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Volumn 349, Issue 7, 2007, Pages 1019-1024

An expedient variant of heck reaction of alkenyl nonaflates: Homogeneous ligand-free palladium catalysis at room temperature

Author keywords

Alkenyl nonaflates; Catalyst poisoning; Heck reaction; Homogeneous catalysis; Kinetics; Ligand free catalysis

Indexed keywords


EID: 34547467685     PISSN: 16154150     EISSN: 15213897     Source Type: Journal    
DOI: 10.1002/adsc.200600388     Document Type: Article
Times cited : (20)

References (66)
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    • Current state of art in elucidation of active species in Heck and Suzuki coupling reactions is summarized in the recent review: a N. T. S. Phan, M. Van Der Sluys, C. W. Jones, Adv. Synth. Catal. 2006, 348, 609-679;
    • Current state of art in elucidation of active species in Heck and Suzuki coupling reactions is summarized in the recent review: a) N. T. S. Phan, M. Van Der Sluys, C. W. Jones, Adv. Synth. Catal. 2006, 348, 609-679;
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    • noteworthy, in the very recent account, a leaching of homogeneous Pd-species from Pd colloids in the ligand-free Heck reaction was proven by a molecular membrane technique: b M. B. Thathagar, J. E. ten Elshof, G. Rothenberg, Angew. Chem. 2006, 118, 2952-2956;
    • noteworthy, in the very recent account, a leaching of homogeneous Pd-species from Pd colloids in the ligand-free Heck reaction was proven by a molecular membrane technique: b) M. B. Thathagar, J. E. ten Elshof, G. Rothenberg, Angew. Chem. 2006, 118, 2952-2956;
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    • Heck reactions of alkenyl triflates (refs. a-d) and nonaflates (refs. e-g) are often carried out without phosphine added: a) A. Arcadi, E. Bernocchi, S. Cacchi, L. Caglioti, F. Marinelli, Tetrahedron Lett. 1990, 31, 2463-2466;
    • Heck reactions of alkenyl triflates (refs. a-d) and nonaflates (refs. e-g) are often carried out without phosphine added: a) A. Arcadi, E. Bernocchi, S. Cacchi, L. Caglioti, F. Marinelli, Tetrahedron Lett. 1990, 31, 2463-2466;
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    • A versatile methodology has been developed that enables an easy one-step access to alkenyl nonaflates from enolizable carbonyl compounds and a commercially available convenient technical product, nonafluorobutane-1-sulfonyl fluoride (NfF, a) via trimethylsilyl enol ethers: I. M. Lyapkalo, M. Webel, H.-U. Reissig, Chem. 2002, 1015-1025;
    • A versatile methodology has been developed that enables an easy one-step access to alkenyl nonaflates from enolizable carbonyl compounds and a commercially available convenient technical product, nonafluorobutane-1-sulfonyl fluoride (NfF); a) via trimethylsilyl enol ethers: I. M. Lyapkalo, M. Webel, H.-U. Reissig, Eur. J. Org. Chem. 2002, 1015-1025;
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    • Effects of solvent, auxiliary base and additives on the reaction rate will be reported in a full account elsewhere
    • Effects of solvent, auxiliary base and additives on the reaction rate will be reported in a full account elsewhere.
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    • [1d,7b,9a].
    • [1d,7b,9a].
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    • In the heterogeneous catalyst, only a fraction of the metal atoms on the surface is active. Therefore, much less than 1 equiv. of the catalytic poison (PPh3, CS2 or thiophene) is sufficient to block the active sites. Complete quenching of the catalytic activity with ≪ 1 equiv. of the above poisons was regarded as a solid evidence for the heterogeneous nature of the Pd(0)-catalyst in Heck coupling of aryl halides. Metallic mercury taken in a large excess amalgamates the colloidal metallic Pd thus deactivating it
    • 2 or thiophene) is sufficient to block the active sites. Complete quenching of the catalytic activity with ≪ 1 equiv. of the above poisons was regarded as a solid evidence for the heterogeneous nature of the Pd(0)-catalyst in Heck coupling of aryl halides. Metallic mercury taken in a large excess amalgamates the colloidal metallic Pd thus deactivating it.
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    • 2 or thiophene were reported.
    • 2 or thiophene were reported.
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    • Indeed, a single-metal Pd(0)-complex efficiently catalyzing a hydrogénation of alkenes was regarded as a truly homogeneous catalyst based on its insensitivity towards poisoning with thiophene: R. van Asselt, C. J. Elsevier, J. Mol. Catal. 1991, 65, L13-L19.
    • Indeed, a single-metal Pd(0)-complex efficiently catalyzing a hydrogénation of alkenes was regarded as a truly homogeneous catalyst based on its insensitivity towards poisoning with thiophene: R. van Asselt, C. J. Elsevier, J. Mol. Catal. 1991, 65, L13-L19.
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    • [19] remarked that Hg(0)-poisoning experiments are not universally applicable as Hg(O) can cause side reactions and interact with some single-metal complexes: a) G. M. Whitesides, M. Hackett, R. L. Brainard, J. P. P. M. Lavalleye, A. F. Sowinski, A. N. Izumi, S. S. Moore, D. W. Brown, E. M. Staudt, Organometallics 1985, 4, 1819-1830;
    • [19] remarked that Hg(0)-poisoning experiments are not universally applicable as Hg(O) can cause side reactions and interact with some single-metal complexes: a) G. M. Whitesides, M. Hackett, R. L. Brainard, J. P. P. M. Lavalleye, A. F. Sowinski, A. N. Izumi, S. S. Moore, D. W. Brown, E. M. Staudt, Organometallics 1985, 4, 1819-1830;
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    • [9a,13a]
    • [9a,13a]
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    • Metallic mercury was added to a reaction mixture at 37 % completion. It was vigorously stirred for 1 h, then stirring stopped, the Hg-phase was allowed to completely settle to the bottom, the clear supernatant organic phase was transferred into the new vial, and the reaction kinetics was monitored further.
    • Metallic mercury was added to a reaction mixture at 37 % completion. It was vigorously stirred for 1 h, then stirring stopped, the Hg-phase was allowed to completely settle to the bottom, the clear supernatant organic phase was transferred into the new vial, and the reaction kinetics was monitored further.
  • 66
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    • The influence of anionic nonaflate on the catalytic activity would be masked by DMF and Et3N which are more nucleophilic, stronger coordinating, and are present in the reaction mixture in greater excess. However, for the ligand-free Heck reactions of aryl halides, a kinetic model was suggested by Dupont and co-workers that accounts for the catalysis deactivation by formation of PdXnm, see ref.[9a] We thank one of the referees for the respective comment
    • [9a] We thank one of the referees for the respective comment.


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