Triplet Energy Transfer Mechanism in Copper Photocatalytic N‐ and O‐Methylation

Triplet Energy Transfer Mechanism in Copper Photocatalytic N‐ and O‐Methylation

Methylation reactions are chemically simple but challenging to perform under mild and non‐toxic conditions. A photochemical energy transfer strategy was merged with copper catalysis to enable fast reaction times of minutes and broad applicability to N‐heterocycles, (hetero−)aromatic carboxylic acids...

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Bibliographic Details
Published in:Chemistry : a European journal Vol. 30; no. 22; pp. e202400560 - n/a
Main Authors: Hoving, Martijn, Haaksma, Jacob‐Jan, Stoppel, Anne, Chronc, Lukas, Hoffmann, Jonas, Beil, Sebastian B.
Format: Journal Article
Language:English
Published: Germany Wiley Subscription Services, Inc 16-04-2024
Subjects:
Carboxylic acids
Catalysis
Copper
copper catalysis
Energy transfer
Functional groups
hypervalent iodine
Iodine
Methylation
photocatalysis
Photochemicals
Reagents
copper catalysis photocatalysis energy transfer methylation hypervalent iodine
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Summary:Methylation reactions are chemically simple but challenging to perform under mild and non‐toxic conditions. A photochemical energy transfer strategy was merged with copper catalysis to enable fast reaction times of minutes and broad applicability to N‐heterocycles, (hetero−)aromatic carboxylic acids, and drug‐like molecules in high yields and good functional group tolerance. Detailed mechanistic investigations, using kinetic analysis, aprotic MS, UV/Vis, and luminescence quenching experiments revealed a triplet‐triplet energy transfer mechanism between hypervalent iodine(III) reagents and readily available photosensitizers. We investigated the photochemical energy transfer mechanism of hypervalent iodine reagents. When coupled to copper catalysis we achieved successful methylation of a diverse set of N‐heterocycles and (hetero−)aromatic carboxylic acids. In addition, we could show application of this methodology to more complex active pharmaceutical intermediates. Mechanistic investigations support our observations and provide the basis for future developments.
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ISSN:0947-6539
1521-3765
DOI:10.1002/chem.202400560