Control of regioselectivity by the lone substituent through steric and electronic effects in the nitrosoarene ene reaction of deuterium-labeled trisubstituted alkenes

Waldemar Adam; Oliver Krebs; Michael Orfanopoulos; Manolis Stratakis

doi:10.1021/jo026198i

Control of regioselectivity by the lone substituent through steric and electronic effects in the nitrosoarene ene reaction of deuterium-labeled trisubstituted alkenes

J Org Chem. 2002 Nov 29;67(24):8395-9. doi: 10.1021/jo026198i.

Authors

Waldemar Adam¹, Oliver Krebs, Michael Orfanopoulos, Manolis Stratakis

Affiliation

¹ Institut für Organische Chemie, Universität Würzburg, Am Hubland, D-97074 Würzburg, Germany.

PMID: 12444616
DOI: 10.1021/jo026198i

Abstract

For the ene reaction of 4-nitronitrosobenzene (ArNO) with a variety of primary and secondary lone alkyl-substituted substrates, the twix/twin regioselectivity is constant at about 85:15. In contrast, for the lone tert-butyl group and for lone aryl substituents, the twix regioisomer is obtained exclusively. These regioselectivities have been rationalized in terms of steric interactions and coordination between the enophile and the substrates in the transition states of the first reaction step.