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. 2012 Nov 14;134(45):18577-80.
doi: 10.1021/ja309635w. Epub 2012 Nov 5.

Direct catalytic anti-markovnikov hydroetherification of alkenols

David S Hamilton  1 , David A Nicewicz
Affiliations

Direct catalytic anti-markovnikov hydroetherification of alkenols

David S Hamilton et al. J Am Chem Soc. .

Abstract

A direct intramolecular anti-Markovnikov hydroetherification reaction of alkenols is described. By employing catalytic quantities of commercially available 9-mesityl-10-methylacridinium perchlorate and 2-phenylmalononitrile as a redox-cycling source of a H-atom, we report the anti-Markovnikov hydroetherification of alkenes with complete regioselectivity. In addition, we present results demonstrating that this novel catalytic system can be applied to the anti-Markovnikov hydrolactonization of alkenoic acids.

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Conflict of interest statement

Funding Sources

The authors declare no competing financial interests.

Figures

Scheme 1
Scheme 1
Divergent Regioselectivity in Alkene Addition reactions
Scheme 2
Scheme 2
Anti-Markovnikov Reactivity of Cation Radicals
Scheme 3
Scheme 3
Proposed Mechanism for the Anti-Markovnikov Hydroetherification of Alkenols
See this image and copyright information in PMC

References

    1. For comprehensive reviews on catalytic functionalization of olefins, see Beller M, Seavad J, Tillack A, Jiao H. Angew Chem Int Ed. 2004;43:3368.Hintermann L. Top Organomet Chem. 2010;31:123.Müller TE, Hultzsch KC, Yus M, Foubelo F, Tada M. Chem Rev. 2008;108:3795.

    1. Catalytic anti-Markovnikov additions of nucleophiles to olefins have been described as one of the “top 10 challenges for catalysis.” See: Haggin J. Chem Eng News. 1993;71:23.

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