Synfacts 2019; 15(06): 0619
DOI: 10.1055/s-0037-1611594
Metals in Synthesis
© Georg Thieme Verlag Stuttgart · New York

Asymmetric C–H Functionalization Using Chiral CpxCo(III) Catalysis

Rezensent(en):
Mark Lautens
,
Egor M. Larin
Ozols K, Jang Y.-S, Cramer N. * École Polytechnique Fédérale de Lausanne, Switzerland
Chiral Cyclopentadienyl Cobalt(III) Complexes Enable Highly Enantioselective 3d-Metal-Catalyzed C–H Functionalizations.

J. Am. Chem. Soc. 2019;
141: 5675-5680
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Publikationsverlauf

Publikationsdatum:
20. Mai 2019 (online)

 

Significance

This work is an important advance in catalytic C–H functionalizations for the following reasons: (1) it is the first example of asymmetric C–H functionalization using a chiral Cpx-ligand-bound Co(III) complex; (2) it outperforms competing rhodium-catalyzed methods; (3) reactions with alkyl alkenes give regioisomeric products opposite to those with rhodium complexes.


Comment

The authors systematically studied the effect of various substituents on the Cpx ligand in the C–H functionalization of chlorobenzamides, a benchmark for chiral CpRh(III) catalysis. The presence of the tert-butyl group greatly influences the approach of the olefin, whereas the naphthyl backbone acts to orient and align the metallocene.