C−H Functionalization of Heterocycles with Triplet Carbenes by means of an Unexpected 1,2‐Alkyl Radical Migration **

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Abstract: The C−H functionalization of indole heterocycles constitutes a key strategy to leverage the synthesis of endogenous signaling molecules such as tryptamine or tryptophol. Herein, we report on the photocatalytic reaction of ethyl diazoacetate with indole, which shows an unusual solvent dependency. While C2‐functionalization occurs under protic conditions, the use of aprotic solvents leads to a complete reversal of selectivity and exclusive C3‐functionalization occurs. To rationalize for this unexpected reactivity switch, we have conducted detailed theoretical and experimental studies, which suggest the participation of a triplet carbene intermediate that undergoes initial C2‐functionalization. A distinct cationic [1,2]‐alkyl radical migration then leads to formation of C3‐functionalized indole. We conclude with the application of this photocatalytic reaction to access oxidized tryptophol derivatives including gram‐scale synthesis and derivatization reactions.

Location: Deutsche Nationalbibliothek Frankfurt am Main

Extent: Online-Ressource

Language: Englisch

Bibliographic citation: C−H Functionalization of Heterocycles with Triplet Carbenes by means of an Unexpected 1,2‐Alkyl Radical Migration ** ; day:13 ; month:04 ; year:2023 ; extent:8
Chemistry - a European journal ; (13.04.2023) (gesamt 8)

Creator: Empel, Claire
Jana, Sripati
Ciszewski, Łukasz W.
Zawada, Katarzyna
Pei, Chao
Gryko, Dorota
Koenigs, Rene M.

DOI: 10.1002/chem.202300214

URN: urn:nbn:de:101:1-2023041415022317614969

Rights: Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.

Last update: 14.08.2025, 10:48 AM CEST

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Associated

Empel, Claire
Jana, Sripati
Ciszewski, Łukasz W.
Zawada, Katarzyna
Pei, Chao
Gryko, Dorota
Koenigs, Rene M.

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