Premium
Oxyfunctionalization of Active Methylene Compounds Using Sodium Chlorite in Water
Author(s) -
Kitanosono Taku,
Tani Shinki,
Kobayashi Shū
Publication year - 2018
Publication title -
asian journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.846
H-Index - 44
eISSN - 2193-5815
pISSN - 2193-5807
DOI - 10.1002/ajoc.201700646
Subject(s) - chemistry , sodium chlorite , methylene , chlorine dioxide , acetonitrile , aqueous solution , redox , methylene blue , selectivity , chlorite , organic chemistry , photochemistry , combinatorial chemistry , catalysis , photocatalysis , paleontology , quartz , biology
A methylene group inserted between proximal carbonyl groups underwent exclusive oxyfunctionalization with sodium chlorite in the presence of redox‐inert Hf IV in water. Direct oxidation methods have conventionally suffered from manifold side reactions such as oxidative fragmentation, dimerization, and overreactions, together with the use of toxic and intractable oxidants. Although alternative routes involving prior α‐functionalization can be executed under mild conditions, preparatively valuable oxidation methods that deliver high levels of both conversion and selectivity remain a prized goal from the standpoint of streamlining organic synthesis. Chlorine dioxide, which was generated as a yellowish gas during the reaction, is considered to be a bona fide oxidant against active methylene compounds. The pivotal role of water was clear, given that the reaction was significantly retarded in both aqueous acetonitrile and ethanol, which can solubilize sodium chlorite.