Citation
Ra. Moss et Sq. Yan, Remote substituent effects on phenylchlorocarbene C-H insertion reactions, ORG LETT, 1(5), 1999, pp. 819-822
Citations number
16
Categorie Soggetti
Organic Chemistry/Polymer Science
Journal title
ORGANIC LETTERS
ISSN journal
15237060
→ ACNP
Volume
1
Issue
5
Year of publication
1999
Pages
819 - 822
Database
ISI
SICI code
1523-7060(19990909)1:5<819:RSEOPC>2.0.ZU;2-K
Abstract
[GRAPHICS]
Phenylchlorocarbene inserts into the tertiary CH bonds of 1,3-dimethyladama
ntane and 1-X-adamantanes (X = H, OMe, COOMe, Cl, CN), There is a good corr
elation between the relative rate constants for these insertions and the in
ductive substituent constants, sigma(I)(X), with rho = -1.5. Absolute rate
constants for the insertions range from 2.5 x 10(5) M-1 S-1 for Ad-Me-2 to
2.5 x 10(4) M-1 S-1 for Ad-CN. B3LYP/6-31G* calculations give a good accoun
t of reactivity in these systems.