Ruthenium olefin metathesis catalysts bearing N-heterocyclic carbene ligands with substituted backbone
This invention relates generally to olefin metathesis, more particularly, to tri- or tetra-substituted imidazolinium salts which are precursors to N-heterocyclic carbene (NHC) ligands with tri- or tetra-substituted imidazolinium rings, organometallic ruthenium complexes comprising gem di-substituted imidazolinium NHC ligands, organometallic ruthenium complexes comprising tri- or tetra-substituted imidazolinium NHC ligands, and to olefin metathesis methods using them. The catalysts and methods of the invention have utility in the fields of catalysis, organic synthesis, and industrial chemistry.
1. An imidazolinium salt of formula (I):
wherein:
a) R 1 and R 4 are methyl; and
R 2 and R 3 are independently selected from methyl, ethyl, or allyl, or R 2 and R 3 together with the carbons carrying them form a fused 6-, 7- or 8-membered carbocylic ring;
R 5 and R 6 are each independently a C 1 -C 10 alkyl, cycloalkyl, a fused or bridged ring, aralkyl, or a group having the structure of formula (II);
wherein,
n ranges from 1 to 3; with the proviso that only one of R 5 or R 6 may be a linear alkyl group having 3 or less carbons;
R 7 is independently selected from hydrogen, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, aryl, aralkyl, and one or more functional groups;
R 8 and R 9 are independently selected from hydrogen, C 1 -C 10 alkyl, fluoride or chloride; with the proviso that R 8 and R 9 are not C 1 -C 10 alkyl at the same time; and,
wherein R 2 and/or R 3 may form a cyclic structure with one or both of R 5 and R 6 , or through one or more links with at least one of R 7 , R 8 and R 9 ;
or,
b) R 1 is methyl;
R 4 is H;
R 2 and R 3 are independently selected from methyl, ethyl, allyl, or isopropyl, or R 2 and R 3 together with the carbons carrying them form a fused 6-, 7- or 8-membered carbocylic ring; with the proviso that R 2 and R 3 are not both isopropyl at the same time;
R 5 and R 6 are each independently a C 1 -C 10 alkyl, cycloalkyl, a fused or bridged ring, aralkyl, or a group having the structure of formula (II);
wherein,
n ranges from 1 to 3; with the proviso that only one of R 5 or R 6 may be a linear alkyl group having 3 or less carbons;
R 7 is independently selected from hydrogen, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, aryl, aralkyl, and one or more functional groups;
R 8 and R 9 are independently selected from hydrogen, C 1 -C 10 alkyl, fluoride or chloride; and,
wherein R 2 and/or R 3 may form a cyclic structure with one or both of R 5 and R 6 , or through one or more links with at least one of R 7 , R 8 and R 9 ;
and,
X − is an anion for the imidazolinium salt.
2. The imidazolinium salt of claim 1 , wherein:
R 1 and R 4 are methyl;
R 2 and R 3 are methyl, or R 2 and R 3 together with the carbons carrying them form a fused 6-membered carbocylic ring;
R 5 and R 6 are independently selected from the group consisting of isopropyl, tertbutyl, neopentyl, phenyl, or a group a group having the structure of formula (II):
wherein n ranges from 1 to 3;
R 7 is independently selected from hydrogen, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, aryl, aralkyl, and one or more functional groups; and,
R 8 and R 9 are independently selected from hydrogen, C 1 -C 10 alkyl, fluoride or chloride; with the proviso that R 8 and R 9 are not C 1 -C 10 alkyl at the same time.
3. The imidazolinium salt of claim 2 , wherein:
R 2 and R 3 are methyl;
R 5 and R 6 are independently selected from phenyl, mesityl, o-tolyl, m-tolyl, p-tolyl, o-difluorophenyl, o-dichlorophenyl or o-isopropylphenyl; and,
X − is chloride, bromide, iodide, tetrafluroborate (BF 4 ) or trifluoroacetate (CF 3 COO).
4. The imidazolinium salt of claim 1 , wherein:
R 1 is methyl;
R 4 is H;
R 2 and R 3 are methyl, or R 2 and R 3 together with the carbons carrying them form a fused 6-membered carbocylic ring;
R 5 and R 6 are independently selected from isopropyl, tertbutyl, neopentyl, phenyl, or a group having the structure of formula (II):
wherein n ranges from 1 to 3;
R 7 is independently selected from hydrogen, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, aryl, aralkyl, and one or more functional groups; and,
R 8 and R 9 are independently selected from hydrogen, C 1 -C 10 alkyl, fluoride or chloride.
5. The imidazolinium salt of claim 4 , wherein:
R 2 and R 3 are methyl, or R 2 and R 3 together with the carbons carrying them form a fused 6-membered carbocylic ring;
R 5 and R 6 are independently selected from phenyl, mesityl, o-tolyl, m-tolyl, p-tolyl, o-difluorophenyl, o-dichloropheynl or o-isopropylphenyl; and,
X − is chloride, tetrafluroborate(BF 4 ) or trifluoroacetate (CF 3 COO).
