Biobased production of functionalized alpha-substituted acrylates and c4-dicarboxylates

A method for making a functionalized alpha substituted acrylate, or a salt or ester thereof, the method comprising contacting a functionalized alpha substituted C4 dicarboxylic acid or functionalized alpha substituted 3-hydroxypropionic acid, or a salt, ester, or lactone thereof, with a metal catalyst.

A method for making a derivative of a functionalized alpha substituted C4 dicarboxylic acid and a compound having formula I, the method comprising contacting a compound selected from formula II, III and IV or a salt, ester or lactone thereof, with a metal catalyst, wherein said derivative of functionalized alpha substituted C4 dicarboxylic acid is selected from:

• wherein:
• each R1 is selected from alkyl (longer than methyl), hydroxy, hydroxyalkyl, branched hydroxyalkyl, alkoxy, branched alkyl, amino, branched amino alkyl, phenyl, alkyl substituted phenyl, —S—, —SH, —SeH, —Se—, hydroxyaromatic, aminoaromatic, formyl, carbamoyl, indolyl, guanidinyl, and carboxylate when n>1, and R2 is individually selected from H and a protecting group, and R2 is individually selected from H and a protecting group, and n is equal to 1 or greater.

A method for making a hydroxyalkyl alpha substituted acrylic acid, or a salt, lactone or ester thereof, the method comprising contacting a hydroxyalkyl alpha substituted C4 dicarboxylic acid, or a salt, ester, or lactone thereof, with a metal catalyst.

The method of method 42, wherein the promoter comprises sulfur.

A composition comprising a functionalized alpha substituted acrylic acid or a salt, ester or lactone thereof, and one or more compounds selected from an alpha-(hydroxymethyl) malic acid, an alpha-(2-hydroxypropyl) malic acid, an alpha-(1-hydroxyethyl) malic acid and an alpha-(2-hydroxyethyl) malic acid or salts or esters thereof.

A recombinant microorganism comprising a functionalized alpha substituted acrylic acid, wherein the functional alpha substitution is selected from an alkyl (longer than methyl), hydroxy, hydroxyalkyl, branched hydroxyalkyl, alkoxy, branched alkyl, amino, branched amino alkyl, phenyl, alkyl substituted phenyl, —S—, —SH, —SeH, —Se—, hydroxyaromatic, aminoaromatic, formyl, carbamoyl, indolyl, guanidinyl, and carboxylate when n>2, and at least one recombinant nucleic acid sequence encoding at least one enzyme selected from a transaminase (FIG. 12, row A), a synthase (FIG. 12, row B), a dehydratase (FIG. 12, row C), a hydratase (FIG. 12, row D), a dehydrogenase (FIG. 12, row E), a cis-trans isomerase (FIG. 12, row F), a cyclase, lactonase, lactamase (FIG. 12, row G), an esterase (FIG. 12, row H), a decarboxylase (FIG. 12, row I), a reductase (FIG. 14, row C), a decarboxylase (FIG. 14, row D), a reductase (FIG. 14, row E), a CoA transferase (FIG. 14, row F), and a 3HP-CoA dehydratase (FIG. 14, row G).

A recombinant microorganism comprising a hydroxymethyl malonyl-CoA and a recombinant nucleic acid sequence encoding an enzyme selected from a CoA transferase (FIG. 16, row A), a CoA carboxylase (FIG. 16, row B), CoA transferase (FIG. 16, row C), a reductase (FIG. 16, row D), a dehydrogenase (FIG. 16, row D), a 3HP CoA-dehydratase (FIG. 16, row E), a CoA transferase (FIG. 16, row F), a carboxylase (FIG. 16, row G), a CoA transferase (FIG. 16, row H), an oxi-reductase (FIG. 16, row I), a reductase (FIG. 16, row J), a dehydratase (FIG. 16, row K), and a CoA transferase (FIG. 16, row L).

A recombinant microorganism comprising a hydroxymethyl malonyl-CoA and a recombinant nucleic acid sequence encoding an enzyme selected from a CoA transferase (FIG. 16, row A), a CoA carboxylase (FIG. 16, row B), CoA transferase (FIG. 16, row C), a reductase (FIG. 16, row D), a dehydrogenase (FIG. 16, row D), a 3HP CoA-dehydratase (FIG. 16, row E), a CoA transferase (FIG. 16, row F), a carboxylase (FIG. 16, row G), a CoA transferase (FIG. 16, row H), an oxi-reductase (FIG. 16, row I), a reductase (FIG. 16, row J), and a CoA transferase (FIG. 16, row L).

A recombinant microorganism comprising a compound selected from 2-methylene-succinyl semialdehyde, alpha-hydroxyethyl acrylate and tulipalin A, and a recombinant nucleic acid sequence encoding an enzyme selected from an oxi-reductase (FIG. 18, Table 7, row A), a reductase (FIG. 18, Table 7, row B), a cyclase (FIG. 18, Table 7, row C), a lactonase (FIG. 18, Table 7, row C), a lactamase (FIG. 18, Table 7, row C) and combinations thereof.

A recombinant microorganism comprising an alpha-substituted 3-hydroxypropionic acid and a recombinant nucleic acid sequence encoding an enzyme selected from a CoA transferase (FIG. 16, row A), a CoA carboxylase (FIG. 16, row B), CoA transferase (FIG. 16, row C), a reductase (FIG. 16, row D), a dehydrogenase (FIG. 16, row D), a carboxylase (FIG. 16, row G), a CoA transferase (FIG. 16, row H), an oxi-reductase (FIG. 16, row I), and a reductase (FIG. 16, row J).

A recombinant microorganism comprising an alpha-substituted malonyl-CoA and a recombinant nucleic acid sequence encoding an enzyme selected from a CoA transferase (FIG. 16, row A), a CoA carboxylase (FIG. 16, row B), CoA transferase (FIG. 16, row C), a reductase (FIG. 16, row D), a dehydrogenase (FIG. 16, row D), a carboxylase (FIG. 16, row G), a CoA transferase (FIG. 16, row H), an oxi-reductase (FIG. 16, row I), and a reductase (FIG. 16, row J).

A recombinant microorganism comprising an alpha-substituted malonic semialdehyde and a recombinant nucleic acid sequence encoding an enzyme selected from a CoA transferase (FIG. 16, row A), a CoA carboxylase (FIG. 16, row B), CoA transferase (FIG. 16, row C), a reductase (FIG. 16, row D), a dehydrogenase (FIG. 16, row D), a carboxylase (FIG. 16, row G), a CoA transferase (FIG. 16, row H), an oxi-reductase (FIG. 16, row I), and a reductase (FIG. 16, row J).

A compound of the formula:

• or a salt thereof,
• wherein:
• each R1 is selected from alkyl (longer than methyl), hydroxy, hydroxyalkyl, branched hydroxyalkyl, alkoxy, branched alkyl, amino, branched amino alkyl, phenyl, alkyl substituted phenyl, —S—, —SH, —SeH, —Se—, hydroxyaromatic, aminoaromatic, formyl, carbamoyl, indolyl, guanidinyl, and carboxylate when n>1, and n is equal to 1 or greater.

A compound of the formula:

• or a salt thereof,
• wherein:
• each R1 is selected from alkyl (longer than methyl), hydroxy, hydroxyalkyl, branched hydroxyalkyl, alkoxy, branched alkyl, amino, branched amino alkyl, phenyl, alkyl substituted phenyl, —S—, —SH, —SeH, —Se—, hydroxyaromatic, aminoaromatic, formyl, carbamoyl, indolyl, guanidinyl, and carboxylate when n>1, and n is equal to 1 or greater.