechanism, with enantioselectivity arising from cooperative noncovalent interactions between the Fe(NSO2Ar) unit and the peripheral substituents of the chiral porphyrin scaffold.


Persistent Identifierhttp://hdl.handle.net/10722/331369
ISSN
2023 Impact Factor: 16.1
2023 SCImago Journal Rankings: 5.300
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorWang, HH-
dc.contributor.authorShao, H-
dc.contributor.authorHuang, GL-
dc.contributor.authorFan, JQ-
dc.contributor.authorTo, WP-
dc.contributor.authorDang, L-
dc.contributor.authorLiu, YE-
dc.contributor.authorChe, CM-
dc.date.accessioned2023-09-21T06:55:08Z-
dc.date.available2023-09-21T06:55:08Z-
dc.date.issued2023-02-16-
dc.identifier.citationAngewandte Chemie International Edition, 2023, v. 62, n. 19-
dc.identifier.issn1433-7851-
dc.identifier.urihttp://hdl.handle.net/10722/331369-
dc.description.abstract<p></p><p>Iron-catalyzed asymmetric amination of C(sp(3))-H bonds is appealing for synthetic applications due to the biocompatibility and high earth abundance of iron, but examples of such reactions are sparse. Herein we describe chiral iron complexes of meso- and beta-substituted-porphyrins that can catalyze asymmetric intramolecular C(sp(3))-H amination of aryl and arylsulfonyl azides to afford chiral indolines (29 examples) and benzofused cyclic sulfonamides (17 examples), respectively, with up to 93 % ee (yield: up to 99 %) using 410 nm light under mild conditions. Mechanistic studies, including DFT calculations, for the reactions of arylsulfonyl azides reveal that the Fe(NSO2Ar) intermediate generated in situ under photochemical conditions reacts with the C(sp(3))-H bond through a stepwise hydrogen atom transfer/radical rebound mechanism, with enantioselectivity arising from cooperative noncovalent interactions between the Fe(NSO2Ar) unit and the peripheral substituents of the chiral porphyrin scaffold.</p>-
dc.languageeng-
dc.publisherWiley-
dc.relation.ispartofAngewandte Chemie International Edition-
dc.rightsThis work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.-
dc.subjectAmination-
dc.subjectAsymmetric Catalysis-
dc.subjectIron-
dc.subjectPhotocatalysis-
dc.subjectPorphyrins-
dc.titleChiral Iron Porphyrins Catalyze Enantioselective Intramolecular C(sp3)−H Bond Amination Upon Visible-Light Irradiation-
dc.typeArticle-
dc.identifier.doi10.1002/anie.202218577-
dc.identifier.scopuseid_2-s2.0-85147992422-
dc.identifier.volume62-
dc.identifier.issue19-
dc.identifier.eissn1521-3773-
dc.identifier.isiWOS:000937297300001-
dc.identifier.issnl1433-7851-

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