Bridged bi-aromatic ligands and transition metal compounds prepared therefrom
Disclosed are novel bridged bi-aromatic phenol ligands and transition metal compounds derived therefrom. Also disclosed are methods of making the ligands and transition metal compounds.
1. A bridged bi-aromatic phenol ligand of formula (I):
wherein each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 is independently selected from the group consisting of hydrogen, halide, optionally substituted hydrocarbyl, heteroatom-containing optionally substituted hydrocarbyl, alkoxy, aryloxy, silyl, boryl, dialkyl amino, alkylthio, arylthio and seleno; optionally two or more R groups can combine together into ring structures with such ring structures having from 3 to 100 non-hydrogen atoms in the ring; A is O, S, NR a wherein R a is optionally substituted hydrocarbyl, or A is —Y-E-Y′— wherein E is a bridging group having from one to 50 non-hydrogen atoms and Y and Y′ are independently selected from O, S, NR a and PR a and A is O, S, NR a and PR a wherein R a is optionally substituted hydrocarbyl, or A is —Y-E-Y′— wherein E is a bridging group having from one to 50 non-hydrogen atoms; Y and Y′ are independently selected from O, S, NR a and PR a wherein R a is optionally substituted hydrocarbyl wherein R a is optionally substituted hydrocarbyl; Ar is, independently, optionally substituted aryl or optionally substituted heteroaryl.
2. A ligand according to claim 1 wherein each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 R 12 , R 13 and R 14 is independently selected from the group consisting of hydrogen, halide, and optionally substituted alkyl, heteroalkyl, aryl, heteroaryl, alkoxyl, aryloxyl, silyl, dialkylamino, alkylthio, and arylthio.
3. A ligand according to claim 1 wherein each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 R 12 , R 13 and R 14 is independently selected from the group consisting of hydrogen, halide, and optionally substituted alkyl, heteroalkyl, aryl, heteroaryl, alkoxyl, and aryloxyl.
4. A ligand according to claim 1 wherein the bridging group E is selected from the group consisting of optionally substituted divalent hydrocarbyl and divalent heteroatom containing hydrocarbyl.
5. A ligand according to claim 1 wherein the bridging group E is selected from the group consisting of optionally substituted divalent alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, carbocycle, heterocarbocycle, aryl, heteroaryl and silyl.
6. A ligand according to claim 1 wherein the bridging group E is represented by the general formula -(QR 15 2-z″ ) z′ — wherein each Q is either carbon or silicon and each R 15 may be the same or different from the others such that each R 15 is selected from the group consisting of hydrogen and optionally substituted hydrocarbyl and heteroatom containing hydrocarbyl, and optionally two or more R 15 groups may be joined into a ring structure having from 3 to 50 atoms in the ring structure not counting hydrogen atoms; z′ is an integer from 1 to 10; and z″ is 0, 1 or 2.
7. A ligand according to claim 1 wherein Ar is, independently, an optionally substituted phenyl, naphthyl, biphenyl, anthracenyl or phenanthrenyl.
8. A ligand according to claim 1 wherein Ar is, independently, an optionally substituted thiophene, pyridine, isoxazole, pyrazole, pyrrole, furan, or benzo-fused analogues of these rings.
9. A ligand according to claim 1 wherein each occurrence of Ar is the same.
10. A ligand according to claim 1 wherein the ligand of formula (I) is of formula (II):
wherein each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , and Ar is as defined in claim 1 .
11. A ligand according to claim 1 wherein the ligand of formula (I) may be of formula (III):
wherein each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , Ar, Y′ and E is as defined in claim 1 .
12. A ligand according to claim 1 wherein the ligand of formula (I) may be of formula (IV):
wherein each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , Ar, and E is as defined in claim 1 .
13. A method of preparing a bridged bi-aromatic phenol ligand according to claim 1 comprising:
deprotecting a compound of formula (VIII)
to yield the bi-aromatic phenol ligand of formula (I) according to claim 1 ; wherein each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 is independently selected from the group consisting of hydrogen, halide, optionally substituted hydrocarbyl, heteroatom-containing optionally substituted hydrocarbyl, alkoxy, aryloxy, silyl, boryl, dialkyl amino, alkylthio, arylthio and seleno; optionally two or more R groups can combine together into ring structures with such ring structures having from 3 to 100 non-hydrogen atoms in the ring; A is O, S, NR a and PR a wherein R a is optionally substituted hydrocarbyl, or A is —Y-E-Y′— wherein E is a bridging group having from one to 50 non-hydrogen atoms; Y and Y′ are independently selected from O, S, NR a and PR a wherein R a is optionally substituted hydrocarbyl; Ar is optionally substituted aryl or heteroaryl; and PG is a protecting group.