6. The N-heterocyclic carbene (NHC) ruthenium olefin metathesis catalyst of formula (III):
wherein:
X 1 and X 2 are independently anionic ligands;
R 10 and R 11 are each independently hydrogen or a substituted or unsubstituted substituent selected from 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 or C 1 -C 20 alkylsulfinyl; or R 10 and R 11 may optionally be linked together to form a cyclic structure via one of the listed substituents;
m is 1 or 2, wherein, when m is 1, L is a neutral 2-electron donor ligand and may optionally be linked to R 11 forming a chelating carbene ligand; and, when m is 2, L is a heteroarene ligand; and
NHC is an N-heterocyclic carbene (NHC) ligand of formula (IV):
a) R 1 and R 4 are methyl; and
R 2 and R 3 are independently selected from methyl, ethyl, and allyl, or R 2 and R 3 together with the carbons carrying them form a fused 6-, 7- or 8-membered carbocylic ring;
R 5 and R 6 are each independently a C 1 -C 10 alkyl, cycloalkyl, a fused or bridged ring, aralkyl, or a group having the structure of formula (II):
wherein,
n ranges from 1 to 3; with the proviso that only one of R 5 or R 6 may be a linear alkyl group having 3 or less carbons;
R 7 is independently selected from hydrogen, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, aryl, aralkyl, and one or more functional groups;
R 8 and R 9 are independently selected from hydrogen, C 1 -C 10 alkyl, fluoride, or chloride; with the proviso that R 8 and R 9 are not C 1 -C 10 alkyl at the same time; and,
wherein R 2 and/or R 3 may form a cyclic structure with one or both of R 5 and R 6 , or through one or more links with at least one of R 7 , R 8 and R 9 ; or
b) R 1 is methyl;
R 4 is H;
R 2 and R 3 are independently selected from methyl, ethyl, allyl and isopropyl, or R 2 and R 3 together with the carbons carrying them form a fused 6-, 7- or 8-membered carbocylic ring; with the proviso that R 2 and R 3 are not both isopropyl at the same time; and
R 5 and R 6 are each independently a C 1 -C 10 alkyl, cycloalkyl, a fused or bridged ring, aralkyl, or a group having the structure of formula (II):
wherein,
n ranges from 1 to 3; with the proviso that only one of R 5 or R 6 may be a linear alkyl group having 3 or less carbons;
R 7 is independently selected from hydrogen, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, aryl, aralkyl, and one or more functional groups;
R 8 and R 9 are hydrogen, C 1 -C 10 alkyl, fluoride or chloride; and,
wherein R 2 and/or R 3 may form a cyclic structure with one or both of R 5 and R 6 , or through one or more links with at least one of R 7 , R 8 and R 9 .
7. The N-heterocyclic carbene (NHC) ruthenium olefin metathesis catalyst of claim 6 , wherein:
R 1 and R 4 are methyl;
R 2 and R 3 are methyl, or R 2 and R 3 together with the carbons carrying them form a fused 6-membered carbocylic ring; and,
R 5 and R 6 are independently selected from isopropyl, tertbutyl, neopentyl, phenyl, or a group having the structure of formula (II):
wherein,
n ranges from 1 to 3;
R 7 is methyl, fluoride or chloride; and,
R 8 and R 9 are as defined in claim 6 .
8. The N-heterocyclic carbene (NHC) ruthenium olefin metathesis catalyst of claim 7 , wherein:
R 2 and R 3 are methyl; and
R 5 and R 6 are independently selected from phenyl, mesityl, o-tolyl, m-tolyl, p-tolyl, o-difluorophenyl, o-dichloropheynl or o-isopropylphenyl.
9. The N-heterocyclic carbene (NHC) ruthenium olefin metathesis catalyst of claim 6 , wherein:
R 1 is methyl;
R 4 is H;
R 2 and R 3 are methyl, or R 2 and R 3 together with the carbons carrying them form a fused 6-membered carbocylic ring; and
R 5 and R 6 are independently selected from isopropyl, tertbutyl, neopentyl, phenyl, or a group having the structure of formula (II):
wherein,
n ranges from 1 to 3;
R 7 is methyl, fluoride or chloride; and,
R 8 and R 9 are as defined in claim 6 .
10. The N-heterocyclic carbene (NHC) ruthenium olefin metathesis catalyst of claim 9 , wherein:
R 2 and R 3 are methyl, or R 2 and R 3 together with the carbons carrying them form a fused 6-membered carbocylic ring; and,
R 5 and R 6 are independently selected from phenyl, mesityl, o-tolyl, m-tolyl, p-tolyl, o-difluorophenyl, o-dichloropheynl or o-isopropylphenyl.
