Control of Regioselectivity by the lone Substituent through Steric and Electronic Effects in the Nitrosoarene Ene Reaction of Deuterium-Labeled Trisubstituted Alkenes

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 exclu...

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Bibliographic Details
Published in:Journal of organic chemistry 2002-11, Vol.67 (24), p.8395-8399
Main Authors: ADAM, Waldemar, KREBS, Oliver, ORFANOPOULOS, Michael, STRATAKIS, Manolis
Format: Article
Language:English
Subjects:
Chemistry
Exact sciences and technology
Kinetics and mechanisms
Organic chemistry
Reactivity and mechanisms
Online Access:Get full text
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Summary: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.
ISSN:0022-3263
1520-6904
DOI:10.1021/jo026198i