Cookies Policy

This site uses cookies. By continuing to browse the site you are agreeing to our use of cookies.

I accept this policy

Find out more here

Substituted 2-Norbornyl Carbenes

No metrics data to plot.
The attempt to load metrics for this article has failed.
The attempt to plot a graph for these metrics has failed.
The full text of this article is not currently available.

Brill’s MyBook program is exclusively available on BrillOnline Books and Journals. Students and scholars affiliated with an institution that has purchased a Brill E-Book on the BrillOnline platform automatically have access to the MyBook option for the title(s) acquired by the Library. Brill MyBook is a print-on-demand paperback copy which is sold at a favorably uniform low price.

This Article is currently unavailable for purchase.
Add to Favorites
You must be logged in to use this functionality

Cover image Placeholder

A series of endo-6-substituted bicyclo[2.2.1 ]hept-2-yl carbenes have been generated by pyrolysis of the sodium salt of the tosylhydrazone precursors. The endo-6-trimethylsilyl and endo-6-thiomethoxy substituted carbenes give 1,3-migration of these substituents to the carbene center. However groups such as methyl, CH2SiMe3, phenyl, and methoxy are ineffective 1,3-migrating groups. The facile 1,3-migration of trimethylsilyl and thiomethoxy has been rationalized in terms of stabilized transition states where the migrating group interacts effectively with the carbene vacant orbital. In the cases of endo-6-thiomethoxy and methoxy derivatives, the carbene also inserts effectively into the methyl group of the substituent. Heteroatom stabilization of the transition state for C-H insertion facilitates these processes. Certain exo-6-substituted bicyclo[2.2.1 ]hept-2-yl carbenes have also been generated. While the exo-6-thiomethoxy and carbomethoxy systems give exclusive 1,3-hydrogen migration, the exo-6-sulfonyl derivative gives, in addition to 1,3-hydrogen migration, an alkene product derived from 1,2-hydrogen migration. The lowered propensity for 1,3-hydrogen migration is attributed to the strong electron-withdrawing sulfonyl group, which decreases the hydridic 1,3-interaction with the carbene vacant orbital.

Affiliations: 1: Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, U.S.A.


Full text loading...


Data & Media loading...

Article metrics loading...



Can't access your account?
  • Key

  • Full access
  • Open Access
  • Partial/No accessInformation