Chiral metallocene compounds and preparation thereof by attachment of chiral center

Claim 3

The method of claim 1 wherein the cyclopentadienyl ligand and the nucleophile are contacted together at a temperature in the range of about -78 to about 200° C., at a pressure in the range of about just above 0 psia to about 2000 psig, for a contacting time in the range of about 0.1 minutes to about 24 hours, and at a mole ratio of the ligand to nucleophile in the range of about 10:1 to about 1:10.

Claim 4

The method of claim 2 wherein the chiral substituted cyclopentadienyl ligands of general formula III are produced at an enantiomeric excess of at least 1 percent.

Claim 5

The method of claim 1 wherein each R is independently selected from the group consisting of radicals of alkyls and aromatics or two R groups are joined together to form a ring of 5 or more carbon atoms; each R' is independently selected from the group consisting of H, and alkyl and aromatic hydrocarbons; R * contains at least one chiral carbon center and is selected from the group consisting of radicals of amino acids, and alkyl and aromatic hydrocarbons; and Y is selected from the group consisting of NH and NR"; and each R" is independently selected from the group consisting of alkyl and aromatic hydrocarbon radicals.

Claim 6

The method of claim 4 wherein the cyclopentadienyl ligand and the nucleophile are contacted together at a temperature in the range of about -78 to about 200° C., at a pressure in the range of about just above 0 psia to about 2000 psig, for a contacting time in the range of about 0.1 minutes to about 24 hours, and at a mole ratio of the ligand to nucleophile in the range of about 10:1 to about 1:10.

Claim 7

The method of claim 5 wherein the chiral substituted cyclopentadienyl ligands of general formula III are produced at an enantiomeric excess of at least 5 percent.

Claim 8

The method of claim 1 wherein the substituted fulvene compound is selected from the group consisting of 1,2,3,4-tetramethylfulyene, 1,2,3,4-tetraethylfulvene and 1,2,3,4,6-pentamethylfulyene, and the chiral nucleophile is an alpha-alkylarylamine selected from the group consisting of alpha-methylbenzyl amine, alpha-ethylbenzyl amine, alpha-propylbenzyl amine, alpha-butylbenzyl amine, alpha-methylnaphtha amine, alpha-ethylnaptha amine, alpha-propylnaptha amine, and alpha-butylnaptha amine.

Claim 9

The method of claim 7 wherein the cyclopentadienyl ligand and the nucleophile are contacted together at a temperature in the range of about -50 to about 100° C., at a pressure in the range of about 1 psia to about 50 psig, for a contacting time in the range of about 0.5 hours to about 16 hours, and at a mole ratio of the ligand to nucleophile in the range of about 3:1 to about 1:3.

Claim 10

The method of claim 1 wherein the substituted fulvene compound is 1,2,3,4-tetramethylfulvene and the chiral nucleophile is alpha-methylbenzyl amine.

Claim 11

The method of claim 9 wherein the cyclopentadienyl ligand and the nucleophile are contacted together at a temperature in the range of about -50 to about 100° C., at a pressure in the range of about 1 psia to about 50 psig, for a contacting time in the range of about 0.5 to about 16 hours, and at a mole ratio of the ligand to nucleophile in the range of about 3:1 to about 1:3.

Claim 12

The method of claim 10 wherein the chiral substituted cyclopentadienyl ligands of general formula III are produced at an enantiomeric excess of at least 5 percent.

Claim 13

The method of claim 10 wherein the cyclopentadienyl ligand and the nucleophile are contacted together at a temperature in the range of about -20 to about 65° C., at a pressure in the range of about 0 psig to about 16 psig, for a contacting time in the range of about 1 to about 8 hours, and at a mole ratio of the ligand to nucleophile in the range of about 1:1:1 to about 1:1.1.

