Citation
Me. Gonzalez-nunez et al., Hyperconjugative control by remote substituents of diastereoselectivity inthe oxygenation of hydrocarbons, ORG LETT, 2(6), 2000, pp. 831-834
Citations number
47
Categorie Soggetti
Organic Chemistry/Polymer Science
Journal title
ORGANIC LETTERS
ISSN journal
15237060
→ ACNP
Volume
2
Issue
6
Year of publication
2000
Pages
831 - 834
Database
ISI
SICI code
1523-7060(20000323)2:6<831:HCBRSO>2.0.ZU;2-7
Abstract
The oxidation of 2-substituted adamantanes (2) with TFDO (1) is reported. T
he data show a stereodifferentiation of the chemical environments induced b
y remote electron-withdrawing substituents which produces remarkable Z/E di
astereoselectivity in the oxidation of the tertiary C-5-H and C-7-H bonds.
The results show a bell-shaped correlation between the Z/E stereoselectivit
y and the substituent constant sigma(1), which is interpreted in terms of h
yperconjugative stabilization of the diastereomeric transition states.