Base-catalyzed isomerization of muconic acid derivatives

A compound of Formula (IVb):

• wherein
• X is CH, O, S, N, P, or C═O;
• R5 is selected from the group consisting of H, C1-20 alkyl, heteroaryl, heterocyclyl, carborane, C1-20 alkyl-O—Zn—O—C1-20 alkyl, C1-20 alkyl-O—Zn—O-heteroaryl, heteroaryl-O—Zn—O-heteroaryl, C1-20 alkyl-O—Zn—O-heterocyclyl, heterocyclyl—O—Zn—O-heterocyclyl, and heterocyclyl—O—Zn—O-heteroaryl, wherein C1-20 alkyl, heteroaryl, and heterocyclyl can be optionally substituted 1 to 3 times with R9;
• R6 can be absent and, if present, is H or C1-6 alkyl;
• R7 is H or C1-6 alkyl;
• R8 is H or C1-6 alkyl;
• R9 is independently selected from the group consisting of H, C1-6 alkyl, SH, NH2, PH2, P(O)(OR10)2, P(O)(OR10)3, P(O)(OR10)2R1, P(O)(OR10)(R11)2 P(O)(R11)2 BH2,
• a is 1, 2, 3, or 4;
• b is 1, 2, or 3;
• c is 1, 2, 3, 4, or 5;
• each R10 is independently selected from the group consisting of H, C1-6 alkyl, C1-6 alkenyl, and aryl, wherein aryl can be optionally substituted 1 to 3 times with halogen, or C1-6 alkyl;
• each R11 is independently selected from the group consisting of H, C1-6 alkyl, C1-6 alkenyl, and aryl, wherein aryl can be optionally substituted 1 to 3 times with halogen, or C1-6 alkyl,
• is the point of attachment of R9 to R5;
• with the proviso that if R7 is H, then R8 is not H,
• or a salt thereof.

A polymer of Formula (X):

• wherein
• Y is NH or O;
• R is independently selected from the group consisting of H and C1-20 alkyl;
• i is 1 to 1,000,000;
• j is 1 to 1,000,000;
• m is 0 to 32;
• s is 0 to 32;
• and
• is a terminal group of the polymer;
• is a single or a double bond, and only one of is a double bond.

A process of making a polymer of Formula (XIII):

• wherein
• Y is NH or O;
• R is independently selected from the group consisting of H and C1-20 alkyl;
• each R′ is independently H or
• and only one of R′ is
• X is CH, O, S, N, P, or C═O;
• R5 is selected from the group consisting of H, C1-20 alkyl, heteroaryl, heterocyclyl, carborane, C1-20 alkyl-O—Zn—O—C1-20 alkyl, C1-20 alkyl-O—Zn—O-heteroaryl, heteroaryl-O—Zn—O-heteroaryl, C1-20 alkyl-O—Zn—O-heterocyclyl, heterocyclyl—O—Zn—O-heterocyclyl, and heterocyclyl—O—Zn—O-heteroaryl, wherein C1-20 alkyl, heteroaryl, and heterocyclyl can be optionally substituted 1 to 3 times with R9;
• R6 can be absent and, if present, is H or C1-6 alkyl;
• R9 is independently selected from the group consisting of H, C1-6 alkyl, SH, NH2, PH2, P(O)(OR10)2, P(O)(OR10)3, P(O)(OR10)2R11, P(O)(OR10)(R11)2 P(O)(R11)2 BH2,
• a is 1, 2, 3, or 4;
• b is 1, 2, or 3;
• c is 1, 2, 3, 4, or 5;
• each R10 is independently selected from the group consisting of H, C1-6 alkyl, C1-6 alkenyl, and aryl, wherein aryl can be optionally substituted 1 to 3 times with halogen, or C1-6 alkyl;
• each R11 is independently selected from the group consisting of H, C1-6 alkyl, C1-6 alkenyl, and aryl, wherein aryl can be optionally substituted 1 to 3 times with halogen, or C1-6 alkyl,
• is the point of attachment of R9 to R5;
• i is 1 to 1,000,000;
• j is 1 to 1,000,000;
• m is 0 to 32;
• s is 0 to 32;
• and
• is a terminal group of the polymer;
• is a single bond attached to one of the positions shown, said process comprises:
• preparing the compound of Formula (IV) by the process of claim 13;
• providing a compound having the structure of Formula (XI):
• providing a compound having the structure of Formula (XII):
• and
• reacting the compound of Formula (IV), the compound of Formula (XI), and the compound of Formula (XII) under conditions effective to produce the polymer of Formula (XIII).