Claim 14

An enantiomerically enhanced composition comprising chiral substituted cyclopentadienyl ligands of general formula III: ##STR8## wherein each R and each R' is independently selected from the group consisting of H, radicals of substituted aliphatic hydrocarbons, unsubstituted aliphatic hydrocarbons, substituted cyclic hydrocarbons, unsubstituted cyclic hydrocarbons, substituted heterocyclic hydrocarbons and unsubstituted heterocyclic hydrocarbons and two neighboring R groups can be joined together to form a ring of five or more carbon atoms; R * contains at least one chiral carbon center and is selected from the group consisting of enantiomerically enhanced chiral radicals of amino acids, substituted aliphatic hydrocarbons, unsubstituted aliphatic hydrocarbons, substituted cyclic hydrocarbons, unsubstituted cyclic hydrocarbons, substituted heterocyclic hydrocarbons and unsubstituted heterocyclic hydrocarbons; Y is selected from the group consisting of NR", NH, O, S, C(R")2, PR" and Si(R") 2 ; and each R" is independently selected from the group consisting of H, radicals of amino acids, substituted aliphatic hydrocarbons, unsubstituted aliphatic hydrocarbons, substituted cyclic hydrocarbons, unsubstituted cyclic hydrocarbons, substituted heterocyclic hydrocarbons and unsubstituted heterocyclic hydrocarbons.

Claim 15

An enantiomerically enhanced composition comprising chiral substituted cyclopentadienyl ligands of general formula III: ##STR8## wherein each R and each R' is independently selected from the group consisting of H, radicals of substituted aliphatic hydrocarbons, unsubstituted aliphatic hydrocarbons, substituted cyclic hydrocarbons, unsubstituted cyclic hydrocarbons, substituted heterocyclic hydrocarbons and unsubstituted heterocyclic hydrocarbons and two neighboring R groups can be joined together to form a ring of five or more carbon atoms; R * contains at least one chiral carbon center and is selected from the group consisting of enantiomerically enhanced chiral radicals of amino acids, substituted aliphatic hydrocarbons, unsubstituted aliphatic hydrocarbons, substituted cyclic hydrocarbons, unsubstituted cyclic hydrocarbons, substituted heterocyclic hydrocarbons and unsubstituted heterocyclic hydrocarbons; Y is selected from the group consisting of NR", NH, O, S, C(R")2, PR" and Si(R") 2 ; and each R" is independently selected from the group consisting of H, radicals of amino acids, substituted aliphatic hydrocarbons, unsubstituted aliphatic hydrocarbons, substituted cyclic hydrocarbons, unsubstituted cyclic hydrocarbons, substituted heterocyclic hydrocarbons and unsubstituted heterocyclic hydrocarbons.

Claim 16

The composition of claim 13 wherein each R is independently selected from the group consisting of radicals of alkyls and aromatics or two R groups are joined together to form a ring of 5 or more carbon atoms; each R' is independently selected from the group consisting of H, and radicals of alkyl and aromatic hydrocarbons; R * contains at least on chiral carbon center and is selected from the group consisting of radicals of amino acids, and alkyl and aromatic hydrocarbons; and Y is selected from the group consisting of NH and NR"; and each R" is independently selected from the group consisting of alkyl and aromatic hydrocarbon radicals.

Claim 17

The composition of claim 14 wherein each R is independently selected from the group consisting of methyl, ethyl, propyl; R' is H; and --Y--R * is an alpha-alkylarylamine radical selected from the group consisting of radicals of alpha-methylbenzyl amine, alpha-ethylbenzyl amine, alpha-propylbenzyl amine, alpha-butylbenzyl amine, alpha-methylnaphtha amine, alpha-ethylnaptha amine, alpha-propylnaptha amine, and alpha-butylnaptha amine.

Claim 18

The composition of claim 15 wherein each R is independently selected from the group consisting of methyl, ethyl and propyl; R' is H; and --Y--R * is an alpha-methylbenzyl amine radical.

Claim 19

An enantiomerically enhanced composition comprising chiral substituted cyclopentadiene compounds of general formula IIIb: ##STR9## wherein each R and each R' is independently selected from the group consisting of H, radicals of substituted aliphatic hydrocarbons, unsubstituted aliphatic hydrocarbons, substituted cyclic hydrocarbons, unsubstituted cyclic hydrocarbons, substituted heterocyclic hydrocarbons, unsubstituted heterocyclic hydrocarbons and two neighboring R groups can be joined together to form a ring of five or more carbon atoms R * contains at least one chiral carbon center and is selected from the group consisting of enantiomerically enhanced chiral radicals of amino acids, substituted aliphatic hydrocarbons, unsubstituted aliphatic hydrocarbons, substituted cyclic hydrocarbons, unsubstituted cyclic hydrocarbons, substituted heterocyclic hydrocarbons and unsubstituted heterocyclic hydrocarbons; Y is selected from the group consisting of NR", NH, O, S, C(R")2, PR" and Si(R")2; each R" is independently selected from the group consisting of H, radicals of amino acids, substituted aliphatic hydrocarbons, unsubstituted aliphatic hydrocarbons, substituted cyclic hydrocarbons, unsubstituted cyclic hydrocarbons, substituted heterocyclic hydrocarbons and unsubstituted heterocyclic hydrocarbons, and Q is selected from the group consisting of thallium, potassium, lithium, sodium and MgX, wherein X is selected from the group consisting of Br, Cl and I.

