Synthesis of Carbamoyl Azides from Redox-Active Esters and TMSN3
Xiaobin Yuan, Yanjie Qu, Yajun Li*, Hongli Bao*
*Fujian Institute of Research on the Structure of Matter,
University of CAS, 155 Yangqiao Road West, Fuzhou, Fujian 350002, P. R. China,
Email: liyajun
fjirsm.ac.cn, hlbaofjirsm.ac.cn
X. Yuan, Y. Qu, Y. Li, H. Bao, Synlett, 2024, 35, 464-468.
DOI: 10.1055/a-2106-5108
Abstract
A convenient, iron-catalyzed azidation of N-hydroxy phthalimide (NHP) esters provides carbamoyl azides with good substrate scope and functional group tolerance. Mechanistic studies were conducted and a two-stage process was identified.
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Details
The document details a study on the synthesis of carbamoyl azides from redox-active esters and TMSN3, conducted by researchers from Fujian Normal University and the Chinese Academy of Sciences. The method involves an iron-catalyzed azidation of N-hydroxy phthalimide (NHP) esters, providing a convenient approach for constructing C–N bonds. This process is significant for synthesizing amines, which are crucial in organic synthesis and bioactive lead discovery. The study highlights the challenges of forming C(sp3)–N bonds under classical conditions and presents an alternative nucleophilic substitution process. The optimal reaction conditions were identified as using ferric acetate in THF at 70°C under nitrogen. The method shows good substrate scope and functional group tolerance, achieving up to 96% yield. Mechanistic studies suggest a two-stage process involving the formation of carbonyl azide intermediates, which then undergo Curtius rearrangement to form carbamoyl azides. The research demonstrates the method's applicability to various NHP esters, including derivatives from bioactive compounds, and provides insights into the reaction mechanism. The study was supported by several grants from the National Natural Science Foundation of China and other research programs.
Key Words
redox-active esters, iron catalysis, NHP esters, azidation, carbamoyl azides, urea derivatives, Curtius rearrangement
ID: J72-Y2024
