Itaconate, dimethyl

Cyclization. Constmction of ben2otrifluorides from aHphatic feedstocks represents a new technique with economic potential. For example, l,l,l-trichloro-2,2,2-trifluoroethane [354-58-5] and dimethyl itaconate [617-52-7] form 4-methoxy-6-trifluoromethyl-2JT-pyran-2-one [101640-70-4] which is converted to methyl 3-(trifluoromethyi)ben2oate [2557-13-3] ixh. acetjdene or norbomadiene (125). 

Apart from poly(ethylene glycol), other hydroxyl-terminated polymers and low-molecular weight compounds were condensed with ACPC. An interesting example is the reaction of ACPC with preformed poly(bu-tadiene) possessing terminal OH groups [26]. The reaction was carried out in chloroform solution and (CH3CH2)3N was used as a catalyst. MAIs based on butadiene thus obtained were used for the thermally induced block copolymerization with styrene [26] and dimethyl itaconate [27]. 

Reaction Characteristics of Immobilized Ru-BINAP Catalysts in Asymmetric Hydrogenation of Dimethyl itaconate... 

In this work, various Ru-BINAP catalysts immobilized on the phosphotungstic acid(PTA) modified alumina were prepared and the effects of the reaction variables (temperature, H2 pressure, solvent and content of triethylamine) on the catalytic performance of the prepared catalysts were investigated in the asymmetric hydrogenation of dimethyl itaconate (DMIT). 

Effect of reaction conditions on the asymmetric hydrogenation of dimethyl itaconate over immobilized Ru-BINAP catalyst... 

Short residence time and high heat transfer capabilities are demanded for the transfer hydrogenation of dimethyl itaconate, as in general for comparable liquid/liquid reactions [117]. 

H-transfer reduction Investigated in Micro Reactors Organic synthesis 63 [OS 63] H-transfer reduction of dimethyl itaconate... 

Figure 4.78 Liquid/liquid H-transfer reduction of dimethyl itaconate to dimethyl methylsuccinate experimental results vs models.

On the other hand, Bolm et al. have reported, more recently, the use of BINOL-derived A -phosphino sulfoximines as ligands in the rhodium-catalysed hydrogenation of dimethyl itaconate and a-acetamidoacrylates, achieving excellent enantioselectivities of up to 99% ee (Scheme 8.12). In the main... 

Table 24.1. Enantioselective hydrogenation of dimethyl itaconate using Rh(l)-complexes ...

These ligands also give excellent results with dimethyl itaconate and a-arylenamides. 

Togni and co-workers have used the convergent methodology to link phosphine-containing chiral ferrocene ligands on the cyclophosphazene core to obtain dendrimeric structures of the type 37 (Fig. 21) (201). The reaction with the cyclophosphazene end occurs by the replacement of the P-Cl bond and by the formation of the P-0 bond. The dendrimers contain twelve and sixteen ferrocene moieties respectively. The phosphine units present can coordinate to Rh(I) to afford metallic dendrimers, which have been shown to be excellent catalysts for the enantioselective hydrogenation of dimethyl itaconate. The product... 

The aqueous biphase hydrogenation of dimethyl itaconate is accomplished with an Ir-(7 )-(7 )-3-benzyl(/>-sulfonate)-2,4-bis(diphenylphosphino)pentane complex.605... 

A 1996 work deposited four different catalytic metals on a p-cyclodextrin— epichlorohydrin copolymer to prepare Pd(Pt, Rh, Ru)-P-cyclodextrin copolymer catalysts.8 These were used to catalyze the asymmetric hydrogenations of the C=C bonds of trans-2-methyl-2-pentenoic acid, and dimethyl itaconate. 

A set of core-functionalized dendrimers was synthesized by Van Leeuwen et al. and one compound was applied in continuous catalysis. [45] The dendritic dppf, Xantphos and triphenylphosphine derivatives (Figures 4.22, 4.30 and 4.31) were active in rhodium-catalyzed hydroformylation and hydrogenation reactions (performed batch-wise). Dendritic effects were observed which are discussed in paragraph 4.5. The dendritic rhodium-dppf complex was applied in a continuous hydrogenation reaction of dimethyl itaconate. 

Upon reaction of elemental tin with dimethyl itaconate in the presence of anhydrous HC1 in ethylene glycol, dimethyl or diethyl ether, 92% of Me02CCH2CH(C02Me)CH2SnCl3 is obtained as sole product299. 

Fu has reported a planar-chiral bisphosphorus ligand 45 with a phosphaferrocene backbone. The ligand has provided enantioselectivity up to 96% ee in the hydrogenation of a-dehydroamino acid derivatives.99 Another planar-chiral ferrocene-based bisphosphorus ligand 46 has been reported by Kagan recently and enantioselectivity up to 95% ee has been obtained in the reduction of dimethyl itaconate.100... 

Other interesting electron-deficient olefin substrates for the asymmetric conjugate addition include cr-acet-amidoacrylic ester SI,101 dimethyl itaconate S2,114 ct,/3-unsaturated sulfones S3,115 and alkenylphosphonate S4116 (Figure 8). 

If Q-symmetric ligands are employed in asymmetric hydrogenation instead of the corresponding C2-symmetric ligands, there coexist principally four stereoiso-meric substrate complexes, namely two pairs of each diastereomeric substrate complex. Furthermore, it has been shown that, for particular catalytic systems, intramolecular exchange processes between the diastereomeric substrate complexes should in principle be taken into account [57]. Finally, the possibility of non-estab-hshed pre-equilibria must be considered [58]. The consideration of four intermediates, with possible intramolecular equilibria and disturbed pre-equihbria, results in the reaction sequence shown in Scheme 10.3. This is an example of the asymmetric hydrogenation of dimethyl itaconate with a Rh-complex, which contains a Q-symmetrical aminophosphine phosphinite as the chiral ligand. 

The hydrogen consumption and enantioselectivities for the asymmetric hydrogenation of dimethyl itaconate with various substituted catalysts of the basic type [Rh(PROPRAPHOS)COD]BF4 are illustrated in Figure 10.13 [61]. The systems are especially suitable for kinetic measurements because of the rapid hydrogenation of COD in the precatalyst. There are, in practice, no disturbances due to the occurrence of induction periods. 

A comparison of the activities for various catalyst derivatives shown in Figure 10.13 seems to prove that the ligand with the cyclohexyl residue leads to the most active catalyst for the hydrogenation of dimethyl itaconate. The catalyst containing the methyl derivative apparently exhibits the lowest activity. 

Table 10.2 Kinetic analysis of the asymmetric hydrogenation of dimethyl itaconate with derivatives of [Rh(PROPRAPHOS)-COD]BF4 (see Fig. 10.13).

Fig. 10.16 Variation of the concentration of dimethyl itaconate for the hydrogenation with [Rh((S)-PROPRAPHOS)COD]BF4.

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