Claim 20

An enantiomerically enhanced composition comprising chiral substituted cyclopentadiene compounds of general formula IIIb: ##STR9## wherein each R and each R' is independently selected from the group consisting of H, radicals of substituted aliphatic hydrocarbons, unsubstituted aliphatic hydrocarbons, substituted cyclic hydrocarbons, unsubstituted cyclic hydrocarbons, substituted heterocyclic hydrocarbons, unsubstituted heterocyclic hydrocarbons and two neighboring R groups can be joined together to form a ring of five or more carbon atoms R * contains at least one chiral carbon center and is selected from the group consisting of enantiomerically enhanced chiral radicals of amino acids, substituted aliphatic hydrocarbons, unsubstituted aliphatic hydrocarbons, substituted cyclic hydrocarbons, unsubstituted cyclic hydrocarbons, substituted heterocyclic hydrocarbons and unsubstituted heterocyclic hydrocarbons; Y is selected from the group consisting of NR", NH, O, S, C(R")2, PR" and Si(R")2; each R" is independently selected from the group consisting of H, radicals of amino acids, substituted aliphatic hydrocarbons, unsubstituted aliphatic hydrocarbons, substituted cyclic hydrocarbons, unsubstituted cyclic hydrocarbons, substituted heterocyclic hydrocarbons and unsubstituted heterocyclic hydrocarbons, and Q is selected from the group consisting of thallium, potassium, lithium, sodium and MgX, wherein X is selected from the group consisting of Br, Cl and I.

Claim 21

The composition of claim 17 wherein each R is independently selected from the group consisting of radicals of alkyls and aromatics or two R groups are joined together to form a ring of 5 or more carbon atoms; each R' is independently selected from the group consisting of H, and radicals of alkyl and aromatic hydrocarbons; R * contains at least on chiral carbon center and is selected from the group consisting of radicals of amino acids, and alkyl and aromatic hydrocarbons; and Y is selected from the group consisting of NH and NR"; and each R" is independently selected from the group consisting of alkyl and aromatic hydrocarbon radicals.

Claim 22

The composition of claim 18 wherein the enantiomeric enhancement is an enantiomeric excess of at least 5 percent.

Claim 23

The composition of claim 18 wherein each R is independently selected from the group consisting of methyl, ethyl, propyl or two R groups are joined together to form a 6 numbered ring; R' is H; and --Y--R * is an alpha-alkylarylamine radical selected from the group consisting of radicals of alpha-methylbenzyl amine, alpha-ethylbenzyl amine, alpha-propylbenzyl amine, alpha-butylbenzyl amine, alpha-methylnaphtha amine, alpha-ethylnaptha amine, alpha-propylnaptha amine, and alpha-butylnaptha amine.

Claim 24

The composition of claim 20 wherein each R is independently selected from the group consisting of methyl, ethyl and propyl or two R groups are joined together to form a 6 numbered ring; R' is H; and -Y-R * is an alpha-methylbenzyl amine radical.

Claim 25

The composition of claim 21 wherein the enantiomeric enhancement is an enantiomeric excess of at least 5 percent.

