✦ LIBER ✦

Probing the mechanism of the anomalous intramolecular C–H insertion reaction of rhodium carbenoids by analysis of kinetic isotope effects

✍ Scribed by J.Stephen Clark; Yung-Sing Wong; Robert J Townsend

Publisher: Elsevier Science
Year: 2001
Tongue: French
Weight: 81 KB
Volume: 42
Category: Article
ISSN: 0040-4039
DOI: 10.1016/s0040-4039(01)01173-x

No coin nor oath required. For personal study only.

✦ Synopsis

The mechanism of the anomalous intramolecular insertion reaction of a rhodium carbenoid into an ethereal C-H bond has been explored using deuterium labelled substrates. Comparison of primary kinetic isotope effects and analysis of ratios of diastereoisomeric deuterated products suggests the reactions leading to the anomalous and conventional C-H insertion products are mechanistically distinct and do not share a common rate-determining step.

📜 SIMILAR VOLUMES

ChemInform Abstract: Anomalous Products

ChemInform Abstract: Anomalous Products from Intramolecular Insertion Reactions of Rhodium Carbenoids into the α-C-H Bonds of Ethers.

✍ J. S. CLARK; A. G. DOSSETTER; C. A. RUSSELL; W. G. WHITTINGHAM 📂 Article 📅 2010 🏛 John Wiley and Sons ⚖ 34 KB

Kinetic isotope effects in the intramole

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

✍ Gary A. Sulikowski; Sangku Lee 📂 Article 📅 1999 🏛 Elsevier Science 🌐 French ⚖ 257 KB

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.