Group 8 transition metal carbene complexes as enantionselective olefin metathesis catalysts

A chiral Group 8 transition metal carbene complex comprising the formula:

• wherein:
• M is a Group 8 transition metal;
• X1 and X2 are independently selected from the group consisting of anionic ligands and a linker attached to a polymeric substrate, or X1 and X2 may be taken together to form a cyclic group;
• n is an integer from 0-5;
• R1 is selected from the group consisting of hydrogen, silyl, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing and carboxy;
• R2 is selected from the group consisting of phenyl and —C═C(CH3)2;
• Y1 and Y2 are heteroatoms independently selected from the group consisting of N, O, S, and P, with the proviso that when Y1 or Y2 is O or S, then R3 or R4 is absent;
• R3 and R1 are independently selected from the group consisting of hydrogen, functional groups, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom- containing hydrocarbyl, and a linker attached to polymeric substrate;
• R5, R6, R7, and R8 define chiral centers at the ring carbons and are independently selected from the group consisting of a linker attached to a polymeric substrate, hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups, optionally substituted with one or more moieties selected from the group consisting of C1-10 alkyl, C1-10 alkoxy, C5-20 aryl, hydroxyl, sulfhydryl, —(CO)—H, halo, and functional groups;
• L is selected from the group consisting of arsine, stibine, ether, amino, amido, imino, sulfoxide, carboxy, nitrosyl, pyridyl, substituted pyridyl, imidazolyl, substituted imidazolyl, pyrazinyl, and thioether, and may or may not be linked to R2, X1, and/or X2 through a spacer moiety;
• and
• wherein any two or more of X1, X2, L, R1, R2, R3, R4, R5, R6, R7, and R8 can be taken together to form a chelating multidentate ligand.

A chiral Group 8 transition metal carbene complex comprising the formula:

• wherein:
• M is a Group 8 transition metal;
• X1 and X 2 are independently selected from the group consisting of anionic ligands and a linker attached to a polymeric substrate, or X1 and X2 may be taken together to form a cyclic group;
• n is an integer from 0-5;
• R1 is selected from the group consisting of hydrogen, silyl, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and carboxy;
• R2 is selected from the group consisting of hydrogen, silyl, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl, or R1 and R2 may be taken together to form a cyclic group;
• Y1 and Y2 are heteroatoms independently selected from the group consisting of N, O, S, and P, with the proviso that when Y1 or Y2 is O or S, then R3 or R4 is absent;
• R3 and R4 are independently selected from the group consisting of hydrogen, functional groups, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom- containing hydrocarbyl, and a linker attached to polymeric substrate and at least one of R3 and R4 is a nitrogen-containing heterocycle;
• R5, R6, R7, and R8 define chiral centers at the ring carbons and are independently selected from the group consisting of a linker attached to a polymeric substrate, hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups, optionally substituted with one or more moieties selected from the group consisting of C1-10 alkyl, C1-10 alkoxy, C5-20 aryl, hydroxyl, sulfhydryl, —(CO)—H, halo, and functional groups;
• L is selected from the group consisting of arsine, stibine, ether, amino, amido, imino, sulfoxide, carboxy, nitrosyl, pyridyl, substituted pyridyl, imidazolyl, substituted imidazolyl, pyrazinyl, and thioether, and may or may not be linked to R2, X1, and/or X2 through a spacer moiety;
• and
• wherein any two or more of more of X1, X2, L, R1, R2, R3, R4, R5, R6, R7, and R8 can be taken together to form a chelating multidentate ligand.

A chiral Group 8 transition metal carbene complex comprising the formula:

