Medium-sized cyclic ethers are commonly encountered structural motifs in natural products, and as such, methods for their synthesis have been a long-standing pursuit. Although there are several approaches currently utilized to access these heterocycles, there were no methods to directly synthesize them from commonly encountered alcohols. Our lab has reported the transformation of commonly encountered benzylic, tertiary alcohol substrates into cyclic ethers, employing [bis(pyridinium)iodo]benzene ditriflate as the electrophilic activator. We now report the extension of this methodology to the oxidative rearrangement of a variety of alkyl, secondary alcohol substrates, which occurs with high chemoselectivity over direct oxidation of the alcohol. These reagents provide complimentary reactivity and selectivity to more traditional hypervalent iodine reagents, allowing access to a variety of cyclic ethers via direct activation of simple alcohols. (Poly)cationic hypervalent iodine reagents enable unique reactivity and represent a promising class of new synthetic reagents.

Synthesis of cyclic ethers via oxidative rearrangement with (poly)cationic hypervalent iodine reagents

254th National Meeting (2017)

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