Complexes
The present invention provides a complex of formula (1), wherein, M is palladium or nickel, R 1 and R 2 are independently organic groups having 1-20 carbon atoms, or R 1 and R 2 are linked to form a ring structure with the phosphorus atom, R 3 is selected from the group consisting of substituted and unsubstituted aryl, substituted and unsubstituted heteroaryl, and substituted and unsubstituted metallocenyl, R 4 is an organic group having 1-20 carbon atoms, n is 0, 1, 2, 3, 4 or 5, and X is an anionic ligand. The invention also provides a process for the preparation of the complex, and its use in carbon-carbon or carbon-nitrogen coupling reactions.
1. A complex of formula (1):
wherein:
M is palladium or nickel,
R 1 and R 2 are, independently, C 1-20 straight-chain alkyl, C 1-20 branched-chain alkyl, or C 3-15 cycloalkyl,
R 3 is a) or b):
a) substituted aryl, wherein the aryl is substituted with one or more halide, C 2-20 alkoxy, substituted C 6-20 aryl, branched-chain (C 1-20 dialkyl)amino, C 2-15 heterocycloalkyl, or tri(halo)methyl; or
b) substituted or unsubstituted heteroaryl that is thienyl, furanyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, thiadiazolyl, thiophenyl, oxadiazolyl, pyridinyl, pyrimidyl, benzoxazolyl, benzthiazolyl, benzimidazolyl, indolyl, or quinolinyl;
R 4 is C 1-20 straight-chain alkyl, C 1-20 branched-chain alkyl, C 3-15 cycloalkyl, C 6-20 aryl, or C 5 -20 heteroaryl;
n is 0, 1, 2, 3, 4 or 5,
X is halo;
wherein each alkyl, alkoxy, heteroalkyl, aryl or heteroaryl is optionally substituted with one or more halo, C(halo) 3 , R a , ═O, ═S, OR a , SR a , NR a R b , ═NR a , ═N—OR a , CN, SCN, NCS, NO 2 , C(O)R a , C(O)OR a , C(S)R a , C(S)OR a , S(O) 2 OH, S(O) 2 R a , S(O) 2 NR a R b , OS(O)R a , or C(O)NR a R b , wherein:
R a and R b are, independently, H, C 1-20 alkyl, C 6-20 aryl, C 6-20 aryl-(C 1-20 alkyl), C 1-20 heteroalkyl, or C 6-20 heteroaryl, or together with the atom to which they are attached form a C 3-15 heterocycloalkyl; and the heteroatoms in the heteroaryl, heteroalkyl or heterocycloalkyl are sulfur, oxygen, or nitrogen.
2. The complex of claim 1 , wherein M is palladium.
3. The complex of claim 1 , wherein R 1 and R 2 are tert-butyl.
4. The complex of claim 1 , wherein R 1 and R 2 are cyclohexyl.
5. The complex of claim 1 , wherein R 3 is furanyl, thiophenyl, pyrrolyl, pyridinyl, or quinolinyl.
6. The complex of claim 1 , wherein X is Cl.
7. The complex of claim 1 , wherein each R 4 is independently methyl, phenyl, or substituted phenyl.
8. A method for preparing a complex of formula (1):
comprising the step of reacting a complex of formula (5) with PR 1 R 2 R 3 ,
wherein:
M is palladium or nickel,
R 1 and R 2 are, independently, C 1-20 straight-chain alkyl, C 1-20 branched-chain alkyl, or C 3-15 cycloalkyl;
R 3 is a) or b):
a) substituted aryl, wherein the aryl is substituted with one or more halide, C 2-20 alkoxy, substituted C 6-20 aryl, branched-chain (C 1-20 dialkyl)amino, C 2-15 heterocycloalkyl, or tri(halo)methyl; or
b) substituted or unsubstituted heteroaryl that is thienyl, furanyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, thiadiazolyl, thiophenyl, oxadiazolyl, pyridinyl, pyrimidyl, benzoxazolyl, benzthiazolyl, benzimidazolyl, indolyl, or quinolinyl;
R 4 is C 1-20 straight-chain alkyl, C 1-20 branched-chain alkyl, C 3-15 cycloalkyl, C 6-20 aryl, or C 5 -20 heteroaryl;
n is 0, 1, 2, 3, 4 or 5;
X is halo;
wherein each alkyl, alkoxy, heteroalkyl, aryl or heteroaryl is optionally substituted with one or more halo, C(halo) 3 , R a , ═O, ═S, OR a , SR a , NR a R b , ═NR a , ═N—OR a , CN, SCN, NCS, NO 2 , C(O)R a , C(O)OR a , C(S)R a , C(S)OR a , S(O) 2 OH, S(O) 2 R a , S(O) 2 NR a R b , OS(O)R a , or C(O)NR a R b , wherein:
R a and R b are, independently, H, C 1-20 alkyl, C 6-20 aryl, C 6-20 aryl-(C 1-20 alkyl), C 1-20 heteroalkyl, or C 6-20 heteroaryl, or together with the atom to which they are attached form a C 3-15 heterocycloalkyl; and
the heteroatoms in the heteroaryl, heteroalkyl or heterocycloalkyl are sulfur, oxygen, or nitrogen.
9. A method for performing a carbon-carbon coupling reaction or a carbon-nitrogen coupling reaction in the presence of a catalyst, the method comprising using a catalyst that is a complex of claim 1 .
10. A method for performing a carbon-carbon coupling reaction or a carbon-nitrogen coupling reaction in the presence of a catalyst, the method comprising using a catalyst that is a complex of claim 2 .