Hypervalent Iodine‐Mediated Azidation Reactions

• Published in: European journal of organic chemistry 2022-09, Vol.2022 (34), p.n/a
• Main Authors: Mironova, Irina A., Kirsch, Stefan F., Zhdankin, Viktor V., Yoshimura, Akira, Yusubov, Mekhman S.
• Format: Article
• Language: English
• Subjects: Azidation; Azide; Azides (organic); Carbon; Hypervalent compounds; Hypervalent iodine; Iodine; Reagents; Sodium azides; Substrates
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/ejoc.202200754

Organic azides have found wide application in various fields of science and technology. This review summarizes recently developed approaches to the direct, one‐step synthesis of diverse organic azides utilizing hypervalent iodine reagents. The first part of review deals with the azidation using unstable azidoiodinanes generated in situ from common hypervalent iodine reagents (such as diacetoxyiodobenzene or iodosylbenzene) and a source of azide anion (TMSN3 or NaN3). The second part of review is dedicated to the application of stable azidobenziodoxoles as useful azidating reagents that allow selective direct azidation of C−H bonds or double carbon‐carbon bonds under mild reaction conditions. The use of azidobenziodoxoles eliminates the main disadvantages of the traditional approaches to organic azides, such as the need in pre‐functionalization of organic substrates and harsh reaction conditions. Synthetic application of azidobenziodoxoles made possible direct selective azidation of a plethora of organic substrates including complex molecules at the late synthetic stage. Recently developed approaches to direct, one‐step synthesis of various organic azides using hypervalent iodine reagents are summarized. Particularly useful azidating reagents are the stable azidobenziodoxoles that allow selective direct azidation of C−H single bonds or carbon‐carbon double bonds under mild reaction conditions.