This disclosure provides for catalyst systems and processes for forming an α,β-unsaturated carboxylic acid or a salt thereof. In an aspect, the catalyst system can comprise: a transition metal precursor comprising a Group 8-11 transition metal and at least one first ligand; optionally, at least one second ligand; an olefin; carbon dioxide (CO.sub.2); a diluent; and an oxoacid anion-substituted polyaromatic resin comprising a sulfonated polyaromatic resin, a phosphonated polyaromatic resin, a sulfinated polyaromatic resin, a thiosulfonated, or a thiosulfinated polyaromatic resin, and further comprising associated metal cations. Methods of regenerating the polyaromatic resin with associated metal cations are described.

The present disclosure discusses (i) a compound having a chemical formula according to Formula (I), or its enantiomer; and (ii) a compound that is reactive with a hydride to produce a compound having a chemical formula according to Formula (I), or its enantiomer. Formula (I) is: Formula (I) where R.sub.1 and R.sub.2 are H, optionally substituted C.sub.1-C.sub.3 alkyl, or linked together to form an optionally substituted C.sub.3 or C.sub.4 alkyl group; R.sub.3 and R.sub.3′ are H; R.sub.4 and R.sub.4′ are the same, and are optionally substituted C.sub.1-C.sub.6 alkyl; and R.sub.5 and R.sub.5′ are the same, and are optionally substituted aryl or heteroaryl. In some examples, R4 and R5 are linked, and R.sub.4′ and R.sub.5′ are linked, where both linking groups are the same. The present disclosure also discusses methods of asymmetric reduction of an imine, and methods of forming the catalysts and pre-catalysts. ##STR00001##

Provided is a method of preparing an acrylonitrile dimer including: supplying an acrylonitrile monomer, a phosphorus-based catalyst, and an alcohol solvent to a reactor to perform a dimerization reaction to produce dimerized reactants (S10); cooling the dimerized reactants to crystallize the phosphorus-based catalyst (S20); separating the crystallized phosphorus-based catalyst (S30); and supplying the dimerized reactants from which the phosphorus-based catalyst is separated to a distillation column to separate the acrylonitrile dimer (S40).

A method for preparing 1,2-propanediol involves reacting propene with hydrogen peroxide in the presence of a catalyst mixture, containing a phase transfer catalyst and a heteropolytungstate, in a liquid reaction mixture containing an aqueous phase with a maximum apparent pH of 6 and an organic phase. The method then involves separating the reaction mixture into an aqueous phase (P.sub.a) containing 1,2-propanediol and formic acid and an organic phase (P.sub.o); recycling at least part of the separated organic phase (P.sub.o) to the reaction; contacting at least a part of the separated aqueous phase (P.sub.a) with a palladium catalyst; and recovering 1,2 propanediol from the aqueous phase provided by the contacting. The contacting of at least a part of the separated aqueous phase (P.sub.a) with the palladium catalyst reduces the content of formic acid.

This disclosure provides for catalyst systems and processes for forming an α,β-unsaturated carboxylic acid or a salt thereof. In an aspect, the catalyst system can comprise: a transition metal precursor comprising a Group 8-11 transition metal and at least one first ligand; optionally, at least one second ligand; an olefin; carbon dioxide (CO.sub.2); a diluent; and an oxoacid anion-substituted polyaromatic resin comprising a sulfonated polyaromatic resin, a phosphonated polyaromatic resin, a sulfinated polyaromatic resin, a thiosulfonated, or a thiosulfinated polyaromatic resin, and further comprising associated metal cations. Methods of regenerating the polyaromatic resin with associated metal cations are described.

This disclosure provides for catalyst systems and processes for forming an ,-unsaturated carboxylic acid or a salt thereof. In an aspect, the catalyst system can comprise: a transition metal precursor comprising a Group 8-11 transition metal and at least one first ligand; optionally, at least one second ligand; an olefin; carbon dioxide (CO.sub.2); a diluent; and an oxoacid anion-substituted polyaromatic resin comprising a sulfonated polyaromatic resin, a phosphonated polyaromatic resin, a sulfinated polyaromatic resin, a thiosulfonated, or a thiosulfinated polyaromatic resin, and further comprising associated metal cations. Methods of regenerating the polyaromatic resin with associated metal cations are described.

The present disclosure discusses (i) a compound having a chemical formula according to Formula (I), or its enantiomer; and (ii) a compound that is reactive with a hydride to produce a compound having a chemical formula according to Formula (I), or its enantiomer. Formula (I) is: Formula (I) where R.sub.1 and R.sub.2 are H, optionally substituted C.sub.1-C.sub.3 alkyl, or linked together to form an optionally substituted C.sub.3 or C.sub.4 alkyl group; R.sub.3 and R.sub.3are H; R.sub.4 and R.sub.4 are the same, and are optionally substituted C.sub.1-C.sub.6 alkyl; and R.sub.5 and R.sub.5 are the same, and are optionally substituted aryl or heteroaryl. In some examples, R4 and R5 are linked, and R.sub.4 and R.sub.5 are linked, where both linking groups are the same. The present disclosure also discusses methods of asymmetric reduction of an imine, and methods of forming the catalysts and pre-catalysts.

##STR00001##

This disclosure provides for catalyst systems and processes for forming an ,-unsaturated carboxylic acid or a salt thereof. In an aspect, the catalyst system can comprise: a transition metal precursor comprising a Group 8-11 transition metal and at least one first ligand; optionally, at least one second ligand; an olefin; carbon dioxide (CO.sub.2); a diluent; and an oxoacid anion-substituted polyaromatic resin comprising a sulfonated polyaromatic resin, a phosphonated polyaromatic resin, a sulfinated polyaromatic resin, a thiosulfonated, or a thiosulfinated polyaromatic resin, and further comprising associated metal cations. Methods of regenerating the polyaromatic resin with associated metal cations are described.

This disclosure provides for routes of synthesis of ,-unsaturated carboxylic acids and their salts, including acrylic acid. For example, disclosed is a process for producing an ,-unsaturated carboxylic acid or its salt, comprising: (1) contacting a group 8-11 transition metal precursor, an olefin, carbon dioxide, a diluent, and a sulfur oxoacid anion-substituted polyaromatic resin or a phosphorus oxoacid anion-substituted polyaromatic resin with associated metal cations to provide a mixture; and (2) applying reaction conditions to the mixture suitable to produce the ,-unsaturated carboxylic acid or a salt thereof. Methods of regenerating the polyaromatic resin with associated metal cations are described.

The catalyst solution used in a hydroformylation process is prepared for storage by first reducing its acid concentration and/or water content, and then storing the solution under a blanket of syngas and/or an inert gas. Alternatively, or in addition to, the catalyst solution can be stored with an aqueous buffer comprising materials that will neutralize and/or absorb the acid species within the catalyst solution.