Cationic Copper(I) Complexes as Highly Efficient Catalysts for Single and Double A3‐Coupling Mannich Reactions of Terminal Alkynes: Mechanistic Insights and Comparative Studies with Analogous Gold(I) Complexes |
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| Authors: | Dr Abdessamad Grirrane Dr Eleuterio Álvarez Prof Hermenegildo García Prof Avelino Corma |
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| Institution: | 1. Instituto Universitario de Tecnología Química CSIC‐UPV, Universidad Politécnica de Valencia, Av. De los Naranjos s/n, 46022 Valencia (Spain), Fax: (+34)?963877809;2. Instituto de Investigaciones Químicas CSIC‐US, Departamento de Química Inorgánica, Av. Américo Vespucio 49, 41092 Sevilla (Spain) |
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| Abstract: | Cationic Cu?L complexes (L=Buchwald‐type phosphane) with N co‐ligands have been characterised by structural and spectroscopic properties. These copper(I) complexes are extremely active catalysts, far more active than analogous gold(I) complexes, to promote the single and double A3 coupling of terminal alkynes, pyrrolidine and formaldehyde. The activity data show the possible ways in which the solvent can influence the catalytic performance by limiting complex solubility, by solvent decomposition or instability of the copper(I) redox state. Isolation of copper(I) complexes that are likely to be the key catalytic species has allowed light to be shed on the reaction mechanism. |
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| Keywords: | coordination chemistry copper homogeneous catalysis reaction mechanisms solvent effects |
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