Asymmetric syntheses
AssigneeUnion Carbide Chemicals & Plastics Technology Corporation
InventorsJames E. Babin, Gregory T. Whiteker
Life of this patent
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Abstract
This invention relates to asymmetric syntheses in which a prochiral or chiral compound is contacted in the presence of an optically active metal-ligand complex catalyst to produce an optically active product.
Claims58
A process which comprises reacting a prochiral or chiral compound in the presence of an optically active metal-ligand complex catalyst to produce an optically active product, said optically active metal-ligand complex catalyst comprising a metal complexed with an optically active ligand having the formula ##STR20## wherein each W is the same or different and is phosphorus, arsenic or antimony, each X is the same or different and is oxygen, nitrogen or a covalent bond linking W and Y, Y is a substituted or unsubstituted hydrocarbon residue, each Z is the same or different and is a substituted or unsubstituted hydrocarbon residue or the Z substituents bonded to W may be bridged together to form a substituted or unsubstituted cyclic hydrocarbon residue, and m is a value equal to the free valence of Y, provided at least one of Y and Z is optically active and provided said process is other than hydroformylation and hydrogenation.
A hydroformylation process which comprises reacting a prochiral or chiral olefinically unsaturated organic compound with carbon monoxide and hydrogen in the presence of an optically active metal-ligand complex catalyst to produce an optically active product, said optically active metal-ligand complex catalyst comprising a metal complexed with an optically active ligand having the formula ##STR22## wherein each W is the same or different and is phosphorus, arsenic or antimony, each X is the same or different and is oxygen, nitrogen or a covalent bond linking W and Y, Y is a substituted or unsubstituted hydrocarbon residue, each Z is the same or different and is a substituted or unsubstituted hydrocarbon residue or the Z substituents bonded to W may be bridged together to form a substituted or unsubstituted cyclic hydrocarbon residue, and m is a value equal to the free valence of Y, provided at least one of Y and Z is optically active;
- with the provisos that when each W is phosphorus and each X is a covalent bond, then the Z substituents cannot all be hydrocarbon residues having a carbon atom directly bonded to phosphorus, and when Y is a substituted 2 carbon aliphatic chain and m is a value of 2 and both W substituents are phosphorus and one X substituent is oxygen and the other X substituent is nitrogen, then the Z substituents cannot all be phenyl, and when Y is a substituted tetrahydropyran and m is a value of 2 and both W substituents are phosphorus and the X substituents are both oxygen, then the Z substituents cannot all be aryl.
An optically active ligand having the formula ##STR24## wherein each W is the same or different and is phosphorus, arsenic or antimony, each X is the same or different and is oxygen, nitrogen or a covalent bond linking W and Y, Y is a substituted or unsubstituted hydrocarbon residue, each Z is the same or different and is a substituted or unsubstituted hydrocarbon residue or the Z substituents bonded to W may be bridged together to form a substituted or unsubstituted cyclic hydrocarbon residue, and m is a value equal to the free valence of Y, provided at least one of Y and Z is optically active;
- with the provisos that when each W is phosphorus and each X is a covalent bond, then the Z substituents cannot all be hydrocarbon residues having a carbon atom directly bonded to phosphorus, and when Y is a substituted 2 carbon aliphatic chain and m is a value of 2 and both W substituents are phosphorus and one X substituent is oxygen and the other X substituent is nitrogen, then the Z substituents cannot all be phenyl, and when Y is a substituted tetrahydropyran and m is a value of 2 and both W substituents are phosphorus and the X substituents are both oxygen, then the Z substituents cannot all be aryl, and when Y is an unsubstituted 3 carbon aliphatic chain and m is a value of 2 and both X substituents are oxygen and both W substituents are phosphorus, then the Z substituents bonded to each phosphorus cannot be bridged together to form substituted -oxy-ethylene-oxy- groups.
An optically active metal-ligand complex catalyst comprising a metal complexed with an optically active ligand having the formula ##STR26## wherein each W is the same or different and is phosphorus, arsenic or antimony, each X is the same or different and is oxygen, nitrogen or a covalent bond linking W and Y, Y is a substituted or unsubstituted hydrocarbon residue, each Z is the same or different and is a substituted or unsubstituted hydrocarbon residue or the Z substituents bonded to w may be bridged together to form a substituted or unsubstituted cyclic hydrocarbon residue, and m is a value equal to the free valence of Y, provided at least one of Y and Z is optically active;
- with the provisos that when each W is phosphorus and each X is a covalent bond, then the Z substituents cannot all be hydrocarbon residues having a carbon atom directly bonded to phosphorus, and when Y is a substituted 2 carbon aliphatic chain and m is a value of 2 and both w substituents are phosphorus and one X substituent is oxygen and the other X substituent is nitrogen, then the Z substituents cannot all be phenyl, and when Y is a substituted tetrahydropyran and m is a value of 2 and both W substituents are phosphorus and the X substituents are both oxygen, then the Z substituents cannot all be aryl, and when Y is an unsubstituted 3 carbon aliphatic chain and m is a value of 2 and both X substituents are oxygen and both W substituents are phosphorus, then the Z substituents bonded to each phosphorus cannot be bridged together to form substituted -oxy-ethylene-oxy- groups.
An optically active metal-ligand complex catalyst precursor composition comprising
- (i) an optically active metal-ligand complex catalyst comprising a metal complexed with an optically active ligand having the formula ##STR28## wherein each W is the same or different and is phosphorus, arsenic or antimony, each X is the same or different and is oxygen, nitrogen or a covalent bond linking W and Y, Y is a substituted or unsubstituted hydrocarbon residue, each Z is the same or different and is a substituted or unsubstituted hydrocarbon residue or the Z substituents bonded to W may be bridged together to form a substituted or unsubstituted cyclic hydrocarbon residue, and m is a value equal to the free valence of Y, provided at least one of Y and Z is optically active;
- with the provisos that when each W is phosphorus and each X is a covalent bond, then the Z substituents cannot all be hdyrocarbon residues having a carbon atom directly bonded to phosphorus, and when Y is a substituted 2 carbon aliphatic chain and m is a value of 2 and both W substituents are phosphorus and one X substituent is oxygen and the other X substituent is nitrogen, then the Z substituents cannot all be phenyl, and when Y is a substituted tetrahydropyran and m is a value of 2 and both W substituents are phosphorus and the X substituents are both oxygen, then the Z substituents cannot all be aryl, and when Y is an unsubstituted 3 carbon aliphatic chain and m is a value of 2 and both X substituents are oxygen and both W substituents are phosphorus, then the Z substituents bonded to each phosphorus cannot be bridged together to form substituted -oxy-ethylene-oxy- groups;
- (ii) an organic solvent;
- and
- (iii) free ligand.
Dependencies are inferred from the claim text.