Claim 26

An enantiomerically enhanced composition comprising chiral compounds of general formula V: ##STR10## wherein each R and each R' is independently selected from the group consisting of H, radicals of substituted aliphatic hydrocarbons, unsubstituted aliphatic hydrocarbons, substituted cyclic hydrocarbons, unsubstituted cyclic hydrocarbons, substituted heterocyclic hydrocarbons, unsubstituted heterocyclic hydrocarbons and two neighboring R groups can be joined together to form a ring of five or more carbon atoms; R * contains at least one chiral carbon center and is selected from the group consisting of enantiomerically enhanced chiral radicals of amino acids, substituted aliphatic hydrocarbons, unsubstituted aliphatic hydrocarbons, substituted cyclic hydrocarbons, unsubstituted cyclic hydrocarbons, substituted heterocyclic hydrocarbons and unsubstituted heterocyclic hydrocarbons; Y is selected from the group consisting of NR", NH, O, S, C(R" 2 , PR" and Si(R") 2 ; each R" is independently selected from the group consisting of H, radicals of amino acids, substituted aliphatic hydrocarbons, unsubstituted aliphatic hydrocarbons, substituted cyclic hydrocarbons, unsubstituted cyclic hydrocarbons, substituted heterocyclic hydrocarbons and unsubstituted heterocyclic hydrocarbons; each Q' is independently a univalent anionic ligand selected from the group consisting of a halide, hydride, substituted or unsubstituted C 1 -C 20 hydrocarbyl, alkoxide, aryloxide, amide, arylamide, phosphide and arylphosphide; M is a transition metal selected from the group consisting of Group IIIB-VIIIB transition metals; m is the transition state of the metal; and n is in the range of about 1 to about m-1.

Claim 27

An enantiomerically enhanced composition comprising chiral compounds of general formula V: ##STR10## wherein each R and each R' is independently selected from the group consisting of H, radicals of substituted aliphatic hydrocarbons, unsubstituted aliphatic hydrocarbons, substituted cyclic hydrocarbons, unsubstituted cyclic hydrocarbons, substituted heterocyclic hydrocarbons, unsubstituted heterocyclic hydrocarbons and two neighboring R groups can be joined together to form a ring of five or more carbon atoms; R * contains at least one chiral carbon center and is selected from the group consisting of enantiomerically enhanced chiral radicals of amino acids, substituted aliphatic hydrocarbons, unsubstituted aliphatic hydrocarbons, substituted cyclic hydrocarbons, unsubstituted cyclic hydrocarbons, substituted heterocyclic hydrocarbons and unsubstituted heterocyclic hydrocarbons; Y is selected from the group consisting of NR", NH, O, S, C(R" 2 , PR" and Si(R") 2 ; each R" is independently selected from the group consisting of H, radicals of amino acids, substituted aliphatic hydrocarbons, unsubstituted aliphatic hydrocarbons, substituted cyclic hydrocarbons, unsubstituted cyclic hydrocarbons, substituted heterocyclic hydrocarbons and unsubstituted heterocyclic hydrocarbons; each Q' is independently a univalent anionic ligand selected from the group consisting of a halide, hydride, substituted or unsubstituted C 1 -C 20 hydrocarbyl, alkoxide, aryloxide, amide, arylamide, phosphide and arylphosphide; M is a transition metal selected from the group consisting of Group IIIB-VIIIB transition metals; m is the transition state of the metal; and n is in the range of about 1 to about m-1.

Claim 28

The composition of claim 23 wherein each R is independently selected from the group consisting of radicals of alkyls and aromatics or two R groups are joined together to form a ring of 5 or more carbon atoms; each R' is independently selected from the group consisting of H, and radicals of alkyl and aromatic hydrocarbons; R * contains at least on chiral carbon center and is selected from the group consisting of radicals of amino acids, and alkyl and aromatic hydrocarbons; and Y is selected from the group consisting of NH and NR"; and each R" is independently selected from the group consisting of alkyl and aromatic hydrocarbon radicals; each Q' is a halogen independently selected from the group consisting of chlorine, bromine and iodine; and M is a transition metal selected from the group consisting of Group IV B, Group VI B and Group VIII B transition metals.

Claim 29

The composition of claim 24 wherein each R is independently selected from the group consisting of methyl, ethyl, propyl or two R groups are joined together to form a 6 numbered ring; R' is H; and --Y--R * is an alpha-alkylarylamine radical selected from the group consisting of radicals of alpha-methylbenzyl amine, alpha-ethylbenzyl amine, alpha-propylbenzyl amine, alpha-butylbenzyl amine, alpha-methylnaphtha amine, alpha-ethylnaptha amine, alpha-propylnaptha amine, and alpha-butylnaptha amine.

Claim 30

The composition of claim 25 wherein the enantiomeric enhancement is an enantiomeric excess of at least 5 percent.

Claim 31

The composition of claim 26 wherein M is a Group IV metal.

Claim 32

The composition of claim 27 wherein --Y--R * is an alpha-methylbenyzlamine radical.

