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Arthurs, Ross A., Horton, Peter N., Coles, Simon J. and Richards, Christopher J. 
ORCID: https://orcid.org/0000-0001-7899-4082
(2018)
Stereoselective and stereospecific reactions of cobalt sandwich complexes: Synthesis of a new class of single enantiomer bulky planar chiral P−N and P−P ligands.
Chemistry - A European Journal, 24 (17).
pp. 4310-4319.
ISSN 0947-6539
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Abstract
Starting from (η5-acetylcyclopentadienyl)(η4-tetraphenylcyclobutadiene)cobalt(I), highly enantioselective (99 % ee) (S)-CBS catalysed ketone reduction followed by stereospecific alcohol-azide exchange, azide reduction and dimethyllation gave (R)-(η5-α-N,N-dimethylaminoethylcyclopentadienyl)(η4-tetraphenylcyclobutadiene) cobalt(I) (Arthurs’ amine). This underwent highly diastereoselective cyclopalladation to give di-μ-acetate-bis-(R)-[(η5-(Sp)-2-(α-N,N-dimethylaminoethyl)cyclopentadienyl, 1-C, N)(η4-tetraphenylcyclobutadiene)cobalt(I)]dipalladium, and highly diastereoselective lithiation to give (R)-(η5-(Sp)-1-(α-N,N-dimethylaminoethyl)-2-(diphenylphosphino)cyclopentadienyl)(η4-tetraphenylcyclobutadiene)cobalt(I) (PPCA) following the addition as electrophile of chlorodiphenylphosphine. This PN-ligand was converted into (R)-(η5-(Sp)-1-(α-dicyclohexylphosphinoethyl)-2-(diphenylphosphino)cyclopentadienyl)(η4-tetraphenylcyclobutadiene)cobalt(I), a PP-ligand (Rossiphos), by stereospecific amine-phosphine exchange using HPCy2. These air-stable P−N and P−P complexes are the first examples of a new class of bulky planar chiral ligands for application in asymmetric catalysis.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | cobalt,sandwich complexes,ligands,diastereoselectivity,enantioselectivity |
| Faculty \ School: | Faculty of Science > School of Chemistry |
| UEA Research Groups: | Faculty of Science > Research Groups > Chemistry of Materials and Catalysis |
| Related URLs: | |
| Depositing User: | Pure Connector |
| Date Deposited: | 03 Jan 2018 07:46 |
| Last Modified: | 22 Oct 2022 03:27 |
| URI: | https://ueaeprints.uea.ac.uk/id/eprint/65837 |
| DOI: | 10.1002/chem.201705113 |
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