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Hypervalent Iodine-mediated/Catalyzed Oxidative Cycloisomerization/Annulation of Alkynes for Metal-free Synthesis of Oxazoles

[ Vol. 24 , Issue. 18 ]

Author(s):

Akio Saito*   Pages 2048 - 2069 ( 22 )

Abstract:


Since oxazoles have found widespread applications not only as synthetic intermediates but also as biologically active compounds, much effort has been focused on developing novel and efficient methods for the synthesis of this heterocycle. From the viewpoint of green and sustainable chemistry, hypervalent iodine and other halogen reagents have gained increasing popularity in metal-free oxidative transformation due to their low toxicity, transition-metal-like reactivity, high stability, easy handling and other benefits. In this account, our two approaches to the metal-free synthesis of oxazoles by means of a peculiar activation of alkynes by iodine species are described with the related contexts. One is iodine(III)-mediated/catalyzed oxidative cycloisomerization reactions of N-propargyl amides for the preparation of oxazoles bearing various functional groups at their side chains. In these reactions, iodine(III) species works as a donor of various heteroatomic functional groups as well as an activator of carbon-carbon triple bonds in a single step. Furthermore, this methodology can be extended to iodine(III)-mediated/catalyzed oxidative annulation of alkynes and nitriles as another approach, in which heteroatoms on iodine(III) species are incorporated in the azole rings.

Keywords:

Alkyne, annulation, cyclization, hypervalent iodine, metal-free method, oxazole.

Affiliation:

Division of Applied Chemistry, Institute of Engineering, Tokyo University of Agriculture and Technology, Tokyo

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