o-DPPB-Directed Copper-Mediated and -Catalyzed Allylic Substitution with Grignard Reagents

✍ Scribed by Peter Demel; Manfred Keller; Bernhard Breit

• Publisher: John Wiley and Sons
• Year: 2006
• Tongue: English
• Weight: 400 KB
• Volume: 12
• Category: Article
• ISSN: 0947-6539
• DOI: 10.1002/chem.200600225

✦ Synopsis

Abstract

The ortho‐diphenylphosphanylbenzoyl (o‐DPPB) group was explored as a directing leaving group in copper‐mediated and copper‐catalyzed allylic substitution with Grignard reagents. Complete control of chemo‐, regio‐ and stereoselectivity with complete syn‐1,3‐chirality transfer was observed as a result of the directed nature of the reaction. No excess of organometallic reagent is required and the directing group can be recovered quantitatively. Coordination studies in the solid state and in solution have shown that two substrates are bound via the phosphine function of the directing group at copper. Dynamic NMR experiments in solution are in agreement with a ligand‐exchange process at copper, a prerequisite for the development of a substoichiometric process.