One-pot Hydroformylation Research Articles

Tandem and One-Pot Hydroformylation/Michael Reactions of Acrylates

The combination of various reactions in one operational step leads to many advantages in synthetic strategies, such as a lower consumption of resources, effort, and time, when intermittent workup and purification steps can be avoided. The hydroformylation reaction of acrylates gives access to 2-formylpropanoates, which thanks to their structural features constitute useful intermediates in the synthesis of more complex compounds. Herein, we report a simple and convenient one-pot strategy to synthesize functionalized carbonyl compounds starting from these readily available substrates, via tandem or one-pot hydroformylation, Michael addition, and aldol reactions.

Rhodium-Complex-Catalyzed Hydroformylation of Olefins with CO2 and Hydrosilane.

A rhodium-catalyzed one-pot hydroformylation of olefins with CO2 , hydrosilane, and H2 has been developed that affords the aldehydes in good chemoselectivities at low catalyst loading. Mechanistic studies indicate that the transformation is likely to proceed through a tandem sequence of poly(methylhydrosiloxane) (PMHS) mediated CO2 reduction to CO and a conventional rhodium-catalyzed hydroformylation with CO/H2 . The hydrosilylane-mediated reduction of CO2 in preference to aldehydes was found to be crucial for the selective formation of aldehydes under the reaction conditions.

Phosphonium-based aminophosphines as bifunctional ligands for sequential catalysis of one-pot hydroformylation–acetalization of olefins

A series of ionic phosphonium-based aminophosphinesL1–L3were prepared and fully characterized, in each of which the involved bifunctional moieties of the phosphine fragment and Lewis acidic phosphonium were linked together by stable chemical bonds and bridged by one N-atom.

Co-catalysis of a bi-functional ligand containing phosphine and Lewis acidic phosphonium for hydroformylation–acetalization of olefins

L2 containing a phosphine and a Lewis acidic phosphonium exhibited synergetic catalysis and sequential catalysis for one-pot hydroformylation–acetalization.

“On-water” rhodium-catalysed hydroformylation for the production of linear alcohols

Optimisation of the reaction conditions for the rhodium-catalysed aldehyde hydrogenation under hydroformylation conditions showed that water used as co-solvent enhances both rate and selectivity towards primary alcohols. One-pot hydroformylation–hydrogenation using rhodium as the only transition metal yielded alcohols in excellent selectivities and good linearities.

Ultranox626 as a selective ligand in rhodium-catalyzed hydroformylation–acetalization of allylbenzene derivatives

Ultranox626 as a diphosphite ligand showed high selectivity and good yields when used with Rh(CO)2(acac) as a catalyst precursor in the hydroformylation of allylbenzene derivatives producing aldehydes, and also in the one-pot hydroformylation–acetalization forming acetals. These reactions proceed smoothly and effectively to produce the linear aldehydes or acetals with high selectivity. The recycling of the rhodium catalyst was carried out after the careful screening and optimization of the reaction conditions in order to maximize the conversion and the selectivity of the reactions.

Rhodium-catalyzed one-pot hydroformylation–cyclization of allylbenzene derivatives: Simple and efficient route to 5,6-dihydronaphthalenes

Abstract The one-pot hydroformylation–cyclization of allylbenzene derivatives by the catalyst system Rh(CO) 2 acac/ultranox626/CO/H 2 /CH 2 Cl 2 led chemoselectively to 5,6-dihydronaphthalene derivatives 5a–d in good yields. The addition of a catalytic amount of H 3 PO 4 enhanced in situ the cyclization process via the nucleophilic attack on the carbonyl group of the linear aldehyde, and finally the elimination of alcohol. The type of substitution on phenyl group of the allylbenzene is of great importance in enhancing the cyclization process.

Ruthenium-catalyzed one-pot hydroformylation of alkenes using carbon dioxide as a reactant

Abstract A new hydroformylation of alkenes using carbon dioxide as a reactant is shown to take place in the presence of ruthenium cluster complexes and halide salts. Similar or even better yields of alcohols were formed as compared to the conventional hydroformylation with CO under the same reaction conditions. The reaction proceeded in three steps: CO2 is first converted to CO; then it is used as a reagent for hydroformylation to give aldehyde; subsequently, it is hydrogenated to alcohol. ESI-mass spectrometric analyses of the reaction solutions indicated formation of four kinds of ruthenium anionic complexes including tetra-, tri-, and mononuclear species. On the basis of experimental findings, possible roles of these complexes are discussed.

One-pot synthesis of secondary and tertiary naphthylpropylamines by rhodium(I)-catalysed carbonylative hydroaminomethylation

Secondary and tertiary naphthylpropylamines are prepared in high yields by the reaction of 2-vinylnaphthalene, primary or secondary amines, carbon monoxide and hydrogen in presence of [Rh(cod)Cl] 2 as catalyst via a one-pot hydroformylation - amine condensation - reduction sequence.

One-pot synthesis of pharmacologically active secondary and tertiary 1-(3,3-diarylpropyl)amines via rhodium-catalysed hydroaminomethylation of 1,1-diarylethenes

Pharmacologically active secondary and tertiary 1-(3,3-diarylpropyl)amines 1 are prepared in high yields and chemoselectivity by the reaction of 1,1-diarylethenes 4, primary or secondary amines 5, carbon monoxide and hydrogen in presence of [Rh(cod)Cl] 2 PBu 3 as catalyst via a one-pot hydroformylation - amine condensation - reduction sequence.