Remarkable temperature effect on intramolecular [3+2] cyclization

doi:10.1016/j.tetlet.2009.07.030

Tetrahedron Letters

Volume 50, Issue 37, 16 September 2009, Pages 5283-5284

https://doi.org/10.1016/j.tetlet.2009.07.030 Get rights and content

Abstract

A preference of intramolecular cyclizations over oligomerization can often be achieved by conducting the reaction at higher temperatures. This effect which has obviously been underestimated so far may be useful in synthetic organic chemistry. Herein, we report a novel example supporting this observation—an intramolecular nitrile oxide 1,3-dipolar cycloaddition. The yield of the desired product rose from 53% at 0 °C to 79% at 80 °C. A plausible kinetic background of this phenomenon is proposed in terms of activation enthalpy.

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Acknowledgments

We thank Dr. Christian Pilger (University of Vienna, Austria) for providing starting material 4a, b and useful discussions, and Dr. Neil Sheddan (LOBA Feinchemie GmbH, Vienna, Austria) for help in the preparation of the manuscript.

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Remarkable temperature effect on intramolecular [3+2] cyclization

Abstract

Graphical abstract

Section snippets

Acknowledgments

Chem. Eur. J.

Carbohydr. Res.

J. Am. Chem. Soc.

Tetrahedron

Tetrahedron Lett.

J. Chem.

J. Am. Chem. Soc.

J. Chem. Soc., Chem. Commun.

Tetrahedron Lett.

J. Org. Chem.

J. Org. Chem.

Org. Lett.

Angew. Chem., Int. Ed.

Org. Lett.

J. Am. Chem. Soc.

J. Chem. Soc., Perkin Trans. 1