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Volumn 13, Issue 36, 2007, Pages 10216-10224

An investigation into the allylic imidate rearrangement of trichloroacetimidates catalysed by cobalt oxazoline palladacycles

Author keywords

Allylic compounds; Asymmetric catalysis; Ligand effects; Metallocenes; Palladium

Indexed keywords

CATALYSIS; CATALYSTS; COBALT COMPOUNDS; ENANTIOMERS; LIGANDS; ORGANOMETALLICS;

EID: 38049156262     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200700873     Document Type: Article
Times cited : (79)

References (80)
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    • 2 has also been used to highlight the dimeric nature of this palladacycle.
    • 2 has also been used to highlight the dimeric nature of this palladacycle.
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    • For other applications of cobalt oxazoline palladacycles as catalysts for the allylic imidate rearrangement see: a J. Kang, T. H. Kim, K. H. Yew, W. K. Lee, Tetrahedron: Asymmetry 2003, 14, 415-418;
    • For other applications of cobalt oxazoline palladacycles as catalysts for the allylic imidate rearrangement see: a) J. Kang, T. H. Kim, K. H. Yew, W. K. Lee, Tetrahedron: Asymmetry 2003, 14, 415-418;
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    • During the preparation of this manuscript, a model for the enantio-selectivity of COP-Cl-catalysed rearrangement of trichloroacetimidates was reported. See
    • During the preparation of this manuscript, a model for the enantio-selectivity of COP-Cl-catalysed rearrangement of trichloroacetimidates was reported. See: M. P. Watson, L. E. Overman, R. G. Bergman, J. Am. Chem. Soc. 2007, 129, 5031-5044.
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    • Watson, M.P.1    Overman, L.E.2    Bergman, R.G.3
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    • Ratios: 2a (1:0), 2b (1:0.7), 2c (1:0.7), 2d (1:0.3), 2e (1:0), 2f (1:0), Isomer mixtures (cis/trans. also referred to as synlanti) are a feature of many bridged palladacycles.
    • Ratios: 2a (1:0), 2b (1:0.7), 2c (1:0.7), 2d (1:0.3), 2e (1:0), 2f (1:0), Isomer mixtures (cis/trans. also referred to as synlanti) are a feature of many bridged palladacycles.
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    • Acetonitrile has been used with catalyst 4 (1 mol% loading) but only at 50°C: see reference [8b].
    • Acetonitrile has been used with catalyst 4 (1 mol% loading) but only at 50°C: see reference [8b].
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    • Examples of palladium-catalysed addition of nucleophiles to alkenes that proceed by means of cis palladation have recently been reported. Oxygen nucleophiles; a) T. Hayashi, K. Yamasaki, M. Mimura, Y. Uozumi, J. Am. Chem. Soc. 2004, 126, 3036-3037;
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    • It has been noted that addition of an excess of silver trifluoroacetate to an iodide-bridged ferrocene oxazoline palladacycle results in the formation of a ferrocenium cation, see reference [3k
    • It has been noted that addition of an excess of silver trifluoroacetate to an iodide-bridged ferrocene oxazoline palladacycle results in the formation of a ferrocenium cation, see reference [3k].
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    • For a statistical distribution of S,pR/S,pR (R,R) R,PS/R,pS (S,S) and 5,pR/R, pS (R,S) dimers (K, 4, eeaux, 50% gives EEprod, 55, EE, extrapolated enantiomeric yield) with g, 0.5 (g, kRS/kRR, Alternatively, for g, 0 an EEprod of 54% is calculated with eeaux, 50% if the component of the meso (R,S) diastereoisomer is 20, See: D. Guillaneux, S.-H. Zhao, O. Samuel, D. Rainford, H. B. Kagan, J. Am. Chem. Soc. 1994, 116, 9430-9439
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    • Models for the origin of enantioselection have been proposed in which the alkene component of the allylic imidate substrate is coordinated cis to the metallocene.[3m,11] This is compatible with a mechanism in which initial coordination of the substrate is followed by isomerisation to the thermodynamic cis isomer, as presumably is also the case with phosphine adducts 3
    • [3m,11] This is compatible with a mechanism in which initial coordination of the substrate is followed by isomerisation to the thermodynamic cis isomer, as presumably is also the case with phosphine adducts 3.


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