Claim 33

The composition of claim 28 wherein each R is methyl.

Claim 34

The composition of claim 25 wherein M is selected from titanium, hafnium and zirconium.

Claim 35

An enantiomerically enhanced composition comprising chiral substituted cyclopentadiene compounds of general formula IIIc: ##STR11## wherein each R and each R' is independently selected from the group consisting of H, radicals of substituted aliphatic hydrocarbons, unsubstituted aliphatic hydrocarbons, substituted cyclic hydrocarbons, unsubstituted cyclic hydrocarbons, substituted heterocyclic hydrocarbons, unsubstituted heterocyclic hydrocarbons and two neighboring R groups can be joined together to form a ring of five or more carbon atoms; R * contains at least one chiral carbon center and is selected from the group consisting of enantiomerically enhanced chiral radicals of amino acids, substituted aliphatic hydrocarbons, unsubstituted aliphatic hydrocarbons, substituted cyclic hydrocarbons, unsubstituted cyclic hydrocarbons, substituted heterocyclic hydrocarbons and unsubstituted heterocyclic hydrocarbons; Y is selected from the group consisting of NR", NH, O, S, C(R") 2 , PR" and Si(R") 2 ; each R" is independently selected from the group consisting of H, radicals of amino acids, substituted aliphatic hydrocarbons, unsubstituted aliphatic hydrocarbons, substituted cyclic hydrocarbons, unsubstituted cyclic hydrocarbons, substituted heterocyclic hydrocarbons and unsubstituted heterocyclic hydrocarbons.

Claim 36

An enantiomerically enhanced composition comprising chiral substituted cyclopentadiene compounds of general formula IIIc: ##STR11## wherein each R and each R' is independently selected from the group consisting of H, radicals of substituted aliphatic hydrocarbons, unsubstituted aliphatic hydrocarbons, substituted cyclic hydrocarbons, unsubstituted cyclic hydrocarbons, substituted heterocyclic hydrocarbons, unsubstituted heterocyclic hydrocarbons and two neighboring R groups can be joined together to form a ring of five or more carbon atoms; R * contains at least one chiral carbon center and is selected from the group consisting of enantiomerically enhanced chiral radicals of amino acids, substituted aliphatic hydrocarbons, unsubstituted aliphatic hydrocarbons, substituted cyclic hydrocarbons, unsubstituted cyclic hydrocarbons, substituted heterocyclic hydrocarbons and unsubstituted heterocyclic hydrocarbons; Y is selected from the group consisting of NR", NH, O, S, C(R") 2 , PR" and Si(R") 2 ; each R" is independently selected from the group consisting of H, radicals of amino acids, substituted aliphatic hydrocarbons, unsubstituted aliphatic hydrocarbons, substituted cyclic hydrocarbons, unsubstituted cyclic hydrocarbons, substituted heterocyclic hydrocarbons and unsubstituted heterocyclic hydrocarbons.

Claim 37

The composition of claim 31 wherein each R is independently selected from the group consisting of radicals of alkyls and aromatics or two R groups are joined together to form a ring of 5 or more carbon atoms; each R' is independently selected from the group consisting of H, and radicals of alkyl and aromatic hydrocarbons; R * contains at least on chiral carbon center and is selected from the group consisting of radicals of amino acids, and alkyl and aromatic hydrocarbons; and Y is selected from the group consisting of NH and NR"; and each R" is independently selected from the group consisting of alkyl and aromatic hydrocarbon radicals.

Claim 38

The composition of claim 32 wherein the enantiomeric enhancement is an enantiomeric excess of at least 5 percent.

Claim 39

The composition of claim 33 wherein each R is independently selected from the group consisting of methyl, ethyl, propyl or two R groups are joined together to form a 6 numbered ring; R' is H; and --Y--R" is an alpha-alkylarylamine radical selected from the group consisting of radicals of alpha-methylbenzyl amine, alpha-ethylbenzyl amine, alpha-propylbenzyl amine, alpha-butylbenzyl amine, alpha-methylnaphtha amine, alpha-ethylnaptha amine, alpha-propylnaptha amine, and alpha-butylnaptha amine.

Claim 40

The cOmposition of claim 34 wherein each R is independently selected from the group consisting of methyl, ethyl and propyl or two R groups are joined together to form a 6 numbered ring; R' is H; and --Y--R" is an alpha-methylbenzyl amine radical.