913822-90-9Relevant academic research and scientific papers
Directed branched-regioselective hydroformylation of 2-substituted allylic o-DPPB esters
Breit, Bernhard,Gruenanger, Christian U.,Abillard, Olivier
, p. 2497 - 2503 (2007)
Branched-regioselective hydroformylation of allylic o-DPPB esters has been accomplished with mono- and disubstituted alkene functions in good to excellent yields and selectivities. Optimized reaction conditions allowed the reaction of even trisubstitued alkenic functions. These reactions occur as a result of a significant rate-accelerating effect exerted by the catalyst-directing o-DPPB group, as exemplified by highly position-, regio-, and diastereoselective hydroformylation of the geranyl and neryl o-DPPB esters. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.
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.
