Olefin metathesis initiators bearing thiazol-2-ylidene ligands
View Patent ↗This invention relates to olefin metathesis catalysts general formula (I): having a thiazol-2-ylidene ligand of general formula (II): The catalysts have been found to be particularly good initiators of (a) ring-closing metathesis reactions used to prepare tetra-substituted cyclic olefins, and (b) cross-metathesis reactions used to prepare tri-substituted and di-substituted olefins.
1. A compound, having general formula (I):
wherein:
M is Ru or Os;
n is 0, 1 or 2;
X 1 and X 2 are independently anionic ligands;
L is any neutral 2-electron donor ligand;
m is 1 or 2;
R 6 and R 7 are each independently hydrogen or a substituted or unsubstituted group selected from the group consisting of C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, aryl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, aryloxy, C 2 -C 20 alkoxycarbonyl, C 1 -C 20 alkylthio, C 1 -C 20 alkylsulfonyl, and C 1 -C 20 alkylsulfinyl; and
L 1 is a thiazol-2-ylidene ligand of formula (II):
wherein
R 4 and R 5 are each independently H, a substituted or unsubstituted C 1 -C 8 alkyl group, substituted or unsubstituted aryl, or, together with the carbons carrying them, form a substituted or unsubstituted, fused 4-8 membered carbocylic ring or a substituted or unsubstituted, fused aromatic ring; and
R 1 , R 2 , and R 3 are collectively defined as combination (a) or combination (b):
(a) each R 1 is independently a primary or secondary C 1 -C 4 alkyl group; each R 2 is independently H; and R 3 is independently H, a substituted or unsubstituted C 1 -C 8 alkyl group, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, or substituted or unsubstituted anthracenyl, or a functional group selected from the group consisting of halo, hydroxyl, sulfhydryl, cyano, cyanato, thiocyanato, amino, nitro, nitroso, sulfa, sulfonato, boryl, borono, phosphono, phosphonato, phosphinato, phospho, phosphino, and silyloxy; or
(b) each R 1 is H; each R 2 is independently H, a substituted or unsubstituted C 1 -C 8 alkyl group, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, or substituted or unsubstituted anthracenyl; and R 3 is H.
2. The compound of claim 1 , wherein R 1 , R 2 , and R 3 in L 1 is defined by combination (a), wherein each R 1 is methyl, ethyl, or iso-propyl; and R 3 is H, iso-butyl, tert-butyl, neopentyl, neohexyl, or phenyl.
3. The compound of claim 2 , wherein each R 1 is methyl or ethyl; and R 3 is H.
4. The compound of claim 1 , wherein R 1 , R 2 , and R 3 in L 1 is defined by combination (b), wherein each R 2 is a secondary or tertiary C 3 -C 10 alkyl or aryl; and R 3 is H, iso-butyl, tert-butyl, neopentyl, neohexyl, or phenyl.
5. The compound of claim 4 , wherein each R 2 is iso-butyl, tert-butyl, neopentyl, neohexyl, or phenyl; and R 3 is H.
6. The compound of claim 1 , wherein R 4 and R 5 are independently H or C 1 -C 4 alkyl, or fused cyclohexyl or phenyl.
7. The compound of claim 1 , wherein X 1 and X 2 are independently selected from the group consisting of halide, C 1 -C 20 alkyl, aryl, C 1 -C 20 alkoxide, aryloxide, C 3 -C 20 alkyldiketonate, aryldiketonate, C 1 -C 20 carboxylate, arylsulfonate, C 1 -C 20 alkylsulfonate, C 1 -C 20 alkylthio, C 1 -C 20 alkylsulfonyl, and C 1 -C 20 alkylsulfinyl.
8. The compound of claim 7 , wherein X 1 and X 2 are independently selected from the group consisting of halide, benzoate, C 1 -C 5 carboxylate, C 1 -C 5 alkyl, phenoxy, C 1 -C 5 alkoxy, C 1 -C 5 alkylthio, aryl, and C 1 -C 5 alkylsulfonate.
9. The compound of claim 8 , wherein X 1 and X 2 are independently selected from the group consisting of halide, CF 3 CO 2 , CH 3 , CO 2 , CFH 2 CO 2 , (CH 3 ) 3 CO, (CF 3 ) 2 (CH 3 )CO, (CF 3 )(CH 3 ) 2 CO, PhO, MeO, EtO, tosylate, mesylate, and trifluoromethanesulfonate.
10. The compound of claim 9 , wherein X 1 and X 2 are each chloride.
11. The compound of claim 1 , wherein R 6 is hydrogen, substituted or unsubstituted C 1 -C 5 alkyl, or substituted or unsubstituted aryl; and R 7 is substituted or unsubstituted C 1 -C 20 alkyl, substituted or unsubstituted C 2 -C 20 alkenyl, or substituted or unsubstituted aryl.
12. The compound of claim 11 , wherein R 6 is hydrogen, and R 7 is phenyl or vinyl, optionally substituted with one or more moieties selected from the group consisting of C 1 -C 5 alkyl, C 1 -C 5 alkoxy, phenyl, chloride, bromide, iodide, fluoride, —NO 2 , and —NMe 2 .
