Rhodium-Catalyzed Homogeneous and Aqueous Biphasic Hydroformylation of the Acrolein Acetal 2-Vinyl-5-Methyl-1,3-Dioxane - Université de Rennes Accéder directement au contenu
Article Dans Une Revue ChemCatChem Année : 2013

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

Résumé

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.

Domaines

Catalyse

Dates et versions

hal-00879952 , version 1 (05-11-2013)

Identifiants

Citer

Jérémy Ternel, Jean-Luc Dubois, Jean-Luc Couturier, Eric Monflier, Jean-François Carpentier. Rhodium-Catalyzed Homogeneous and Aqueous Biphasic Hydroformylation of the Acrolein Acetal 2-Vinyl-5-Methyl-1,3-Dioxane. ChemCatChem, 2013, 5 (6), pp.1562-1569. ⟨10.1002/cctc.201200630⟩. ⟨hal-00879952⟩
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