Chiral Cyclopentadienyl Iridium(III) Complexes Promote Enantioselective Cycloisomerizations Giving Fused Cyclopropanes

The cyclopentadienyl (Cp) group is a very important ligand for many transition‐metal complexes which have been applied in catalysis. The availability of chiral cyclopentadienyl ligands (Cpx) lags behind other ligand classes, thus hampering the investigation of enantioselective processes. We report a...

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Bibliographic Details
Published in:Angewandte Chemie (International ed.) 2015-10, Vol.54 (41), p.12149-12152
Main Authors: Dieckmann, Michael, Jang, Yun-Suk, Cramer, Nicolai
Format: Article
Language:English
Subjects:
asymmetric catalysis
Asymmetry
Availability
Catalysis
Complexation
cycloisomerization
cyclopentadienyl ligands
Derivatives
enantioselectivity
iridium
Isomerization
Ligands
Organic compounds
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Summary:The cyclopentadienyl (Cp) group is a very important ligand for many transition‐metal complexes which have been applied in catalysis. The availability of chiral cyclopentadienyl ligands (Cpx) lags behind other ligand classes, thus hampering the investigation of enantioselective processes. We report a library of chiral CpxIrIII complexes equipped with an atropchiral Cp scaffold. A robust complexation procedure reliably provides CpxIrIII complexes with tunable counterions. In a proof‐of‐concept application, the iodide‐bearing members are shown to be highly selective for enyne cycloisomerization reactions. The dehydropiperidine‐fused cyclopropane products are formed in good yields and enantioselectivities. Be selective! A set of chiral CpxIrIII complexes (Cpx=chiral cyclopentadienyl) based on atropchiral cyclopentadienyl ligands are presented. The complexes, in particular the tert‐butoxy‐substituted derivative (see picture), are shown to promote the asymmetric cycloisomerization of enynes to form fused cyclopropanes with high enantioselectivities.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201506483