65038-34-8

Upstream product

• 623-43-8 methyl crotonate 
• 201230-82-2 carbon monoxide 
• 625-38-7 but-3-enoic acid 
• 3724-55-8 methyl but-3-enoate 
• 623-43-8 crotonic acid methyl ester 
• 80-62-6 methacrylic acid methyl ester 

Downstream Products

• 87433-77-0 trans-5-n-butyl-4-methyl-4,5-dihydro-2(3H)-furanone 
• 89163-43-9 cis-5-n-butyl-4-methyl-4,5-dihydro-2(3H)-furanone 
• 374936-65-9 4-tert-butylcarbamoyl-4-(1-methoxycarbonyl-2-phenyl-ethylamino)-3-methyl-butyric acid methyl ester 
• 26620-41-7 (RS,SR)-γ-hydroxy-β-methyl-γ-phenylbutanoic acid lactone 
• 26704-17-6 trans-3-methyl-4-phenylbutan-4-olide 
• 143585-36-8 trans-4,5-Dihydro-4-methyl-5-(3-oxo-3-phenyl-2-propyl)-2(3H)-furanone 
• 143585-36-8 cis-4,5-Dihydro-4-methyl-5-(3-oxo-3-phenyl-2-propyl)-2(3H)-furanone 
• 143585-34-6 trans-4,5-Dihydro-4-methyl-5-(2-methyl-3-oxo-3-phenyl-2-propyl)-2(3H)-furanone 
• 143585-34-6 cis-4,5-Dihydro-4-methyl-5-(2-methyl-3-oxo-3-phenyl-2-propyl)-2(3H)-furanone 

Relevant academic research and scientific papers

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.

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.

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.

A supramolecular catalyst for regioselective hydroformylation of unsaturated carboxylic acids

(Chemical Equation Presented) The quest to capture the catalytic power of enzymes is one of the great challenges of modern chemistry. A novel system inspired by the principles of enzymatic catalysis combines recognition of the substrate and transition-metal catalysis (see scheme; Do = donor, FG = functional group) and mimics enzyme properties - high efficiency, substrate selectivity, and reaction-site selectivity.

Influence of 1,4-Bis(diphenylphosphino)butane on the Hydroformylation of α,β-Unsaturated Esters Catalyzed by Zwitterionic, Cationic, and Neutral Rhodium(I) Complexes. The Asymmetric Hydroformylation od α-Methylene-γ-Butyrolactone

An investigation was made of the effect of 1,4-bis(diphenylphosphino)butane (dppb) on the regioselectivity of the hydroformylation of α,β-unsaturated esters with synthesis gas, catalyzed by rhodium(I) complexes.Excellent regioselectivity was obtained when dppb was added as a ligand for the reaction of methyl acrylate and α-methylene-γ-butyrolactone with synthesis gas.However, it inhibits the reaction when methyl methacrylate is used as the substrate.The asymmetric hydroformylation of α-methylene-γ-butyrolactone using (+)Cl(-) as the catalyst and (R)-BINAP as the chiral ligand (6:1 ratio of (R)-BINAP/Rh) gave an aldehydic lactone, containing a quaternary chiral center, in up to 37percent ee.

A Flexible and Efficient Synthesis of Methyl 4-Oxo-2-alkenoates

The title compounds E are obtained in good yield by low temperature ring cleavage of the easily available methyl 2-siloxycyclopropanecarboxylates C with bromine and subsequent elimination of hydrogen bromide.Due to the variability of C a high flexibility concerning substituents R1 - R4 in products E is guaranteed. 2-Alkyl- and 2-methylthio-substituted olefins are thus effectively synthesized.In several cases the initially formed methyl 2-bromo-4-oxoalkanoates F are stable enough to be isolated in high yield.

HYDROFORMYLATION OF OLEFINS WITH PARAFORMALDEHYDE CATALYZED BY RHODIUM COMPLEXES

The addition of formaldehyde to olefins is efficiently catalyzed by RhH2(O2COH)2 and gives the corresponding aldehydes in neutral solution.

Application of the Water-gas Shift Reaction. I. Hydrogenation and Hydroformylation Reactions of Olefins with Carbon Monoxide and Water Catalyzed by Rhodium Phosphine Complexes

The hydrogenation of methyl crotonate with CO and H2O is efficiently catalyzed by RhH2(O2COH)2 or 2/P(i-Pr)3/n-BuLi (C7H8=norbornadiene).Both catalyst precursors are shown to form the same active species; trans-Rh(OH)(CO)2.The catalytic activity of the system (2/phosphine/n-BuLi) increases with increase of the basicity of the phosphine ligands (phosphine=P(i-Pr)3 > P(n-Bu)3 > PPh(i-Pr)2 > PPh2(i-Pr) > PPh3).This reaction is also applicable to the hydrogenation of the C=C bond of electron-withdrawing olefins and the C=O bondof ketones and aldehydes.Interestingly, the catalysis for the C=C bond, to which less electron-withdrawing groups are attached, gives dominantly aldehydes due to hydroformylation.The mechanism is also discussed.