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InChI:InChI=1/C6H10O3/c1-2-5-9-6(8)3-4-7/h4H,2-3,5H2,1H3

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• 591-87-7 Allyl acetate 
• 201230-82-2 carbon monoxide 
• 55378-40-0 2-(acetoxymethyl)propan-1-ol 

Relevant academic research and scientific papers

Hydroformylation of unsaturated esters and 2,3-dihydrofuran under solventless conditions at room temperature catalysed by rhodium: N-pyrrolyl phosphine catalysts

Rhodium complexes of the type HRh(CO)L3 (where L is an N-pyrrolyl phosphine, such as P(NC4H4)3, PPh(NC4H4)2, or PPh2(NC4H4)) were applied in the hydroformylation of less reactive unsaturated substrates, namely allyl acetate, butyl acrylate, methyl acrylate, 2,3-dihydrofuran and vinyl acetate. Even at room temperature, these catalysts enabled complete substrate conversion and high chemoselectivity towards the corresponding aldehydes. High conversion of vinyl acetate (88% in 6 h) to the branched aldehyde was obtained with HRh(CO)[P(NC4H4)3]3 at 25 °C. An increase of the turnover frequency, TOF, up to 2000 mol mol-1 h-1 was achieved in this reaction under 20 bar of syngas (H2/CO = 1) at 80 °C. The introduction of chiral phosphines, BINAP or Ph-BPE, to this system resulted in the production of a branched aldehyde with enantioselectivity, ee, up to 44 and 81%, respectively. High activity combined with high enantioselectivity was achieved due to the formation of the mixed rhodium hydrides HRh(CO)[P(NC4H4)3](BINAP) and HRh(CO)[P(NC4H4)3](Ph-BPE), identified by the NMR method.

Liquid-Liquid Extraction Protocol for the Removal of Aldehydes and Highly Reactive Ketones from Mixtures

The reaction of the bisulfite ion with aldehydes to form charged bisulfite adducts is a well-established method for the purification of aldehydes. This reaction has been modified to create a convenient liquid-liquid extraction method for the removal of aldehydes from mixtures. The use of a water-miscible solvent allows the reaction to occur during a simple 30 s shaking protocol by increasing the contact between the bisulfite ion and the aldehyde. The introduction of an immiscible solvent allows for the extraction of the uncharged organic components away from the bisulfite adduct. The developed protocol is applicable to a wide range of aldehydes, including sterically hindered neopentyl aldehydes. Sterically unhindered cyclic and linear ketones, as well as highly electrophilic ketones, are also removed using this protocol. The mild conditions tolerate a wide range of functional groups, allowing for excellent aldehyde contaminant removal rates with high levels of recovery of the desired component.

Highly Regio- and Enantioselective Hydroformylation of Vinyl Esters Using Bidentate Phosphine,P-Chiral Phosphorodiamidite Ligands

Hybrid bidentate phosphine-phosphorodiamidite ligands based on a chiral Betti base backbone and diphenylphosphinoaniline derivatives have been prepared (BettiPhos). The ligands possess a stereogenic P atom at the phosphorodiamidite moiety, whose configuration can be largely controlled by the synthetic route and the choice of base and solvent. The new ligands were applied in the rhodium-catalyzed asymmetric hydroformylation (AHF) of vinyl esters and vinyl amides. Very high enantioselectivities of up to 97% ee accompanied by excellent regioselectivities (up to b/l > 1000) were obtained using the BettiPhos ligand (SC,SC,RP,SC)-4b bearing an additional chiral group at the aniline nitrogen. The catalyst resting state [RhH(CO)2{(SC,SC,RP,SC)-4b}] was investigated by high pressure-NMR studies, revealing an equatorial-apical coordination of the bidentate ligand where the two phosphorus donors rapidly exchange their positions through an intermediate with the ligand bound via the phosphine group only.

Allyl acetate hydroformylation process

A process for the production of 4-acetoxybutyraldehyde is described. The process comprises reacting allyl acetate with a mixture of carbon monoxide and hydrogen in the presence of a solvent and a catalyst comprising a rhodium complex and a diphosphine. The diphoshine is a substituted or unsubstituted 2,2′-bis(dihydrocarbylphosphino)diphenyl ether. The process gives a high ratio of 4-acetoxybutyraldehyde:3-acetoxy-2-methylpropionaldehyde.

Rhodium-catalyzed asymmetric hydroformylation of n-allvlamides: Highly enantioselective approach to β2-amino aldehydes

(Figure Presented) You're having a lahf I The asymmetric hydroformylation (AHF) of allylic compounds, catalyzed by a rhodium-yanphos complex, is a direct and concise route to ss2-amino aldehydes, acids, and alcohols with excellent enantioselectivity (see scheme; TON =turnover number, acac = acetylacetonate).

