Chemo- and Enantioselective Oxidative α-Azidation of Carbonyl Compounds
We report high-performance I+/H2O2 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+/H2O2 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.
Hattori, Yuhei,Ishihara, Kazuaki,Sahara, Naoto,Tsukahara, Mayuko,Uyanik, Muhammet
p. 17110 - 17117
(2020/08/10)
β-Deuterium Secondary Isotope Effects in Heterolytic Decarboxylation Reactions. Manifestations of Negative Hyperconjugation
Although β-deuterium kinetic isotope effects have been recognized as useful probes of transition-state strucutures in cabanion-forming reactions, measurements of these effects in heterolytic decarboxylation reactions have not previously been reported.In t
Kluger, Ronald,Brandl, Michael
p. 3964 - 3968
(2007/10/02)
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