JOURNAL ARTICLE
RESEARCH SUPPORT, NON-U.S. GOV'T
Add like
Add dislike
Add to saved papers

The molecular mechanism of palladium-catalysed cyanoesterification of methyl cyanoformate onto norbornene.

Potential energy surface mapping was completed for the entire catalytic cycle of palladium-catalysed cyanoesterification onto norbornene (NBE) using density functional theory calculations. We found that after the oxidative addition step of the reagent methyl cyanoformate, the reaction proceeds through an insertion of olefin into a Pd(II)-COOMe bond first. Subsequently, reductive elimination occurs by transferring the cyanide group from the Pd center to NBE. This rearrangement is triggered by the rotation of the ester group into a π-interaction with the Pd(II) centre. The regioselectivity of olefin insertion is controlled by ionic and covalent interactions in the precursor π-complex formation step. Importantly, all of the intermediates and transition states along the exo pathway were found to be more stable than the corresponding structures of the endo pathway without any sign of crossing over between the two surfaces via isomerization. The rate-determining step is the reductive elimination despite the fact that the corresponding activation barrier is reduced by conformational changes via the rotation of a MeOOC-C(NBE) bond.

Full text links

We have located links that may give you full text access.
Can't access the paper?
Try logging in through your university/institutional subscription. For a smoother one-click institutional access experience, please use our mobile app.

For the best experience, use the Read mobile app

Mobile app image

Get seemless 1-tap access through your institution/university

For the best experience, use the Read mobile app

All material on this website is protected by copyright, Copyright © 1994-2024 by WebMD LLC.
This website also contains material copyrighted by 3rd parties.

By using this service, you agree to our terms of use and privacy policy.

Your Privacy Choices Toggle icon

You can now claim free CME credits for this literature searchClaim now

Get seemless 1-tap access through your institution/university

For the best experience, use the Read mobile app