Premium
One‐Pot Synthesis of Diazirines and 15 N 2 ‐Diazirines from Ketones, Aldehydes and Derivatives: Development and Mechanistic Insight
Author(s) -
Ibert Quentin,
Cauwel Madeleine,
Glachet Thomas,
Tite Tony,
Le NahenecMartel Patricia,
Lohier JeanFrançois,
Renard PierreYves,
Franck Xavier,
Reboul Vincent,
Sabot Cyrille
Publication year - 2021
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.202100679
Subject(s) - diazirine , chemistry , imine , trifluoromethylation , combinatorial chemistry , organic chemistry , ammonia , methanol , trifluoromethyl , photochemistry , catalysis , alkyl
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 (NH 3 ) 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 15 N 2 ‐diazirine with complete 15 N 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%.