11. The N-heterocyclic carbene (NHC) ruthenium olefin metathesis catalyst of claim 6 , wherein:
X 1 and X 2 are halide, or a substituted or unsubstituted group selected from benzoate, C 1 -C 5 carboxylate, C 1 -C 5 alkyl, phenoxy, C 1 -C 5 alkoxy, C 1 -C 5 alkylthio, aryl, or C 1 -C 5 alkyl sulfonate;
R 10 is hydrogen, C 1 -C 5 alkyl or aryl;
R 11 is a substituted or unsubstituted group selected from C 1 -C 20 alkyl, C 2 -C 20 alkenyl, or aryl;
m is 1; and,
L is selected from phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, imine, sulfoxide, carboxyl, nitrosyl, pyridine, or thioether, or is linked to R 11 forming a chelating carbene ligand.
12. The N-heterocyclic carbene (NHC) ruthenium olefin metathesis catalyst of claim 11 , wherein:
X 1 and X 2 are each 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, or trifluoromethanesulfonate;
R 10 is hydrogen, C 1 -C 5 alkyl or aryl;
R 11 is a substituted or unsubstituted group selected from the group consisting of C 1 -C 20 alkyl, C 2 -C 20 alkenyl, and aryl;
m is 1; and,
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, or is linked to R 11 forming a chelating carbene ligand.
13. The N-heterocyclic carbene (NHC) ruthenium olefin metathesis catalyst of claim 12 , wherein:
X 1 and X 2 are each chloride;
R 10 is hydrogen;
R 11 is phenyl, vinyl or —CH═C(CH 3 ) 2 ;
m is 1; and
L is selected from P(cyclohexyl) 3 , P(cyclopentyl) 3 , P(isopropyl) 3 , or P(phenyl) 3 , or is linked to R 11 forming a chelating carbene ligand.
14. The N-heterocyclic carbene (NHC) ruthenium olefin metathesis catalyst of claim 6 , wherein the catalyst of formula (III) has the structure of formula (V):
wherein,
NHC is an N-heterocyclic carbene (NHC) ligand of formula (IV), as defined in claim 6 ;
Y is a heteroatom selected from oxygen, sulfur, nitrogen, or phosphorus;
X 1 and X 2 are independently anionic ligands;
Z is selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, functionalized alkyl, or functionalized aryl, wherein the functional group(s) may independently be selected from alkoxy, aryloxy, halogen, carbonyl, carboxylic acid, ketone, aldehyde, nitrate, nitrile, nitro, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, sulfide, sulfonyl, sulfinyl, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, borate, or combinations thereof; each optionally substituted with an alkyl, halogen, alkoxy, aryl, aryloxy, or heteroaryl moiety;
R a , R b , R c , and R d are independently selected from hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, functionalized alkyl, or functionalized aryl, wherein the functional group(s) may independently be selected from alkoxy, aryloxy, halogen, carbonyl, carboxylic acid, ketone, aldehyde, nitrate, nitrile, nitro, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, sulfide, sulfonyl, sulfinyl, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, borate, or combinations thereof; each optionally substituted with an alkyl, halogen, alkoxy, aryl, aryloxy, or heteroaryl moiety, wherein any two or more of R a , R b , R c , and R d may be independently linked through hydrocarbon or functionalized hydrocarbon groups forming an aliphatic or aromatic ring.
15. The N-heterocyclic carbene (NHC) ruthenium olefin metathesis catalyst of claim 13 , wherein the catalyst of formula (III) is selected from:
16. The N-heterocyclic carbene (NHC) ruthenium olefin metathesis catalyst of claim 11 , wherein the catalyst of formula (III) is selected from:
17. The N-heterocyclic carbene (NHC) ruthenium olefin metathesis catalyst of claim 13 , wherein L is selected from P(cyclohexyl) 3 , P(cyclopentyl) 3 , P(isopropyl) 3 , or P(phenyl) 3 .
18. The N-heterocyclic carbene (NHC) ruthenium olefin metathesis catalyst of claim 11 , wherein L is selected from P(cyclohexyl) 3 , P(cyclopentyl) 3 , P(isopropyl) 3 , or P(phenyl) 3 .
19. A ring-closing metathesis method for preparing a tetrasubstituted cyclic olefin comprising:
contacting an olefinic compound having at least two terminal olefins which are substituted at the beta-carbon of each terminal olefin with an N-heterocyclic carbene (NHC) ruthenium olefin metathesis catalyst of claim 6 under metathesis conditions to form a cyclic tetra-substituted olefin.
20. The method of claim 19 wherein the catalyst is present in an amount ranging from about 25 ppm to about 10 mol %.
21. An olefin metathesis reaction comprising the step of:
contacting an olefin with an N-heterocyclic carbene (NHC) ruthenium olefin metathesis catalyst of claim 6 under metathesis conditions.
22. A cross-metathesis reaction comprising the step of contacting an olefin and a tri-substituted olefin or a di-substituted olefin having further substitution at the allylic carbon with an N-heterocyclic carbene (NHC) ruthenium olefin metathesis catalyst of claim 6 under metathesis conditions.