Evidence for a concerted mechanism in a palladium trimethylenemethane cycloaddition Academic Article

abstract

• Carbon kinetic isotope effects were determined at natural abundance for the palladium trimethylenemethane cycloaddition of ester-amide 5. Substantial intermolecular 13C KIEs were observed for both olefinic carbons of 5. In contrast, a Michael addition to 5 exhibits a significant 13C KIE only at the carbon to the ester group. Intramolecular KIEs determined for the product-determining step(s) for reaction of the Pd-TMM intermediate would require a surprising isotope-dependent selection between diastereomeric ring closures. These results cannot be reconciled with a stepwise cycloaddition mechanism but are readily interpreted in terms of a concerted cycloaddition.

authors

• Singleton, Daniel

published proceedings

• JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

author list (cited authors)

• Singleton, D. A., & Schulmeier, B. E.

citation count

• 32

complete list of authors

• Singleton, DA||Schulmeier, BE

publication date

• October 1999

publisher

• American Chemical Society (ACS)  Publisher

published in

• Journal of the American Chemical Society  Journal

keywords

• 34 Chemical Sciences
• 3405 Organic Chemistry
• 3407 Theoretical And Computational Chemistry

Digital Object Identifier (DOI)

• 10.1021/ja9919229

start page

• 9313

end page

• 9317

volume

• 121

issue

• 40

URL

• http%3A%2F%2Fdx.doi.org%2F10.1021%2Fja9919229