Highly Regioselective and Rapid Hydroformylation of Alkyl Acrylates Catalyzed by a Rhodium Complex with a Tetraphosphorus Ligand

Abstract

Alkyl acrylates have been hydroformylated to the linear aldehydes with high regioselectivity (linear/branch > 99/1) and extraordinarily high average turnover frequencies (up to 5400 h À1 ) by using a rhodium complex with a tetraphosphorus ligand. This protocol is in sharp contrast to the most of other processes that favor production of the branched aldehyde (typically > 95% branched for most Rh-catalyzed reaction systems). The high turnover number achieved by this new catalytic system is also remarkable considering the less reactive character of alkyl acrylates to the hydroformylation reaction conditions.

Synthesis and characterization of TiO2 nanotube supported Rh-nanoparticle catalysts for regioselective hydroformylation of vinyl acetate

“…[2][3][4][5][6] With the regioselective hydroformylation of functionalized alkenes, target products having functional groups at different positions can be synthesized. 7,8 For example, the hydroformylation of vinyl acetate provides bifunctional products (Scheme 1), which can be further converted into synthetically useful compounds, e.g. lactic acid and so on.…”

Hydroformylation of 2,5‐norbornadiene in organic/aqueous two‐phase system and acceleration by cationic surfactants

“…Recently, much attention has been concentrated on the hydroformylation of special olefins because of its high added value in the manufacture of fine chemicals . Thus, the hydroformylation of 2,5‐norbornadiene (NBD) is of interest, since the carboxylated derivatives of its dialdehyde products are applied in the manufacture of advanced photoelectron instruments .…”

Selective hydroformylation of alkyl acrylates using [2,2′-bis(dipyrrolylphosphinooxy)-1,1′-(±)-binaphthyl]/Rh catalyst: reversal of regioselectivity

“…Recently, researchers have developed a consuming passion for the hydroformylation of functionalized olens, like styrene, 1,2 dicyclopentadiene, [3][4][5] vinylacetate, 6 allyl alcohol, 7,8 alkyl acrylate [9][10][11][12] and so on. Hydroformylation of alkyl acrylate could provide 1,3-and 1,4-bifunctional carbonyl compounds (corresponding to branched and linear aldehydes), and these compounds could transform to malonic acids, 1,4-dicarboxylic acid, lactones, 2-methyl-1,3-propanediol and 1,4-butanediol 13,14 (shown in Scheme 1), which are useful intermediates for the production of ne chemicals, pharmaceuticals, resin, adhesives, oil paints, plasticizers and so on.…”

“…C, 9 however, the synthesis of the tetraphosphorus ligand seems to be a little complicated and be of high cost. And the mechanism of high linear regioselectivity was unclear.…”

“…It is suggested that phosphorus ligands possessing strong p-acceptor were effective in terms of activity and regioselectivity, for example, the good performance made with the above CF 3 -or pyrrolyl-substituted phosphorus ligands could be ascribed to that the electron-withdrawing character improved the p-acceptor ability of phosphorus. 9,20,24 In this study, ve accessible ligands L1-L5 (Fig. 1) were employed to Rh-catalyzed hydroformylation of alkyl acrylate.…”