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Rhodium-Catalyzed Homogeneous and Aqueous Biphasic Hydroformylation of the Acrolein Acetal 2-Vinyl-5-Methyl-1,3-Dioxane

Authors

  • Dr. Jérémy Ternel,

    1. Organometallics, Materials and Catalysis, UMR 6226 Institut Sciences Chimiques de Rennes, CNRS-University of Rennes 1, F-35042 Rennes (France), Fax: (+33) 0223-236-939
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  • Dr. Jean-Luc Dubois,

    1. ARKEMA, 420 Rue d'Estienne d'Orves, F-92705 Colombes (France)
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  • Dr. Jean-Luc Couturier,

    1. ARKEMA, CRRA, BP 63, Rue Henri Moissan, F-69493 Pierre Bénite (France)
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  • Prof.Dr. Eric Monflier,

    1. Unité de Catalyse et de Chimie du Solide, UMR 8181 Université d'Artois, Faculté des Sciences Jean Perrin, Rue Jean Souvraz, SP 18- F-62307 Lens (France)
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  • Prof.Dr. Jean-François Carpentier

    Corresponding author
    1. Organometallics, Materials and Catalysis, UMR 6226 Institut Sciences Chimiques de Rennes, CNRS-University of Rennes 1, F-35042 Rennes (France), Fax: (+33) 0223-236-939
    • Organometallics, Materials and Catalysis, UMR 6226 Institut Sciences Chimiques de Rennes, CNRS-University of Rennes 1, F-35042 Rennes (France), Fax: (+33) 0223-236-939
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Abstract

The rhodium-catalyzed hydroformylation of 2-vinyl-5-methyl-1,3-dioxane (VMD), the acetal derived from acrolein and 2-methyl-1,3-propanediol, has been investigated. Under homogeneous conditions, phosphane-based catalysts afforded perfect chemoselectivity for the aldehydes. Catalysts based on diphosphine ligands with a narrow bite angle of approximately 85°, such as 1,2-bis(phenylphosphino)ethane, were found to favor the branched aldehyde 2, with selectivities of up to 78 %, whereas diphosphine ligands with a large bite angle of approximately 110°, such as xantphos, produce the linear aldehyde 1 with up to 91 % selectivity. Control of the 1/2 regioselectivity by means of the P[BOND]Rh[BOND]P bite angle was ascertained with a variety of ethylene-, hydrazino- and CNC-bridged diphosphines, irrespective of electronic factors induced by these ligands. Under aqueous biphasic conditions, chemoselective hydroformylation of VMD proved feasible only with disulfonated xantphos; in this case, remarkable activities (turnover frequencies of up to 1075 molaldehyde molRh−1 h−1 at 120 °C) were observed, with up to 82 % yield for the linear aldehyde. On the other hand, the catalyst based on tetrasulfonated dppe systematically induced the formation of very large amounts of the hydrogenated product.

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