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Chemo‐ and Enantioselective Oxidative α‐Azidation of Carbonyl Compounds
Author(s) -
Uyanik Muhammet,
Sahara Naoto,
Tsukahara Mayuko,
Hattori Yuhei,
Ishihara Kazuaki
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202007552
Subject(s) - enantioselective synthesis , chemistry , catalysis , oxidative coupling of methane , azide , oxidative phosphorylation , ammonium iodide , oxidative addition , combinatorial chemistry , isoindoline , reactivity (psychology) , iodide , radical , organic chemistry , medicine , biochemistry , alternative medicine , pathology
We report high‐performance I + /H 2 O 2 catalysis for the oxidative or decarboxylative oxidative α‐azidation of carbonyl compounds by using sodium azide under biphasic neutral phase‐transfer conditions. To induce higher reactivity especially for the α‐azidation of 1,3‐dicarbonyl compounds, we designed a structurally compact isoindoline‐derived quaternary ammonium iodide catalyst bearing electron‐withdrawing groups. The nonproductive decomposition pathways of I + /H 2 O 2 catalysis could be suppressed by the use of a catalytic amount of a radical‐trapping agent. This oxidative coupling tolerates a variety of functional groups and could be readily applied to the late‐stage α‐azidation of structurally diverse complex molecules. Moreover, we achieved the enantioselective α‐azidation of 1,3‐dicarbonyl compounds as the first successful example of enantioselective intermolecular oxidative coupling with a chiral hypoiodite catalyst.