370867-96-2Relevant academic research and scientific papers
Tandem-directed regioselective hydroformylation/β-elimination: A practical method for the synthesis of enals
Bruch, Achim,Gebert, Antje,Breit, Bernhard
experimental part, p. 2169 - 2176 (2009/04/10)
A practical synthesis of α,β-unsaturated aldehydes by a tandem-directed hydroformylation/β-elimination process of allylic o-DPPB esters is reported. The o-DPPB group served as an effective controller for regioselectivity of the hydroformylation towards th
O-DPPB-directed copper-mediated and -Catalyzed allylic substitution with grignard reagents
Demel, Peter,Keller, Manfred,Breit, Bernhard
, p. 6669 - 6683 (2008/09/16)
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 or ganometallic 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.
