Green, copper-catalyzed disproportionation of aromatic and heteroaromatic carboxylates to dicarboxylates

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

• wherein
• is aryl or heteroaryl, wherein aryl and heteroaryl can be optionally substituted from 1 to 3 times with a substituent selected independently at each occurrence thereof from C1-6 alkyl, C3-8 cycloalkyl, aryl, and heteroaryl;
• or a salt thereof, comprising:
• providing a compound of Formula (III):
• wherein M is a metal;
• providing a copper(I) containing compound;
• and
• reacting the compound of Formula (III) in the presence of the copper(I) containing compound to form the compound of Formula (I).

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

• wherein
• is aryl or heteroaryl, wherein aryl and heteroaryl can be optionally substituted from 1 to 3 times with a substituent selected independently at each occurrence thereof from C1-6 alkyl, C3-8 cycloalkyl, aryl, and heteroaryl;
• R is C1-6 alkyl;
• or a salt thereof, comprising:
• providing a compound of Formula (I):
• providing an alkylating agent;
• reacting the compound of Formula (I) with the alkylating agent to form the compound of Formula (IV).

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

• wherein
• is aryl or heteroaryl, wherein aryl and heteroaryl can be optionally substituted from 1 to 3 times with a substituent selected independently at each occurrence thereof from C1-6 alkyl, C3-8 cycloalkyl, aryl, and heteroaryl;
• R is C1-6 alkyl;
• or a salt thereof, comprising:
• providing a compound of Formula (II):
• wherein M is a metal;
• providing an oxide of carbon;
• providing a copper(I) containing compound;
• providing an alkylating agent;
• and
• reacting the compound of Formula (II) with the oxide of carbon in the presence of the copper(I) containing compound and the alkylating agent to form the compound of Formula (IV).