One-Pot Synthesis of Diazirines and N-15(2)-Diazirines from Ketones, Aldehydes and Derivatives: Development and Mechanistic Insight

Broad scope one-pot diazirine synthesis strategies have been developed using two different oxidants depending on the nature of the starting material. In all cases, an inexpensive commercial solution of ammonia (NH3) in methanol (MeOH) was employed, avoiding the difficult use of liquid ammonia. With...

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Published inAdvanced synthesis & catalysis Vol. 363; no. 18; pp. 4390 - 4398
Main Authors Ibert, Quentin, Cauwel, Madeleine, Glachet, Thomas, Tite, Tony, Le Nahenec-Martel, Patricia, Lohier, Jean-Francois, Renard, Pierre-Yves, Franck, Xavier, Reboul, Vincent, Sabot, Cyrille
Format Journal Article
LanguageEnglish
Published WEINHEIM Wiley 21.09.2021
Subjects
Chemistry
Chemistry, Applied
Chemistry, Organic
Physical Sciences
Science & Technology
TARGET
PIDA
diazirine
IMINES
PHOTO-CROSS-LINKERS
DIAZIRIDINES
ammonia
t-BuOCl
CELL
diaziridine
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Summary:Broad scope one-pot diazirine synthesis strategies have been developed using two different oxidants depending on the nature of the starting material. In all cases, an inexpensive commercial solution of ammonia (NH3) in methanol (MeOH) was employed, avoiding the difficult use of liquid ammonia. With aliphatic ketones, t-butyl hypochlorite (t-BuOCl) was found to be the best oxidant whereas it is preferable to use phenyliodine diacetate (PIDA) with aromatic ketones, aldehydes and imines. The nature of the imine-protecting group is essential and only t-butyl imine allowed the synthesis of N-15(2)-diazirine with complete N-15 incorporation, emphasizing a key trans-imination step in the reaction mechanism. These methods are operationally simple, and tolerant to most functional groups, providing diazirines with yields ranging from 20 to 99%.
ISSN:1615-4150
1615-4169
DOI:10.1002/adsc.202100679