A polymer of Formula (XIII):

• wherein
• Y is NH or O;
• R is independently selected from the group consisting of H and C1-20 alkyl;
• each R′ is independently H or
• and only one of R′ is
• X is CH, O, S, N, P, or C═O;
• R5 is selected from the group consisting of H, C1-20 alkyl, heteroaryl, heterocyclyl, carborane, C1-20 alkyl-O—Zn—O—C1-20 alkyl, C1-20 alkyl-O—Zn—O-heteroaryl, heteroaryl-O—Zn—O-heteroaryl, C1-20 alkyl-O—Zn—O-heterocyclyl, heterocyclyl—O—Zn—O-heterocyclyl, and heterocyclyl—O—Zn—O-heteroaryl, wherein C1-20 alkyl, heteroaryl, and heterocyclyl can be optionally substituted 1 to 3 times with R9;R6 can be absent and, if present, is H or C1-6 alkyl;
• R9 is independently selected from the group consisting of H, C1-6 alkyl, SH, NH2, PH2, P(O)(OR10)2, P(O)(OR10)3, P(O)(OR10)2R11, P(O)(OR10)(R11)2 P(O)(R11)2 BH2,
• a is 1, 2, 3, or 4;
• b is 1, 2, or 3;
• c is 1, 2, 3, 4, or 5;
• each R10 is independently selected from the group consisting of H, C1-6 alkyl, C1-6 alkenyl, and aryl, wherein aryl can be optionally substituted 1 to 3 times with halogen, or C1-6 alkyl;
• each R11 is independently selected from the group consisting of H, C1-6 alkyl, C1-6 alkenyl, and aryl, wherein aryl can be optionally substituted 1 to 3 times with halogen, or C1-6 alkyl,
• is the point of attachment of R9 to R5;
• i is 1 to 1,000,000;
• j is 1 to 1,000,000;
• m is 0 to 32;
• s is 0 to 32;
• and
• is a terminal group of the polymer;
• is a single bond attached to one of the positions shown.

A process for preparation of a compound of Formula (XIV):

• wherein
• R13 is YR17R18;
• R14 is ZR19R20;
• Y and Z are independently selected from CH, O, S, N, P, or C═O;
• R17 and R19 are independently selected from the group consisting of H, C1-20 alkyl, heteroaryl, heterocyclyl, carborane, C1-20 alkyl-O—Zn—O C1-20 alkyl, C1-20 alkyl-O—Zn—O heteroaryl, heteroaryl-O—Zn—O-heteroaryl, C1-20 alkyl-O—Zn—O-heterocyclyl, heterocyclyl O—Zn—O heterocyclyl, and heterocyclyl O—Zn—O heteroaryl, wherein C1-20 alkyl, heteroaryl, and heterocyclyl can be independently optionally substituted 1 to 3 times with R21,
• R18 and R20 independently can be absent and, if present, are independently H or C1-6 alkyl;
• R21 is independently selected from the group consisting of H, C1-6 alkyl, SH, NH2, PH2, P(o)(OR22)2, P(O)(OR22)3, P(O)(OR22)2R23, P(O)(OR22)(R23)2, P(O)(R23)2, BH2,
• a is 1, 2, 3, or 4;
• b is 1, 2, or 3;
• c is 1, 2, 3, 4, or 5;
• each R22 is independently selected from the group consisting of H, C1-6 alkyl, C1-6 alkenyl, and aryl, wherein aryl can be optionally substituted 1 to 3 times with halogen, or C1-6 alkyl;
• each R23 is independently selected from the group consisting of H, C1-6 alkyl, C1-6 alkenyl, and aryl, wherein aryl can be optionally substituted 1 to 3 times with halogen, or C1-6 alkyl,
• is the point of attachment of R21 to R17 or R19
• or a salt thereof,
• this process comprises:
• providing a compound of Formula (XV) having the structure:
• wherein
• R15 is H or C1-6 alkyl;
• R16 is H or C1-6 alkyl;
• and
• forming the compound of Formula (I) from the compound of Formula (II).