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o ‐DPPB‐Directed Copper‐Mediated and ‐Catalyzed Allylic Substitution with Grignard Reagents
Author(s) -
Demel Peter,
Keller Manfred,
Breit Bernhard
Publication year - 2006
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200600225
Subject(s) - allylic rearrangement , reagent , copper , phosphine , chemistry , stereoselectivity , ligand (biochemistry) , substitution reaction , medicinal chemistry , catalysis , group (periodic table) , leaving group , chirality (physics) , combinatorial chemistry , organic chemistry , symmetry breaking , receptor , biochemistry , chiral symmetry breaking , physics , quantum mechanics , nambu–jona lasinio model
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.