65038-34-8Relevant articles and documents
Precise supramolecular control of selectivity in the Rh-catalyzed hydroformylation of terminal and internal alkenes
Dydio, Pawel,Detz, Remko J.,Reek, Joost N. H.
supporting information, p. 10817 - 10828 (2013/08/23)
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.
METHOD FOR HYDROFORMYLATION
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Page/Page column 12, (2010/10/03)
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.
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
Lee, Chul Woo,Alper, Howard
, p. 499 - 503 (2007/10/02)
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.