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Abstract 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 generatedin situfrom common hypervalent iodine reagents (such as diacetoxyiodobenzene or iodosylbenzene) and a source of azide anion (TMSN3or 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.
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A Physical Organic Approach towards Statistical Modeling of Tetrazole and Azide Decomposition**
Abstract Nitrogen atom‐rich heterocycles and organic azides have found extensive use in many sectors of modern chemistry from drug discovery to energetic materials. The prediction and understanding of their energetic properties are thus key to the safe and effective application of these compounds. In this work, we disclose the use of multivariate linear regression modeling for the prediction of the decomposition temperature and impact sensitivity of structurally diverse tetrazoles and organic azides. We report a data‐driven approach for property prediction featuring a collection of quantum mechanical parameters and computational workflows. The statistical models reported herein carry predictive accuracy as well as chemical interpretability. Model validation was successfully accomplished via tetrazole test sets with parameters generated exclusively in silico. Mechanistic analysis of the statistical models indicated distinct divergent pathways of thermal and impact‐initiated decomposition.
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- PAR ID:
- 10409191
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Angewandte Chemie International Edition
- Volume:
- 62
- Issue:
- 17
- ISSN:
- 1433-7851
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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