13. The compound of claim 12 , wherein R 7 is phenyl or —C═C(CH 3 ) 2 .
14. The compound of claim 1 , wherein m is 1, n is 0, and L is linked to R 7 forming a chelating carbene ligand.
15. The compound of claim 14 , wherein L is linked to R 7 through a spacer moiety, where the space moiety is substituted or unsubstituted alkyl group, a substituted or unsubstituted cycoloalkyl group, or a substituted or unsubstituted aryl group.
16. The compound of claim 14 , wherein M is Ru, and L and R 7 are linked to form a complex selected from the group consisting of
17. The compound of claim 1 , wherein m is 2, and each L ligand is independently pyridine or substituted pyridine.
18. The compound of claim 1 , wherein L is selected from the group consisting of phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, imine, sulfoxide, carboxyl, nitrosyl, pyridine, thioether, and L 1 .
19. The compound of claim 18 , wherein L is a phosphine of the formula PR′R″R′″, where R′, R″, and R′″ are each independently aryl; C 1 -C 10 alkyl; or C 3 -C 6 cycloalkyl.
20. The compound of claim 19 , wherein L is selected from the group consisting of P(cyclohexyl) 3 , P(cyclopentyl) 3 , P(isopropyl) 3 , and P(phenyl) 3 .
21. The compound of claim 1 , having the formula:
wherein R 1 , R 2 , R 3 , R 4 , and R 5 are defined in claim 1 .
22. The compound of claim 1 , having the formula:
wherein R 1 , R 2 , R 3 , R 4 , and R 5 are defined in claim 1 , and wherein R 6 is a C 1 -C 4 alkyl.
23. The compound of claim 1 , wherein the compound is selected from the group consisting of:
24. A method of preparing a tetra-substituted cyclic olefin through a ring-closing metathesis reaction, comprising contacting an olefinic compound with a compound of claim 1 under metathesis conditions to form a cyclic tetra-substituted olefin, wherein the olefinic compound has at least two terminal olefins that are substituted at the beta-carbon of each terminal olefin.
25. The method of claim 24 , wherein the olefinic compound has a structure according to general formula (III):
wherein
Q is selected from the group consisting of hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, and substituted heteroatom-containing hydrocarbylene;
Q 1 and Q 2 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, halide, hydroxyl, sulfhydryl, cyano, cyanato, thiocyanato, amino, nitro, nitroso, sulfo, sulfonato, boryl, borono, phosphono, phosphonato, phosphinato, phospho, phosphino, and silyloxy
with the proviso that Q 1 and Q 2 cannot both be hydrogen.
26. The method of claim 25 , wherein neither Q 1 nor Q 2 are hydrogen.
27. A method of preparing a tri-substituted olefin or a di-substituted olefin that is further substituted at the allylic carbon, through a cross-metathesis reaction, comprising contacting two olefins with a compound of claim 1 under metathesis conditions to form a tri-substituted olefin, wherein the first olefin is monosubstituted at the β-carbon and either unsubstituted or monosubstituted at the ∝-carbon, and the second olefin is either disubstituted at the β-carbon or monosubstituted at the β-carbon with a further substitution at the allylic carbon, and either monosubstituted or unsubstituted at the ∝-carbon.
28. The method of claim 27 , wherein the tri-substituted olefin has the formula Q 1 Q 2 C═CHQ 3 , wherein Q 1 , Q 2 , and Q 3 are independently selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, halide, hydroxyl, sulfhydryl, cyano, cyanato, thiocyanato, amino, nitro, nitroso, sulfo, sulfonato, boryl, borono, phosphono, phosphonato, phosphinato, phospho, phosphino, and silyloxy, wherein Q 1 , Q 2 , and/or Q 3 may be linked as part of a cyclic olefin.
29. The method of claim 27 , wherein the di-substituted olefin has the formula Q 1 Q 2 C═CH 2 or Q 1 HC═CHQ 2 , wherein Q 1 and Q 2 are independently selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, halide, hydroxyl, sulfhydryl, cyano, cyanato, thiocyanato, amino, nitro, nitroso, sulfo, sulfonato, boryl, borono, phosphono, phosphonato, phosphinato, phospho, phosphino, and silyloxy, wherein Q 1 and Q 2 may be linked as part of a cyclic olefin.
30. The method of claim 27 , wherein the di-substituted olefin having a further substitution at the allylic carbon has the formula Q 1 HC═CHCQ 2 Q 3 Q 4 , wherein Q 1 , Q 2 , Q 3 , and Q 4 are independently selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, halide, hydroxyl, sulfhydryl, cyano, cyanato, thiocyanato, amino, nitro, nitroso, sulfo, sulfonato, boryl, borono, phosphono, phosphonato, phosphinato, phospho, phosphino, and silyloxy, wherein Q 1 , Q 2 , Q 3 and/or Q 4 may be linked as part of a cyclic olefin.
31. A method for synthesizing a polymer using a ring-opening metathesis polymerization reaction, comprising contacting a cyclic olefin with a compound of claim 1 .
32. A method for synthesizing a cyclic olefin by ring-closing metathesis, comprising contacting an acyclic diene in the presence of a compound of claim 1 to yield a cyclic olefin.
33. The method of claim 32 , wherein the cyclic olefin is macrocyclic olefin.