Synthesis of Carbamoyl Azides from Redox-Active Esters and TMSN3

Xiaobin Yuan; Yanjie Qu; Yajun Li; Hongli Bao

doi:10.1055/a-2106-5108

Synlett, Table of Contents

Synlett 2024; 35(04): 464-468
DOI: 10.1055/a-2106-5108

cluster

11th Singapore International Chemistry Conference (SICC-11)

Synthesis of Carbamoyl Azides from Redox-Active Esters and TMSN₃

Xiaobin Yuan

^aCollege of Chemistry and Materials Science, Fujian Normal University, Fuzhou 350117, P. R. of China

^bKey Laboratory of Coal to Ethylene Glycol and Its Related Technology, State Key Laboratory of Structural Chemistry, Center for Excellence in Molecular Synthesis, Chinese Academy of Sciences, 155 Yangqiao Road West, Fujian, Fuzhou 350002, P. R. of China

,

Yanjie Qu

^aCollege of Chemistry and Materials Science, Fujian Normal University, Fuzhou 350117, P. R. of China

^bKey Laboratory of Coal to Ethylene Glycol and Its Related Technology, State Key Laboratory of Structural Chemistry, Center for Excellence in Molecular Synthesis, Chinese Academy of Sciences, 155 Yangqiao Road West, Fujian, Fuzhou 350002, P. R. of China

,

Yajun Li∗

^bKey Laboratory of Coal to Ethylene Glycol and Its Related Technology, State Key Laboratory of Structural Chemistry, Center for Excellence in Molecular Synthesis, Chinese Academy of Sciences, 155 Yangqiao Road West, Fujian, Fuzhou 350002, P. R. of China

,

Hongli Bao ∗

^bKey Laboratory of Coal to Ethylene Glycol and Its Related Technology, State Key Laboratory of Structural Chemistry, Center for Excellence in Molecular Synthesis, Chinese Academy of Sciences, 155 Yangqiao Road West, Fujian, Fuzhou 350002, P. R. of China

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Abstract

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Abstract

An efficient method for construction of C–N bonds is reported here. The iron-catalyzed azidation of N-hydroxy phthalimide (NHP) esters provides a convenient approach for the synthesis of carbamoyl azides with good substrate scope and functional group tolerance. Both aryl carbon C(sp²) and alkyl carbon C(sp³) sources can be used deliver the carbamoyl azides. Mechanistic studies were conducted and a two-stage process was identified.

Key words

redox-active esters - iron catalysis - NHP esters - azidation - carbamoyl azides

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References

References and Notes

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15 Typical Procedure: A flame-dried reaction tube with a magnetic stirring bar was charged with NHP ester 1a (0.5 mmol, 133 mg), ferric acetate (10 mol%, 9.5 mg) and THF (5.0 mL) under a nitrogen atmosphere. TMSN₃ (1.5 mmol, 0.2 mL) was then injected into the tube and the mixture was heated at 70 °C (oil bath) for 24 h. After reaction completion as detected by TLC, the solid was removed by filtration and the filtrate was concentrated. The residue was purified by column chromatography (silica gel, PE/EtOAc = 10:1) to afford the carbamoyl azide 2a (73.7 mg, 91% yield) as a white solid; mp 105–106 °C. ¹H NMR (600 MHz, CDCl₃): δ = 7.42 (d, J = 8.1 Hz, 2 H), 7.35–7.31 (m, 2 H), 7.12 (t, J = 7.4 Hz, 1 H), 6.83 (br, 1 H). ¹³C NMR (151 MHz, CDCl₃): δ = 154.00, 136.95, 129.31, 124.75, 119.27.

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