Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 23, Issue 10, Pages 2448-2460Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201605244
Keywords
1,2-additions; boronic acids; ferrocene; imine; transmetallation
Categories
Funding
- Deutsche For-schungsgemeinschaft (DFG) [PE 818/4-1, PE 818/4-2]
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Benzylic N-substituted stereocenters constitute a frequent structural motif in drugs. Their highly enantioselective generation is hence of technical importance. An attractive strategy is the arylation of imines with organoboron reagents. Chiral Rh complexes have reached a high level of productivity for this reaction type. In this article we describe that an electron rich Pd-II catalyst also performs well in the arylation of aldimines, comparable to the best Rh catalysts. The ferrocenyl palladacycle-acetate catalyst allows for a broad substrate scope and very high enantioselectivities. Commonly observed side reactions like aryl-aryl homocouplings and imine hydrolysis could be blocked. Mechanistic studies implicate that a) the acetate ligand is crucial for transmetallation, b) the active catalyst is most likely a palladacycle-OAc monomer, c) the rate limiting step is probably the product release. By added KOAc the arylation could also be applied to ketimines.
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