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Synlett 2005(5): 0713-0731
DOI: 10.1055/s-2005-864793
DOI: 10.1055/s-2005-864793
ACCOUNT
© Georg Thieme Verlag Stuttgart · New York
Mechanistic Studies in Triazolinedione Ene Reactions
Further Information
Received
11 August 2004
Publication Date:
09 March 2005 (online)
Publication History
Publication Date:
09 March 2005 (online)
Abstract
Triazolinediones react with olefins bearing allylic hydrogens in an ene fashion to afford N-allylurazoles. This reaction, apart from considerable mechanistic attention, shows also substantial synthetic utility. Extensive experimental data, such as deuterium kinetic isotope effects, trapping of intermediates, and stereochemical studies, and to a lesser extent computational work, support a two-step mechanism with irreversible formation of a three-membered ring intermediate (aziridinium imide). On the basis of recent experimental and theoretical work, an open biradical has been proposed as the key intermediate.
1 Introduction and Background
2 Isotope Effects
3 Regioselectivity and Diastereoselectivity Studies
3.1 Regioselectivity
3.1.1 Regioselectivity with Simple Alkenes
3.1.2 Regioselectivity with Substituted Alkenes, Styrenes, α,β-Unsaturated Esters, Carbonyl Compounds and Sulfoxides
3.2 Diastereoselectivity
4 Solvent Trapping Studies
5 Stereochemistry: Simple Alkenes, Non-Polar Solvents
6 Theoretical Calculations
7 Concluding Remarks
Key words
ene reactions - regioselectivity - diastereoselectivity - stereochemistry - kinetic isotope effects
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