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Volumn 13, Issue 19, 2007, Pages 5492-5502

A comparison of phosphaferrocene and phospharuthenocene ligands in Rh +-catalysed enamide hydrogenation reactions: Superior performance of the phospharuthenocene

Author keywords

Enamides; Enantioselectivity; Hydrogenation; Metallocenes; Phosphorus heterocycles

Indexed keywords

CRYSTAL STRUCTURE; ENANTIOSELECTIVITY; HYDROGENATION; NEGATIVE IONS; ORGANOMETALLICS;

EID: 34547368125     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200601715     Document Type: Article
Times cited : (32)

References (89)
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    • Opposite behaviour is found when the coordinating functions are on different rings. In such cases, the wider bite angle associated with the ruthenocene generally brings the ligand chirality into closer proximity to any coordinated substrate, with an associated increase in ee. For the case of metallocene-1.1′-bis(diphenylmethylate)-2,2′-bis(oxazoline) -catalysed arylation of aromatic aldehydes by phenylzincs see: C. Bolm, N. Hermanns, M. Kesselgruber, J. P. Hildebrand, J. Organomet. Chem. 2001, 624, 157;
    • Opposite behaviour is found when the coordinating functions are on different rings. In such cases, the wider bite angle associated with the ruthenocene generally brings the ligand chirality into closer proximity to any coordinated substrate, with an associated increase in ee. For the case of metallocene-1.1′-bis(diphenylmethylate)-2,2′-bis(oxazoline) -catalysed arylation of aromatic aldehydes by phenylzincs see: C. Bolm, N. Hermanns, M. Kesselgruber, J. P. Hildebrand, J. Organomet. Chem. 2001, 624, 157;
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    • for Pd-catalysed asymmetric silylations of allylic chlorides or ring-closing cyclisation of dimethyl-(Z)-2-butenylenedicarbonate with methylacetoacetate, see T. Hayashi, A. Ohno, S. J. Lu, Y. Matsumoto, E. Fukuyo, K. Yanagi, J. Am. Chem. Soc. 1994, 116, 4221
    • for Pd-catalysed asymmetric silylations of allylic chlorides or ring-closing cyclisation of dimethyl-(Z)-2-butenylenedicarbonate with methylacetoacetate, see T. Hayashi, A. Ohno, S. J. Lu, Y. Matsumoto, E. Fukuyo, K. Yanagi, J. Am. Chem. Soc. 1994, 116, 4221.
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    • Strong interactions between the substitutents of the five-membered rings might also be likely to produce results which contradict this simple model see Coordination section
    • Strong interactions between the substitutents of the five-membered rings might also be likely to produce results which contradict this simple model (see "Coordination" section).
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    • To the best of our knowledge, the only available datum concerns a palladium-catalysed hydrosilylation of 5,5-dimethyl-1-hexene-3-yne using complex atropomeric monodentate monophosphametallocene ligands. In this case, the phosphaferrocene gave a better ee (84%) than the phospharuthenocene (75%).[24]
    • To the best of our knowledge, the only available datum concerns a palladium-catalysed hydrosilylation of 5,5-dimethyl-1-hexene-3-yne using complex atropomeric monodentate monophosphametallocene ligands. In this case, the phosphaferrocene gave a better ee (84%) than the phospharuthenocene (75%).[24]
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    • For small-scale separations of diastereomeric Cp*-containing phosphaferrocene-oxazolines, see; references [13] and [20].
    • For small-scale separations of diastereomeric Cp*-containing phosphaferrocene-oxazolines, see; references [13] and [20].
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    • An enantiopure pianostool phosphacymantrene methylphosphane complex has also been reported; see B. Deschamps, F. Mathey, Heteroat. Chem. 2005, 16, 458
    • An enantiopure pianostool phosphacymantrene methylphosphane complex has also been reported; see B. Deschamps, F. Mathey, Heteroat. Chem. 2005, 16, 458.
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    • See the Supporting Information. The compounds appear to be isomorphous and could not be separated by crystallisation
    • See the Supporting Information. The compounds appear to be isomorphous and could not be separated by crystallisation.
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    • It is well established that this has no causal link to enantioselection: H. J. Drexler, S. L. Zhang, A. L. Sun, A. Spannenberg, A. Arrieta, A. Preetz, D. Heller, Tetrahedron: Asymmetry 2004, 15, 2139;
