40630-06-6

Usage

Synthesis Reference(s)

The Journal of Organic Chemistry, 40, p. 1617, 1975 DOI: 10.1021/jo00899a021

InChI:InChI=1/C7H12O3/c1-6(5-8)3-4-7(9)10-2/h5-6H,3-4H2,1-2H3

Upstream product

• 818-58-6 methyl (E)-pent-3-enoate 
• 201230-82-2 carbon monoxide 
• 3724-55-8 methyl but-3-enoate 
• 818-57-5 Methyl 4-pentenoate 

Downstream Products

• 98512-82-4 (S)-2-((2R,3R)-3-Methyl-6-oxo-tetrahydro-pyran-2-yl)-thiopropionic acid S-phenyl ester 
• 1572246-85-5 C₂₀H₃₀N₂O₃S 
• 1572246-88-8 C₂₀H₃₀N₂O₃S 
• 1572246-54-8 C₂₂H₃₄N₂O₄S 
• 1572246-56-0 C₂₂H₃₄N₂O₄S 
• 884315-12-2 (1'R,5S)-(-)-1-(2'-hydroxy-1'-phenylethyl)-5-methylpiperidin-2-one 
• 1572246-13-9 (S)-5-{[(1R)-2-hydroxy-1-phenylethyl]amino}-4-methyl-1-pentanol 
• 155796-96-6 (2'R,3S)-(-)-2-(3-methylpiperidin-1-yl)-2'-phenylethanol 
• 1572246-40-2 (S)-4-methyl-5-[(2-nitrobenzenesulfonyl)amino]-1-pentanol 
• 1572246-44-6 (S)-4-methyl-5-[(p-methylbenzenesulfonyl)amino]-1-pentanol 
• 1572246-47-9 (S)-4-methyl-5-[N-(2-nitrobenzenesulfonyl)-10-undecenylamino]-1-pentanol 
• 1572246-52-6 N-[2-methyl-5-hexenyl]-N-(2-nitrobenzenesulfonyl)-10-undecenamine 
• 1572246-69-5 (S)-5-[(tert-butyldimethylsilyl)oxy]-2-methyl-N-tosylpentanamine 
• 1572246-72-0 (S)-5-[(tert-butyldimethylsilyl)oxy]-2-methyl-N-[3-(phthalimido)propyl]-N-tosylpentanamine 

Relevant academic research and scientific papers

Cyclodextrin-phosphane possessing a guest-tunable conformation for aqueous rhodium-catalyzed hydroformylation

The inclusion of a guest inside the cavity of a new water-soluble cyclodextrin-phosphane allows controlling the natural conformation of this ligand leading to an inversion of the regioselectivity during aqueous hydroformylation reaction.

Precise supramolecular control of selectivity in the Rh-catalyzed hydroformylation of terminal and internal alkenes

In this study, we report a series of DIMPhos ligands L1-L3, bidentate phosphorus ligands equipped with an integral anion binding site (the DIM pocket). Coordination studies show that these ligands bind to a rhodium center in a bidentate fashion. Experiments under hydroformylation conditions confirm the formation of the mononuclear hydridobiscarbonyl rhodium complexes that are generally assumed to be active in hydroformylation. The metal complexes formed still strongly bind the anionic species in the binding site of the ligand, without affecting the metal coordination sphere. These bifunctional properties of DIMPhos are further demonstrated by the crystal structure of the rhodium complex with acetate anion bound in the binding site of the ligand. The catalytic studies demonstrate that substrate preorganization by binding in the DIM pocket of the ligand results in unprecedented selectivities in hydroformylation of terminal and internal alkenes functionalized with an anionic group. Remarkably, the selectivity controlling anionic group can be even 10 bonds away from the reactive double bond, demonstrating the potential of this supramolecular approach. Control experiments confirm the crucial role of the anion binding for the selectivity. DFT studies on the decisive intermediates reveal that the anion binding in the DIM pocket restricts the rotational freedom of the reactive double bound. As a consequence, the pathway to the undesired product is strongly hindered, whereas that for the desired product is lowered in energy. Detailed kinetic studies, together with the in situ spectroscopic measurements and isotope-labeling studies, support this mode of operation and reveal that these supramolecular systems follow enzymatic-type Michaelis-Menten kinetics, with competitive product inhibition.

