Quantum mechanical study of regioselectivity of radical additions to substituted olefins

✍ Scribed by Arnaud, Roger; Vetere, Valentina; Barone, Vincenzo

• Publisher: John Wiley and Sons
• Year: 2000
• Tongue: English
• Weight: 374 KB
• Volume: 21
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/(sici)1096-987x(200006)21:8<675::aid-jcc7>3.0.co;2-e

✦ Synopsis

Regiochemical trends in the addition of free radicals to substituted olefins are investigated by different quantum chemical approaches with special reference to oxygen centered radicals. From a methodological point of view, density functional methods provide correct general trends but they do not reach quantitative accuracy, especially for intermediate complexes. More reliable results are obtained by single point post-Hartree-Fock computations at density functional geometries. A number of test computations show that reoptimization of the geometry and computation of vibrational frequencies by correlated methods can be safely avoided. As a consequence, the overall computational approach has very reasonable computer costs. From a more chemical point of view, a careful analysis of computational results points out the significant role of anomeric and polar effects in tuning the common filicity of carbon centered radicals.