Dimethyl muconate

Conjugated dienes are a special substrate for the TMM synthon because they can potentially undergo [3 + 2] as well as [4 + 3] cycloaddition. While dimethyl ( . )-muconate gives only seven-membered ring [4 + 3] adducts, methyl 2,4-pentadienoate reacts exclusively at the terminal double bond with (79) to give a vinylmethylenecyclopropane (equation 100). The diphenyl system (81) also reacts with simple 1,3-dienes to produce only diphenylidenecyclopentanes in the presence of Ni or Pd catalysts (equation 101). ... 

The seven-membered ring product (49 equation 17) is obtained as a mixture of the trans and cis isomers (82 18) in 67% yield from the reaction of (26) with dimethyl muconate (48) in the presence of a... 

In another patent application Frost et al. claim the synthesis of dimethyl cyclohex-2-ene-l,4-dicarboxylate starting from /rani,/rani-dimethyl muconate, using high pressures ethylene at 150-170 °C. According to the patent application, dimethyl cyclohex-2-ene-l,4-dicarboxylate can be successfully converted into TA by reacting it over Pt/C in the presence of oxygen and... 

Another example of template polycondensation was described by Ogata and co-workers (82-85). Polycondensation of dimethyl tartrate or dimethyl muconate with hexamethylenediamine was increased by the presence of poly(vinylpyrrolidinone) and poly(vinyl alcohol). It was also foimd that polysaccharides increase the polycondensation rate. It seems that hydroxyl groups play a substantial role in the absorption of monomers onto the template. 

Small amounts of dimethyl muconate and dimethyl fumarate accompanied the main product, dimethyl maleate (85% selectivity). Dimethyl muconate could be made to become the major product simply by inverting the C2H2/CO ratio. A more efficient system was later found to be Pdl2-tiourea. To the catalytic complex the formula Pd(l)(H2NCSNH2)3+r was assigned. ... 

Some kinds of bacteria can oxidise aromatic compounds when yet another substrate is present [108]. In the presence of hexadecane, for example, Nocardia cooxidizes ethyl benzene to phenylacetic acid and p-xylene to a,a -dimethyl muconic acid [108] (Fig. 2). 

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