Hydroformylation with unmodified rhodium catalysts in supercritical carbon dioxide

The present invention relates to processes for the preparation of oxo products by the hydroformylation of substrates having C═C double bonds using unmodified rhodium catalysts in a reaction mixture essentially consisting of the substrates, the catalyst and carbon dioxide in a supercritical state (scCO2). In particular, the invention relates to such processes for the preparation of products which contain substantial proportions of branched i-oxo products. Further, the invention relates to such processes for the hydroformylation of substrates which do not correspond to the general formula CnH2n. The invention further relates to such processes in which the separation of product and catalyst is effected using the special solvent properties of scCO2.

Construction of chiral Ti(IV)-Rh(I)-salenophos complexes and their application in the asymmetric hydroformylation of functionalised olefins

The synthesis of new chiral salenophos-type ligands bearing 'hard' and 'soft' coordination sites is described. The polyfunctionalised ligands are used for the construction of monometallic and early-late heterobimetallic complexes. In the reaction with titanium(IV) reagents the salen subunit selectively coordinated to the 'hard' metal. The phosphine groups in turn can be coordinated to rhodium(I). The coordination geometry of the diphosphine- Rh subunit is strongly influenced by the counter ligands COD or CO and Cl, respectively. In the asymmetric hydroformylation of vinyl acetate with one of the Rh-Ti-complexes, the branched aldehyde is predominantly formed with 30% ee.

P/O ligand systems: Facile synthesis, structure, and catalytic tests of 2′-phosphanyl-1,1′-bipheny 1-2-ols and 2′-phosphanyl-1,1′-binaphthyl-2-ols

A facile synthesis of 2′-phosphanyl-1,1′-biphenyl- and 2′-phosphanyl-l,1′-binaphthyl-2-ols and their silyl ethers has been developed, consisting of electron-transfer-catalyzed ring-opening of dibenzofuran and dinaphthofuran, respectively, subsequent reaction with chlorophosphanes, and work-up with acetic acid or ClSiMe3. Studies of the molecular and crystal structures reveal the presence of P...H-O bridging bonds in the more basic /BuPhP derivative and a nearly perpendicular arrangement of the aryl planes in the biphenyl derivatives. The barrier to rotation of the aryl planes about the C-C axis was determined by NMR in the case of the P-asymmetric derivative 3d, using the appearance of diastereoisomers by atropisomerism and P-asymmetry. Comparative screening tests of the title compounds, phosphanylphenols and phosphanylnaphthols in homogeneous Rh-catalyzed reactions demonstrate catalytic activity in hydroformylation reactions and superior properties of the biphenyl- and binaphthyl-2-ol derivatives in relation to other P-O ligands. WILEY-VCH Verlag GmbH, 1997.

The Regioselective Hydroformylation of Allyl Acetate Catalysed by Cationic and Zwitterionic Rhodium Complexes

Cationic and zwitterionic rhodium complexes, with added 1,4-bis(diphenylphosphino)butane (dppb), are efficient catalysts for the highly regioselective hydroformylation of allyl acetate and related esters to yield the linear aldehyde (up to 95percent) under mild conditions.

Acyclic Stereoselection. 25. Stereoselective Synthesis of the C-1 to C-7 Moiety of Erythronolide A.

A stereoselective synthesis of aldehyde ester 1, a synthon for the C-1 to C-7 section of erythronolide A, is reported.The synthesis begins with β,γ-unsaturated aldehyde 12, which is prepared from mesityl oxide as shown in eq 2.Aldehyde 12 reacts with the preformed lithium enolates of reagents 13 and 5 to give, in each case, a 15:1 mixture of two aldols (eq 3 and 4).Reduction of the major isomer 16 from the reaction of 5 with lithium aluminum hydride followed by periodate cleavage of the resulting vicinal diol provides β-hydroxy aldehyde 20.This material is protected as triethylsilyl derivative 21, which is treated with the lithium enolate of BHT O-benzyllactate (22c).The resulting 5:1 mixture of aldols is converted into acetonides 27c and 28c, which are separated by chromatography.The stereostructure of the major acetonide 27c was elucidated by single-crystal X-ray analysis (Figure 1).Lithium aluminum hydride reduction of 27c gives alcohol 29, which is converted into acetate 34.Ozonolysis of this material gives aldehyde 35, which is oxidized by pyridinium dichromate in DMF.Diazomethane esterification provides diester 36, which is methanolized to hydroxy ester 37.Swern oxidation of 35 provides racemic ester aldehyde 1.Enantiomerically homogeneous 1 is obtained in similar sequence, via the O-methylmandelates 39a and 39b.