• wherein:
• M is a Group 8 transition metal;
• X1 and X2 are independently selected from the group consisting of anionic ligands and a linker attached to a polymeric substrate, or X1 and X2 may be taken together to form a cyclic group;
• n is an integer from 0-5;
• R1 is selected from the group consisting of hydrogen, silyl, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and carboxy;
• R2 is selected from the group consisting of hydrogen, silyl, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl, or R1 and R2 may be taken together to form a cyclic group;
• Y1 and Y2 are heteroatoms independently selected from the group consisting of N, O, S, and P, with the proviso that when Y1 or Y2 is O or S, then R3 or R4 is absent;
• R3 and R4 are independently selected from the group consisting of hydrogen, functional groups, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom- containing hydrocarbyl, and a linker attached to polymeric substrate;
• R5, R6, R7, and R8 define chiral centers at the ring carbons and are independently selected from the group consisting of a linker attached to a polymeric substrate, hydrogen hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups, optionally substituted with one or more moieties selected from the group consisting of C1-10 alkyl, C1-10 alkoxy, C5-20 aryl, hydroxyl, sulfhydryl, —(CO)—H, halo, and functional groups;
• L is a nitrogen-containing heterocycle and may or may not be linked to R2, X1, and/or X2 through a spacer moiety;
• and
• wherein any two or more of X1, X2, L, R1, R2, R3, R4, R5, R6, R7 and R8 can be taken together to form a chelating multidentate ligand.

A chiral ruthenium carbene complex of the formula:

• wherein:
• X1 and X2 are independently selected from the group consisting or anionic ligands and a linker attached to a polymeric substrate, or X1 and X2 may be taken together to form a cyclic group;
• R1 is selected from the group consisting of hydrogen, silyl, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and carboxyl;
• R2 is selected from the group consisting of hydrogen, silyl, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl, or R1 and R2 may be taken together to form a cyclic group;
• Y1 and Y2 are heteroatoms independently selected from the group consisting of N, O, S, and P, with the proviso that when Y1 or Y2 is O or S, then the appended aryl group is absent;
• R5 and R6 define chiral centers at the ring carbons and are independently selected from the group consisting of a linker attached to a polymeric substrate, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups, optionally substituted with one or more moieties selected from the group consisting of C1-10 alkyl, C1-10 alkoxy, C5-20 aryl, hydroxyl, sulfhydryl, —(CO)—H, halo, and functional groups;
• R20 and R21 are independently selected from the group consisting of hydrogen, C1-10 alkyl, substituted C1-20 alkyl, perfluoronated C1-20 alkyl, C1-20 heteroalkyl, substituted C1-20 heteroalkyl, C1-20alkoxy, C5-20 aryl, substituted C5-20 aryl, heteroaryl, C5-30 aralkyl, C5-30 alkaryl, and halo;
• and
• L is selected from the group consisting of arsine, stibine, ether, amino, amido, imino, sulfoxide, carboxy, nitrosyl, pyridyl, substituted pyridyl, imidazolyl, substituted imidazolyl, pyrazinyl, and thioether.

A method of controlling the enantioselectivity of an olefin metathesis reaction comprising catalyzing the reaction with a chiral Group 8 transition metal carbene complex of the formula:

• wherein:
• M is a Group 8 transition metal;
• X1 and X2 are independently selected from the group consisting of anionic ligands and a linker attached to a polymeric substrate, or X1 and X2 may be taken together to form a cyclic group;
• n is an integer from 0-5;
• R1 is selected from the group consisting of hydrogen, silyl, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and carboxy;
• R2 is selected from the group consisting of hydrogen, silyl, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl, or R1 and R2 may be taken together to form a cyclic group;
• Y1 and Y2 are heteroatoms independently selected from the group consisting of N, O, S, and P, with the proviso that when Y1 or Y2 is O or S, then R3 or R4 is absent;
• R3 and R4 are independently selected from the group consisting of hydrogen, functional groups, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl;
• R5, R6, R7, and R8 define chiral centers at the ring carbons and are independently selected from the group consisting of a linker attached to a polymeric substrate, hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups, optionally substituted with one or more moieties selected from the group consisting of C1-10 alkyl, C1-10 alkoxy, C5-20 aryl, hydroxyl, sulfhydryl, —(CO)—H, halo, and functional groups;
• L is selected from the group consisting of arsine, stibine, ether, amino, amido, imino, sulfoxide, carboxy, nitrosyl, pyridyl, substituted pyridyl, imidazolyl, substituted imidazolyl, pyrazinyl, and thioether, and may or may not be linked to R2, X1, and/or X2 through a spacer moiety;
• and
• wherein any two or more of X1, X2, L, R1, R2, R3, R4, R5, R6, R7, and R8 can he taken together to form a chelating multidentate ligand.