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Kinetic isotope effects in the intramolecular insertion of a metal carbene into a CH bond adjacent to nitrogen

✍ Scribed by Gary A. Sulikowski; Sangku Lee

Publisher: Elsevier Science
Year: 1999
Tongue: French
Weight: 257 KB
Volume: 40
Category: Article
ISSN: 0040-4039
DOI: 10.1016/s0040-4039(99)01686-x

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✦ Synopsis

An internal competition was used to estimate the kinetic isotope effect of an intramolecular metal carbene C-H insertion reaction alpha to a nitrogen atom. A stereoelectronic effect is proposed to explain the difference in magnitude of the observed KIEs for cis and trans diastereomers.

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Separation of the primary and secondary kinetic isotope effects at a reactive center using starting material reactivities. Application to the FeCl3-Catalyzed oxidation of CH bonds with tert-butyl hydroperoxide

✍ Steven R. Merrigan; Valerie N. Le Gloahec; Jason A. Smith; Derek H.R. Barton; Da 📂 Article 📅 1999 🏛 Elsevier Science 🌐 French ⚖ 256 KB

A method is reported for the determination of both the primary and secondary kinetic isotope effects at a reactive center based on starting material reactivities. This allows the determination of the separate KIEs in reactions for which neither product analysis nor absolute rate measurements are app