Itaconic production conditions

The biosynthesis of itaconic acid is currently achieved by a submerged batch culture process using a high-producing strain of A. terreus. As substrate, typically sucrose or glucose (molasses) is used, and as second substrate oxygen is needed in order to achieve the oxidation to itaconic acid. The itaconic acid production conditions have been reviewed in more detail by Okabe, Willke, and Klement et al. [8, 32, 33] and here only the current development and the major critical... 

Hydroformylation of norbomene proceeds slowly in spite of the expected reactivity of the strained double bond. Racemization of the product aldehyde does not occur under the reaction conditions. The hydroformylation of methyl methacrylate gives only one isomer, which is a useful chiral synthon. Dimethyl itaconate also can be hydroformylated using (12) as the chiral ligand to give aldehyde product in 82% ee accompanied by hydrogenated ester.64... 

Levinson, W.E., Kurtzman, C.P. and Kuo, T.M. 2006. Production of Itaconic Acid by Pseudozyma Antarctica NRRL Y-7808 Under Nitrogen-Limited Growth Conditions. Enzyme Microb. Technol., 39, 824-827. 

Hydrogenation of Itaconic Acid. Compared to the hydrogenation of amidoacylic acids, enols, and enamides, the Rh(/ -SpirOP)+ catalyzed hydrogenation of itaconic acid was less successful. After optimizing the hydrogenation conditions, 76.8% ee of the corresponding product was obtained in isopropanol at ambient temperature under 100 psi H2 for 2 h (eq 3). 

Propargylic alcohols are less reactive than their esters, and their carbonylation has been carried out under somewhat harsh conditions (100 °C, 100 atm) [10,11]. The carbonylation products under these conditions are different from those obtained by the carbonylation of the corresponding carbonates under milder conditions. Carbonylation of propargyl alcohol (82) in methanol without using a phosphine ligand proceeded in the presence of hydrochloric acid to afford dimethyl itaconate (79) as a main product and trimethyl aconitate (83) as a minor product (Scheme 11-24). PdCl2 or Pd/charcoal is an active catalyst [11]. 

Aqueous acidic conditions favor the formation of the iminothiazinone (227) from the reaction of itaconic acid (228) and thiourea. However, if the reaction is carried out in water alone the product is the amino tautomer (229) (Scheme 43) <91IJC(B)886>. 

Hydrogenations to produce enantiomerically pure compounds are particularly interesting for pharmaceutical and fine chemicals production. Stephenson and co-workers (102,103) have examined the continuous asymmetric hydrogenation of dimethyl itaconate using a supported chiral Rh catalyst in SCCO2. The process occurs under mild conditions with minimal catalyst leaching and can achieve high enantiomeric excess (83%) of the desired product. 

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