Moss, RA and Fu, X and Sauers, RR and Wipf, P
(2005)
Endo entry to the nortricyclyl-norbornenyl cation system: Stereochemistry in the fragmentation of endo-5-norbornenyl-2-oxychlorocarbene.
Journal of Organic Chemistry, 70 (21).
8454 - 8460.
ISSN 0022-3263
![[img]](http://d-scholarship-dev.library.pitt.edu/style/images/fileicons/text_plain.png) |
Plain Text (licence)
Available under License : See the attached license file.
Download (1kB)
|
Abstract
Fragmentation of (S)-endo-5-norbornenyl-2-oxychlorocarbene [(S)-8] in cyclohexane-d12 gives ∼20% (S)-endo-2-chloro-5-norbornene [(S)-7] with ∼50% ee, 65-70% (R)-exo-2-chloro-5-norbornene [(R)-4] with >95% ee, and ∼12% (R)-3-nortricyclyl chloride [(R)-5] with ∼22% ee. (Analogous stereochemical results were also obtained starting with the enantiomeric carbene (R)-8.) The (S)-8 to (S)-7 and (S)-8 to (R)-4 conversions are ascribed mainly to retention and inversion SNi transition states, respectively. These have been located by computational methods and are nearly isoenergetic. In more polar solvents (CDCl3 and CD3CN), the fragmentation of (S)-8 increasingly occurs via competitive ion pair pathways in which steroselectivity is diminished, and escape to the norbornenyl-nortricyclyl cation directs the products away from endo-2-chloro-5-norbornene toward exo-chloride 4 and nortricyclyl chloride 5. © 2005 American Chemical Society.
Share
| Citation/Export: |
|
| Social Networking: |
|
Details
Metrics
Monthly Views for the past 3 years
Plum Analytics
Altmetric.com
Actions (login required)
 |
View Item |
![[feed]](/images/feed-icon-32x32.png){kind=icon}