Aminoacylation of Alkenes by Cooperative NHC and Photoredox Catalysis

Lena Lezius; Jannik Reimler; Nadine Döben; Michael Hamm; Constantin G. Daniliuc; Armido Studer

doi:10.1055/a-2145-8697

Synlett, Table of Contents

Synlett 2024; 35(04): 445-450
DOI: 10.1055/a-2145-8697

cluster

11th Singapore International Chemistry Conference (SICC-11)

Aminoacylation of Alkenes by Cooperative NHC and Photoredox Catalysis

Lena Lezius‡

,

Jannik Reimler‡

,

Nadine Döben

,

Michael Hamm

,

Constantin G. Daniliuc

,

Armido Studer ∗

Abstract

All articles of this category

Abstract

Cooperative NHC and photoredox catalysis has gained significant attention as an emerging research field in recent years. Herein, we report a cyclizing aminoacylation of alkenes, which is enabled through the combination of these two catalytic modes. The key step is a radical/radical cross-coupling between a persistent ketyl radical and a transient benzylic or aliphatic C-radical, which is generated through radical cyclization of an oxidatively formed amidyl radical. Several carbamates, amides and sulfonamides containing an alkene moiety and different acyl fluorides can be used as substrates. The resulting products are obtained in moderate to good yields.

Key words

NHC catalysis - photoredox catalysis - radical cyclization - radical acylation - nitrogen radicals

Full Text

References

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20 Aminoacylation of Alkenes; General Procedure 4CzIPN (1.6 mg, 2.0 μmol, 2.0 mol%), the NHC precursor A (6.3 mg, 20 μmol, 20 mol%), Cs₂CO₃ (65.2 mg, 0.200 mmol, 2.0 equiv.), an alkene (if solid, 0.10 mmol, 1.0 equiv.) and an acyl fluoride (if solid, 0.40 mmol, 4.0 equiv.) were added to a Schlenk tube. Afterwards, the tube was evacuated and refilled with Ar three times. An alkene (if liquid, 0.10 mmol, 1.0 equiv.), an acyl fluoride (if liquid, 0.40 mmol, 4.0 equiv.) and DCM (1.0 mL) were added and the reaction mixture was degassed via two freeze-pump-thaw cycles. The mixture was irradiated with a 456 nm LED for 48 h. After that time, the crude product was purified by column chromatography (SiO₂, Et₂O/pentane).
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