Water-soluble diphosphadiazacyclooctanes as ligands for aqueous organometallic catalysis

Two new water-soluble diphosphacyclooctanes been synthesized and characterized by NMR and surface tension measurements. Both phosphanes proved to coordinate rhodium in a very selective way as well-defined bidentates were obtained. When used in Rh-catalyzed hydroformylation of terminal alkenes, both ligands positively impacted the reaction chemoselectivity.

Remote supramolecular control of catalyst selectivity in the hydroformylation of alkenes

In the pocket: The supramolecular interactions between a Rh phosphine catalyst equipped with an anion-binding pocket and alkenes that contain anionic functionalities (see picture) provide an excellent design concept to achieve remote control of the regioselectivity in hydroformylation reactions. The 4-pentenoate and 3-butenylphosphonate, which fit tightly between the Rh center and the pocket, were hydroformylated with unprecedented selectivity.

Synthesis, rhodium complexes and catalytic applications of a new water-soluble triphenylphosphane-modified β-cyclodextrin

A new triphenylphosphane based on a β-cyclodextrin skeleton (PM-β-CD-OTPP) was synthesized. This ligand can be dispersed in water by using the nanoprecipitation method. Transmission electron microscopy and NMR spectroscopy showed that PM-β-CD-OTPP is aggregated in water and forms a stable dispersion. Its aqueous solubility can be dramatically increased in the presence of selected water-soluble guests by formation of inclusion complexes. Associated to a rhodium precursor, PM-β-CD-OTPP is able to generate soluble rhodium species in water. In addition, NMR experiments showed that the cyclodextrin cavity remains accessible for a guest even when PM-β-CD-OTPP is coordinated to rhodium. Finally, this ligand was efficient for rhodium-catalyzed hydrogenation and hydroformylation performed in aqueous medium.

METHOD FOR HYDROFORMYLATION

The present invention relates to a process for the hydroformylation of compounds of the formula (I), where X is C, P(Rx), P(O—Rx) S or S(═O), where Rx is H, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl; A is a divalent bridging group having from 1 to 4 bridging atoms; and R1 is H, alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl; or salts thereof; in which the compound of the formula (I) is reacted with carbon monoxide and hydrogen in the presence of a catalyst comprising a complex of a metal of transition group VIII with a compound of the formula (II), where Pn is a pnicogen atom; W is a divalent bridging group having from 1 to 8 bridging atoms; R2 is a functional group capable of forming an intermolecular, noncovalent bond with the group —X(═O)OH; R3, R4 are each alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl; a, b, c are each 0 or 1; and Y1, Y2 and Y3 are each O, S, NRa or SiRbRc; and also compounds of the formula (II.a), where W′ is a divalent bridging group having from 1 to 5 bridging atoms between the flanking bonds, Z is O, S, S(═O), S(═O)2, N(RIX) or C(RIX)(RX); and RI to RX are each, independently of one another, H, halogen, nitro, cyano, amino, alkyl, etc.; or two radicals RI, RII, RIV, RVI, RVIII and RIX together represent the second part of a double bond.

New phosphane based on a β-cyclodextrin, exhibiting a solvent-tunable conformation, and its catalytic properties

A new diphenylphosphane based on a β-cyclodextrin skeleton that exhibits a dual solubility in water and in organic solvent was synthesised. Interestingly, a solvent-dependent conformation change was evidenced by NMR spectroscopy studies; the self-inclusion of a phenyl group of the phosphane moiety into cyclodextrin cavity observed in water disappeared in organic solvents due to a change in conformation. Hydrogenation or hydroformylation reactions performed in water and in organic solvents showed that this ligand was able to stabilise catalytically active rhodium species in solution. In the case of the hydroformylation reaction, it was demonstrated that regioselectivity was influenced by the solventdependent conformation of the ligand.

Highly regioselective hydroformylation of internal, functionalized olefins applying Pt/Sn complexes with large bite angle diphosphines

The regioselective hydroformylation of methyl 3-pentenoate (M3P) leading to linear 5-formyl methyl pentanoate (3-FMP) was studied. For this purpose Pt/Sn catalyst systems were modified by diphosphine ligands derived from heteroaromatic xanthene-type hydrocarbons. These xantphos ligands possess a large bite angle combined with a rigid backbone. The (P∩P)PtCl2 catalyst precursor complexes were prepared and characterized by 1H- and 31P NMR-spectroscopy. The catalysts show unprecedented high regioselectivity to the terminal aldehyde. In addition, the undesired hydrogenation of the substrate and the products is largely suppressed. It was shown that activity as well as selectivity are controlled both by the bite angle and the rigidity of the backbone of the ligands.