    • It is well established that this has no causal link to enantioselection: H. J. Drexler, S. L. Zhang, A. L. Sun, A. Spannenberg, A. Arrieta, A. Preetz, D. Heller, Tetrahedron: Asymmetry 2004, 15, 2139;
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    • It could reasonably be argued that the nature of the comparison between a rac-sample of 18 and enantiopure 19 might lead to the observed differences in molecular structures, but this hypothesis becomes much less tenable once it is recognised that the differences between the structures of rac-18 and enantiopure (+)-24 complexes are minuscule.
    • It could reasonably be argued that the nature of the comparison between a rac-sample of 18 and enantiopure 19 might lead to the observed differences in molecular structures, but this hypothesis becomes much less tenable once it is recognised that the differences between the structures of rac-18 and enantiopure (+)-24 complexes are minuscule.
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    • Mechanism of Enantioselective Hydrogenation: J. M. Brown, in Handbook of Homogeneous Hydrogenation 3 (Eds.: J G. de Vries, C. J. Elsevier), 2006, Wiley-VCH, Weinheim, p. 1073.
    • "Mechanism of Enantioselective Hydrogenation": J. M. Brown, in Handbook of Homogeneous Hydrogenation Vol. 3 (Eds.: J G. de Vries, C. J. Elsevier), 2006, Wiley-VCH, Weinheim, p. 1073.
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    • An analogue of 24 that has P(o-tol)2 groups instead of PPh2, which shows improved stability and performance in allylic isomerisation reactions, has also been characterised structurally. Its torsional angle data are much closer to those of the phospharuthenocene complex 19 than to 24.[18,19
    • 2, which shows improved stability and performance in allylic isomerisation reactions, has also been characterised structurally. Its torsional angle data are much closer to those of the phospharuthenocene complex 19 than to 24.[18,19]
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    • The superior phospharuthenocene performance was also carried through (albeit with attenuation) into a study of the hydrogenation of dimethylitaconate, for which an ee of 90% was found in favour of the (R)-product for 19; 87 % for 18.
    • The superior phospharuthenocene performance was also carried through (albeit with attenuation) into a study of the hydrogenation of dimethylitaconate, for which an ee of 90% was found in favour of the (R)-product for 19; 87 % for 18.
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    • 31PMR spectroscopy prior to catalysis, so as to minimise the possibility of catalyst labelling errors.
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    • For further typical examples, see also: T. Imamoto, K. Yashio, K. V. L. Crépy, K. Katagiri, H. Takahashi, M. Kouchi, I. D. Gridnev, Organometallics 2006, 25, 908;
    • For further typical examples, see also: T. Imamoto, K. Yashio, K. V. L. Crépy, K. Katagiri, H. Takahashi, M. Kouchi, I. D. Gridnev, Organometallics 2006, 25, 908;
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    • 2-addition transition state (see R. Giernoth, H. Heinrich, N. J. Adams, R. J. Deeth, J. Bargon, J. M. Brown, J. Am. Chem. Soc. 2000, 122, 12381)
    • 2-addition transition state (see R. Giernoth, H. Heinrich, N. J. Adams, R. J. Deeth, J. Bargon, J. M. Brown, J. Am. Chem. Soc. 2000, 122, 12381)
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    • which is central to Gridnev and Imamoto's recent reformulation of the quadrant rule (I. D. Gridnev, T. Imamoto, Acc. Chem. Res. 2004, 37, 633, and references therein). For more general caveats concerning the relationship between precatalyst crystal structures and the outcome of enamide hydrogenations,
    • which is central to Gridnev and Imamoto's recent reformulation of the quadrant rule (I. D. Gridnev, T. Imamoto, Acc. Chem. Res. 2004, 37, 633, and references therein). For more general caveats concerning the relationship between precatalyst crystal structures and the outcome of enamide hydrogenations,
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    • 1-symmetrical ligands (J. A. Ramsden, T. D. W. Claridge, J. M. Brown, J. Chem. Soc. Chem. Commun. 1995, 2469).
    • 1-symmetrical ligands (J. A. Ramsden, T. D. W. Claridge, J. M. Brown, J. Chem. Soc. Chem. Commun. 1995, 2469).


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