Biradical and zwitterionic cyclizations of oxy-substituted enyne-allenes

Authors
Cramer, CJ Kormos, BL Seierstad, M Sherer, EC Winget, P
Citation
Cj. Cramer et al., Biradical and zwitterionic cyclizations of oxy-substituted enyne-allenes, ORG LETT, 3(12), 2001, pp. 1881-1884
Citations number
30
Categorie Soggetti
Organic Chemistry/Polymer Science
Journal title
ORGANIC LETTERS
ISSN journal
15237060 → ACNP
Volume
3
Issue
12
Year of publication
2001
Pages
1881 - 1884
Database
ISI
SICI code
1523-7060(20010614)3:12<1881:BAZCOO>2.0.ZU;2-K
Abstract
[GRAPHICS] Oxyanion substitution of enyne-allenes causes both Myers-Saito and Schmitte l cyclizations to switch their product formation preferences from diradical s to polar, closed-shell singlets, The oxyanion stabilization is larger for the Schmittel products than the Myers-Saito products because the latter mu st sacrifice aromaticity to maximize interaction. The changing character of the different reaction paths is reflected in their activation energies.