14. A method according to claim 13 comprising the steps of:
a) treating a protected bi-aromatic phenol of formula (V) with a lithiating agent to yield a dilithio protected bi-aromatic phenol of formula (VI);
b) treating the dilithio protected bi-aromatic phenol of formula (VI) with a zinc compound and a compound of formula ArX in the presence of a catalyst, to yield the protected bi-aromatic phenol of formula (VIII)
wherein each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 is independently selected from the group consisting of hydrogen, halide, optionally substituted hydrocarbyl, heteroatom-containing optionally substituted hydrocarbyl, alkoxy, aryloxy, silyl, boryl, dialkyl amino, alkylthio, arylthio and seleno; optionally two or more R 1 to R 14 groups can combine together into ring structures with such ring structures having from 3 to 100 non-hydrogen atoms in the ring; A is O, S, NR a and PR a wherein R a is optionally substituted hydrocarbyl, or A is —Y-E-Y′— wherein E is a bridging group having from one to 50 non-hydrogen atoms; Y and Y′ are independently selected from O, S, NR a and PR a wherein R a is optionally substituted hydrocarbyl; Ar is optionally substituted aryl or heteroaryl; X is halide; PG is a protecting group.
15. A method according to claim 13 comprising the steps of:
a) treating a compound of formula (X) with a zinc halide and a compound of formula ArX in the presence of a catalyst to yield a compound of formula (XI);
b) treating the compound of formula (XI) with a lithiating agent to yield a compound of formula (XII);
c) treating the compound of formula (XII) with zinc halide and a compound of formula (XIII) in the presence of a catalyst to yield the compound of formula (VIII); and
d) deprotecting the compound of formula (VIII) to yield the bi-aromatic phenol ligand of formula (I)
wherein each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 is independently selected from the group consisting of hydrogen, halide, optionally substituted hydrocarbyl, heteroatom-containing optionally substituted hydrocarbyl, alkoxy, aryloxy, silyl, boryl, dialkyl amino, alkylthio, arylthio and seleno; optionally two or more R groups can combine together into ring structures with such ring structures having from 3 to 100 non-hydrogen atoms in the ring; A is O, S, NR a and PR a wherein R a is optionally substituted hydrocarbyl, or A is —Y-E-Y′— wherein E is a bridging group having from one to 50 non-hydrogen atoms; Y and Y′ are independently selected from O, S, NR a and PR a wherein R a is optionally substituted hydrocarbyl; Ar is optionally substituted aryl or heteroaryl; X is halide; PG is a protecting group.
16. A method according to claim 13 wherein each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 R 12 , R 13 and R 14 is independently selected from the group consisting of hydrogen, halide, and optionally substituted alkyl, heteroalkyl, aryl, heteroaryl, alkoxyl, aryloxyl, silyl, dialkylamino, alkylthio, and arylthio.
17. A method according to claim 13 wherein each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 R 12 , R 13 and R 14 is independently selected from the group consisting of hydrogen, halide, and optionally substituted alkyl, heteroalkyl, aryl, heteroaryl, alkoxyl, and aryloxyl.
18. A method according to claim 13 wherein the bridging group E is selected from the group consisting of optionally substituted divalent hydrocarbyl and divalent heteroatom containing hydrocarbyl.
19. A method according to claim 13 wherein the bridging group E is selected from the group consisting of optionally substituted divalent alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, carbocycle, heterocarbocycle, aryl, heteroaryl and silyl.
20. A method according to claim 13 wherein the bridging group E is represented by the general formula -(QR 15 2-z″ ) z′ — wherein each Q is either carbon or silicon and each R 15 may be the same or different from the others such that each R 15 is selected from the group consisting of hydrogen and optionally substituted hydrocarbyl and heteroatom containing hydrocarbyl, and optionally two or more R 15 groups may be joined into a ring structure having from 3 to 50 atoms in the ring structure not counting hydrogen atoms; z′ is an integer from 1 to 10; and z″ is 0, 1 or 2.