Regiodivergent Epoxide Opening: A Concept in Stereoselective Catalysis beyond Classical Kinetic Resolutions and Desymmetrizations

✍ Scribed by Andreas Gansäuer; Chun-An Fan; Florian Keller; Peter Karbaum

• Publisher: John Wiley and Sons
• Year: 2007
• Tongue: English
• Weight: 478 KB
• Volume: 13
• Category: Article
• ISSN: 0947-6539
• DOI: 10.1002/chem.200701021

✦ Synopsis

Abstract

An approach to highly regiodivergent epoxide openings (REOs) is presented. The very popular kinetic resolutions of epoxides and openings of meso‐epoxides constitute subclasses of such REOs. REOs are attractive for parallel resolutions, double asymmetric reactions of enantiomerically enriched epoxides, and for semisynthetic applications in the functionalization of natural products. They have been notoriously difficult to realize by means of S~N~2 mechanisms. Our titanocene‐catalyzed radical REO addresses this issue by decoupling epoxide opening and radical trapping and is firmly based on a mechanistic study of the reductive epoxide opening.