Itaconic acid transfer hydrogenation

Another biofuel candidate that can be derived from LA is 2-methyl tetrahydro-furan (2-MTHF), which is obtained via the intermediate yVl in a reaction pathway that includes both dehydration and hydrogenation steps [99, 100]. In a comparable reaction, itaconic acid, a platform chemical produced industrially by fermentation of carbohydrates such as glucose, can be converted into 3-methyl tetrahydrofuran [100]. The hydrogen required to produce yVl may be obtained from formic acid, via transfer... 

A example, typically enantioselective, is the transfer hydrogenation of itaconic acid, which is reduced to methylsuccinic acid with the formic acid/triethylamine azeotrope (Scheme 1). 

Scheme 1. Transfer hydrogenation of itaconic add to give methylsuccinic acid with the...

Asymmetric hydrogen transfer from EtOH, /-PrOH or triethylammonium formate to Z-a-acetamidocinnamic acid Z-3.32 (R = Ph, Z = COMe, R = H) or to itaconic acid 7.7 (R = H) is highly enantioselective when the catalyst is a binap-Ru complex [873, 1333] (Figure 7.14). The relationship between the absolute configuration of the saturated add and the binap ligand is the same as in the catalytic hydrogenation. However, hydrogen transfer to other a,P-unsaturated acids, such as the precursor of naproxen (7.15), is less enantioselective [1333],... 

Water-soluble Rh(I) complexes containing TPPTS catalyzed the transfer hydrogenation of itaconic, mesaconic, citraconic and tiglic acids as well as that of a-acetamidoacrylic and a-acetamidocinnamic acids from HCOOM (M = Na+, K+, NH,+) [235], The reactions were ran at 50 °C for 15-67 h, during which 48-100 % conversions were achieved. Use of the chiral tetrasulfonated cyclobutanediop, 37, led to an enantiomeric excess of up to 43 %, which is close to the value obtained in biphasic hydrogenations catalyzed by the same rhodium complex [100],... 

Scheme 12.17. Enantioselective hydrogenation of itaconic acid as a mechanistic probe for hydrogen transfer processes in SCCO2.

---