Multi-component orbital interactions during oxyacyl radical addition reactions involving imines and electron-rich olefins

Kyne, Sara and Schiesser, Carl H. and Matsubara, Hiroshi (2007) Multi-component orbital interactions during oxyacyl radical addition reactions involving imines and electron-rich olefins. Organic & Biomolecular Chemistry, 5 (24). pp. 3938-3943. ISSN 1477-0520

Full content URL: http://pubs.rsc.org/en/content/articlehtml/2007/ob...

Documents
Multi-component orbital interactions during oxyacyl radical addition reactions involving imines and electron-rich olefins

Request a copy
[img] PDF
Org. Biomol. Chem. 2007 Kyne.pdf - Whole Document
Restricted to Repository staff only

419kB
Item Type:Article
Item Status:Live Archive

Abstract

Ab initio and DFT calculations reveal that oxyacyl radicals add to imines and electron-rich olefins through simultaneous SOMO-pi*, SOMO-pi and pi*-HOMO interactions between the radical and the radicalophile. At the BHandHLYP/aug-cc-pVDZ level, energy barriers of 20.3 and 22.0 kJ mol -1 are calculated for the attack of methoxycarbonyl radical at the carbon and nitrogen ends of methanimine, respectively. In comparison, barriers of 22.0 and 8.6 kJ mol-1 are calculated at BHandHLYP/aug-cc-pVDZ for reaction of methoxycarbonyl radical at the 1- and 2-positions in aminoethylene, respectively. Natural bond orbital (NBO) analysis at the BHandHLYP/6- 311G** level of theory reveals that SOMO-pi*, SOMO-pi and pi*-LP interactions are worth 111, 394 and 55 kJ mol-1 respectively in the transition state (8) for reaction of oxyacyl radical at the nitrogen end of methanimine; similar interactions are observed for the chemistry involving aminoethylene. These multi-component interactions are responsible for the unusual motion vectors associated with the transition states involved in these reactions.

Keywords:Density functional theory, Intermolecular radical addition, Imine
Subjects:F Physical Sciences > F160 Organic Chemistry
F Physical Sciences > F190 Chemistry not elsewhere classified
Divisions:College of Science > School of Chemistry
Related URLs:
ID Code:17622
Deposited On:12 Jun 2015 08:23

Repository Staff Only: item control page