Allyl complexes for use in coupling reactions
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, X is an anionic ligand. A process for the preparation of the complex, and its use in carbon-carbon or carbon-nitrogen coupling reactions is also provided.
1. A complex of formula (1):
wherein:
M is palladium or nickel;
R 1 and R 2 are, independently, C 1 -C 20 straight-chain alkyl, C 1 -C 20 branched-chain alkyl, C 3 -C 15 cycloalkyl, C 5 -C 20 aryl, or C 3 -C 20 heteroaryl;
R 3 is:
(a) dimethylaminophenyl; or
(b) a substituted metallocenyl of formula (2):
wherein:
R 10 is C 1 -C 20 alkyl, C 6 -C 20 aryl, (C 1 -C 20 alkyl)HN—, (C 1 -C 20 dialkyl)N—, (C 1 -C 20 dialkyl)amino-C 1 -C 20 -alkyl or C 1 -C 20 alkoxy-C 1 -C 20 -alkyl;
R 11 is C 1 -C 20 alkyl or C 6 -C 20 aryl;
p is 0, 1, 2, 3 or 4, wherein when p is 2, 3 or 4, each R 10 is the same or different;
q is 2, 3, 4 or 5, wherein each R 11 is the same or different,
R 4 is C 1 -C 20 straight-chain alkyl, C 1 -C 20 branched-chain alkyl, C 3 -C 15 cycloalkyl, C 6 -C 20 aryl, or C 5 -C 20 heteroaryl,
n is 0, 1, 2, 3, 4 or 5; and
X is a halo group,
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), or C 1-20 heteroalkyl, 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 according to claim 1 , wherein M is palladium.
3. The complex according to claim 1 , wherein R 3 is dimethylaminophenyl.
4. The complex according to claim 1 , wherein R 3 is of formula (3):
wherein:
R 11 is C 1-20 alkyl or aryl; and
q is 2, 3, 4 or 5.
5. The complex according to claim 1 , wherein:
R 11 is phenyl, naphthyl, methoxyphenyl, halophenyl, methylphenyl, or F 3 C-phenyl; and
q is 4 or 5.
6. The complex according to claim 1 , wherein:
R 11 is phenyl, methoxyphenyl, methylphenyl, or F 3 C-phenyl; and
q is 4 or 5.
7. The complex according to claim 1 , wherein R 3 is of formula (4):
8. The complex according to claim 1 , that is:
9. 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 -C 20 straight-chain alkyl, C 1 -C 20 branched-chain alkyl, C 3 -C 15 cycloalkyl, C 5 -C 20 aryl, or C 3 -C 20 heteroaryl;
R 3 is:
(a) dimethylaminophenyl; or
(b) a substituted metallocenyl of formula (2):
wherein:
R 10 is C 1 -C 20 alkyl, C 6 -C 20 aryl, (C 1 -C 20 alkyl)HN—, (C 1 -C 20 dialkyl)N—, (C 1 -C 20 dialkyl)amino-C 1 -C 20 -alkyl or C 1 -C 20 alkoxy-C 1 -C 20 -alkyl;
R 11 is C 1 -C 20 alkyl or C 6 -C 20 aryl;
p is 0, 1, 2, 3 or 4, wherein when p is 2, 3 or 4, each R 10 is the same or different;
q is 2, 3, 4 or 5, wherein each R 11 is the same or different;
R 4 is C 1 -C 20 straight-chain alkyl, C 1 -C 20 branched-chain alkyl, C 3 -C 15 cycloalkyl, C 6 -C 20 aryl, or C 5 -C 20 heteroaryl;
n is 0, 1, 2, 3, 4 or 5;
X is a halo group;
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), or C 1-20 heteroalkyl, 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.
10. The complex according to claim 1 , wherein:
(a) both R 1 and R 2 are tert-butyl;
(b) R 4 is phenyl or methyl and n is 1 or 2;
(c) n is 0;
(d) X is chlorine;
(e) two or more of (a), (b), and (d); or
(f) two or more of (a), (c), and (d).