Isotope effects and heavy-atom tunneling in the Roush allylboration of aldehydes. Academic Article

abstract

• Intermolecular (13)C kinetic isotope effects (KIEs) for the Roush allylboration of p-anisaldehyde were determined using a novel approach. The experimental (13)C KIEs fit qualitatively with the expected rate-limiting cyclic transition state, but they are far higher than theoretical predictions based on conventional transition state theory. This discrepancy is attributed to a substantial contribution of heavy-atom tunneling to the reaction, and this is supported by multidimensional tunneling calculations that reproduce the observed KIEs.

authors

• Singleton, Daniel

author list (cited authors)

• Vetticatt, M. J., & Singleton, D. A

citation count

• 29

complete list of authors

• Vetticatt, Mathew J||Singleton, Daniel A

publication date

• January 2012

publisher

• American Chemical Society (ACS)  Publisher

published in

• Organic Letters  Journal

keywords

• Aldehydes
• Benzaldehydes
• Boron Compounds
• Isotopes
• Models, Theoretical
• Molecular Structure
• Temperature
• Thermodynamics

PubMed Central ID

• 22506639

Digital Object Identifier (DOI)

• 10.1021/ol300789a

start page

• 2370

end page

• 2373

volume

• 14

issue

• 9

URL

• http%3A%2F%2Fdx.doi.org%2F10.1021%2Fol300789a