These are preliminary reports that have not been peer-reviewed. They should not be regarded as conclusive, guide clinical practice/health-related behavior, or be reported in news media as established information. For more information, please see our FAQs.
2 files

Metal-Bound or Free Ylides as Reaction Intermediates in Metal-Catalyzed [2,3]-Sigmatropic Rearrangements? It Depends.

submitted on 02.11.2020, 04:09 and posted on 03.11.2020, 12:47 by Croix Laconsay, Dean Tantillo

Density functional theory calculations were applied to study four previously published metal-catalyzed [2,3]-rearrangements from onium ylide intermediates, in pursuit of generalizations about when, during these types of reactions, catalysts dissociate. Our results corroborate past studies where free ylide mechanisms were proposed to be operative. Calculations on case studies predict that the origin of metal-catalyst ‘falling off’ (dissociation) can be attributed primarily to the steric bulkiness of functional groups adjacent to the carbene carbon.


Email Address of Submitting Author


University of California, Davis


United States

ORCID For Submitting Author


Declaration of Conflict of Interest

No conflict of interest