High metathesis activity ruthenium and osmium metal carbene complexes
Ruthenium and osmium carbene compounds that are stable in the presence of a variety of functional groups and can be used to catalyze olefin metathesis reactions on unstrained cyclic and acyclic olefins are disclosed. Also disclosed are methods of making the carbene compounds. The carbene compounds are of the formula where M is Os or Ru; R 1 is hydrogen; R is selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl; X and X 1 are independently selected from any anionic ligand; and L and L 1 are independently selected from any neutral electron donor. The ruthenium and osmium carbene compounds of the present invention may be synthesized using diazo compounds, by neutral electron donor ligand exchange, by cross metathesis, using acetylene, using cumulated olefins, and in a one-pot method using diazo compounds and neutral electron donors. The ruthenium and osmium carbene compounds of the present invention may be used to catalyze olefin metathesis reactions including, but not limited to, ROMP, RCM, depolymerization of unsaturated polymers, synthesis of telechelic polymers, and olefin synthesis.
1. A process for synthesizing telechelic polymers by metathesis polymerization, comprising contacting a cyclic olefin with a compound of the formula:
in the presence of an α,ω-difunctional olefin, wherein:
M is selected from the group consisting of Os and Ru;
R 1 is hydrogen;
R is selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl;
X and X 1 are independently selected from any anionic ligand;
L and L 1 is selected from any neutral electron donor.
2. A process for synthesizing olefins by cross metathesis, comprising contacting a first acyclic olefin with a compound of the formula:
in the presence of a second acyclic olefin,
wherein:
M is selected from the group consisting of Os and Ru;
R 1 is hydrogen;
R is selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl;
X and X 1 are independently selected from any anionic ligand;
L and L 1 are selected from any neutral electron donor.
3. The process of claim 1 , wherein the substituted alkyl includes one or more moieties selected from the group consisting of aryl, alcohol, thiol, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, and halogen.
4. The process of claim 1 , wherein the substituted aryl includes one or more moieties selected from the group consisting of alkyl, aryl, alcohol, thiol, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, and halogen.
5. The process of claim 1 , wherein R is selected from the group consisting of (a) hydrogen; (b) C 1 -C 20 alkyl; (c) aryl; (d) C 1 -C 20 alkyl substituted with one or more moieties selected from the group consisting of aryl, halide, hydroxy, C 1 -C 20 alkoxy, and C 2 -C 20 alkoxycarbonyl; and (e) aryl substituted with one or more moieties selected from the group consisting of C 1 -C 20 alkyl, aryl, hydroxyl, C 1 -C 5 alkoxy, amino, nitro, and halide.
6. The process of claim 5 , wherein R is phenyl or phenyl substituted with a moiety selected from the group consisting of chloride, bromide, iodide, fluoride, —NO 2 , —NMe 2 , methoxy, and methyl.
7. The process of claim 5 , wherein R is selected from the group consisting of hydrogen, methyl, ethyl, n-butyl, iso-propyl, —CH 2 Cl, —CH 2 CH 2 CH 2 OH, and —CH 2 OAc.
8. The process of claim 2 , wherein the substituted alkyl includes one or more moieties selected from the group consisting of aryl, alcohol, thiol, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, and halogen.
9. The process of claim 2 , wherein the substituted aryl includes one or more moieties selected from the group consisting of alkyl, aryl, alcohol, thiol, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, and halogen.
10. The process of claim 2 , wherein R is selected from the group consisting of (a) hydrogen; (b) C 1 -C 20 alkyl; (c) aryl; (d) C 1 -C 20 alkyl substituted with one or more moieties selected from the group consisting of aryl, halide, hydroxy, C 1 -C 20 alkoxy, and C 2 -C 20 alkoxycarbonyl; and (e) aryl substituted with one or more moieties selected from the group consisting of C 1 -C 20 alkyl, aryl, hydroxyl, C 1 -C 5 alkoxy, amino, nitro, and halide.
11. The process of claim 10 , wherein R is phenyl or phenyl substituted with a moiety selected from the group consisting of chloride, bromide, iodide, fluoride, —NO 2 , —NMe 2 , methoxy, and methyl.
12. The process of claim 10 , wherein R is selected from the group consisting of hydrogen, methyl, ethyl, n-butyl, iso-propyl, —CH 2 Cl, —CH 2 CH 2 CH 2 OH, and —CH 2 OAc.
13. A compound of formula:
wherein:
M is selected from the group consisting of Os and Ru;
R 1 is hydrogen;
R is a substituted or unsubstituted C 2 -C 20 alkenyl group; with the proviso that when R is a C 2 alkenyl group, it is not substituted with both a methyl and a phenyl group, disubstituted with phenyl groups, or disubstituted with methyl groups;
X and X 1 are independently selected from any anionic ligand; and
L and L′ are independently selected from any neutral electron donor.
14. The compound of claim 13 , wherein the substituted alkenyl includes one or more moieties selected from the group consisting of aryl, alcohol, thiol, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, and halogen.
15. The compound of claim 13 , wherein the substituted alkenyl includes one or more moieties selected from the group consisting of C 1 -C 20 alkyl, aryl, alcohol, thiol, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, halogen, and aryl substituted with one or more moieties selected from the group consisting of C 1 -C 20 alkyl, aryl, hydroxyl, C 1 -C 5 alkoxy, amino, nitro, and halide.
16. The compound of claim 13 , wherein the substituted alkenyl includes one or more moieties selected from the group consisting of N-Ts, N-Fmoc, N-Boc, COOEt, OSiEt 3 , phenyl, SiMe 2 , OBn, OR, NCOOtBu, and SO 2 Ph.
17. The compound of claim 13 , wherein the substitution of the substituted alkenyl takes place in the backbone of the alkenyl group.
18. The compound of claim 13 , wherein the substitution of the substituted alkenyl takes place outside the backbone of the alkenyl group.
19. The compound of claim 13 , wherein R is a substituted or unsubstituted C 3 -C 20 alkenyl group.
20. The compound of claim 13 , wherein R is an unsubstituted C 2 alkenyl group, or a C 2 alkenyl group substituted with one or more moieties selected from the group consisting of aryl, alcohol, thiol, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, and halogen.