Gutenberg Open Science: Two paths to oxidative C−H amination under basic conditions : a theoretical case study reveals hidden opportunities provided by electron upconversion

Please use this identifier to cite or link to this item: http://doi.org/10.25358/openscience-8700

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DC Field	Value	Language
dc.contributor.author	Eckhardt, Paul	-
dc.contributor.author	Elliot, Quintin	-
dc.contributor.author	Alabugin, Igor V.	-
dc.contributor.author	Opatz, Till	-
dc.date.accessioned	2023-01-30T08:26:42Z	-
dc.date.available	2023-01-30T08:26:42Z	-
dc.date.issued	2022	-
dc.identifier.uri	https://openscience.ub.uni-mainz.de/handle/20.500.12030/8716	-
dc.description.abstract	Traditionally, cross-dehydrogenative coupling (CDC) leads to C−N bond formation under basic and oxidative conditions and is proposed to proceed via a two-electron bond formation mediated by carbenium ions. However, the formation of such high-energy intermediates is only possible in the presence of strong oxidants, which may lead to undesired side reactions and poor functional group tolerance. In this work we explore if oxidation under basic conditions allows the formation of three-electron bonds (resulting in “upconverted” highly-reducing radical-anions). The benefit of this “upconversion” process is in the ability to use milder oxidants (e. g., O2) and to avoid high-energy intermediates. Comparison of the two- and three-electron pathways using quantum mechanical calculations reveals that not only does the absence of a strong oxidant shut down two-electron pathways in favor of a three-electron path but, paradoxically, weaker oxidants react faster with the upconverted reductants by avoiding the inverted Marcus region for electron transfer.	en_GB
dc.description.sponsorship	Gefördert durch die Deutsche Forschungsgemeinschaft (DFG) - Projektnummer 491381577	de
dc.language.iso	eng	de
dc.rights	CC BY-NC-ND	*
dc.rights.uri	https://creativecommons.org/licenses/by-nc-nd/4.0/	*
dc.subject.ddc	540 Chemie	de_DE
dc.subject.ddc	540 Chemistry and allied sciences	en_GB
dc.title	Two paths to oxidative C−H amination under basic conditions : a theoretical case study reveals hidden opportunities provided by electron upconversion	en_GB
dc.type	Zeitschriftenaufsatz	de
dc.identifier.doi	http://doi.org/10.25358/openscience-8700	-
jgu.type.dinitype	article	en_GB
jgu.type.version	Published version	de
jgu.type.resource	Text	de
jgu.organisation.department	FB 09 Chemie, Pharmazie u. Geowissensch.	de
jgu.organisation.number	7950	-
jgu.organisation.name	Johannes Gutenberg-Universität Mainz	-
jgu.rights.accessrights	openAccess	-
jgu.journal.title	Chemistry - a European journal	de
jgu.journal.volume	28	de
jgu.journal.issue	60	de
jgu.pages.alternative	e202201637	de
jgu.publisher.year	2022	-
jgu.publisher.name	Wiley-VCH	de
jgu.publisher.place	Weinheim	-
jgu.publisher.issn	1521-3765	de
jgu.organisation.place	Mainz	-
jgu.subject.ddccode	540	de
jgu.publisher.doi	10.1002/chem.202201637	de
jgu.organisation.ror	https://ror.org/023b0x485	-
jgu.subject.dfg	Naturwissenschaften	de
Appears in collections:	DFG-491381577-H

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