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Letter

The Woodward−Hoffmann−De Puy Rule Revisited^†

Supporting Info

Olalla Nieto Faza, Carlos Silva López, Rosana Álvarez, and Ángel R. de Lera*

Departamento de Qumica Orgnica, Facultade de Qumica, Universidade de Vigo, Lagoas-Marcosende s/n, 36200 Vigo, Spain

Org. Lett., 2004, 6 (6), pp 905–908

DOI: 10.1021/ol036449p

Publication Date (Web): February 19, 2004

†

Dedicated to Professor Charles H. DePuy on occasion of his 75th birthday.

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

, qolera@uvigo.es

Abstract

An estimate of the kinetic advantage, in the gas phase and in MeOH, of one of the two allowed disrotatory movements in the electrocyclic ring opening of cyclopropyl derivatives has been theoretically obtained at the B3LYP/6-311++G** level. Confirming the Woodward−Hoffmann−DePuy rule, the torquoselectivity of this process is attributed to charge donation from the dissociating C−C bond to the antibonding orbital of the breaking C−Br bond. Substituents do not modify the inherent torquoselectivity.

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