Handbook of Functionalized Organometallics Applications in S

(HO) 3B
O
NMe 3
N
N
O
Br
3.2 Preparation and Reaction of Functionalized Aryl and Heteroaryl Boranes 67
Me
N
Pd(OAc) 2 (5 mol %)
TPPDS (20 mol %)
THF/H2O (4:1), 40 ºC, 40 h
2 n N
87: (1 equiv)
O
N
Me
O N
2 n
88: n=1-3:16-22%
TPPDS = triphenylphosphine disulfonic acid disodium salt
Scheme 3.38 Solid-phase intramolecular macrocyclization.
Dehaen has developed several approaches for the synthesis of highly soluble rodlike
diketopyrrolopyrrole oligomers of specified lengths by employing Pd-catalyzed
Suzuki cross-coupling reactions of bis-boronate 89 and the brominated 1,4-dioxo-3,6diphenylpyrrolo[3,4-c]pyrroles
(DPP) 90 and 91 [58]. An example of a convergent
approach for the synthesis of trimer of DPPS (92) is shown. These compounds are
useful for the construction of organic light emitting devices (Scheme 3.39).
t-Bu
R
t-Bu
t-Bu
R
N
O
N
90: R=H
91: R=Br
O
t-Bu
N
N
t-Bu
Br
O t-Bu
O
t-Bu
t-Bu
n-Hex
n-Hex
n-Hex
O B
O
O
B O
89
n-Hex
Pd(PPh 3) 4, Na 2CO 3
toluene, heating
t-Bu
O
t-Bu
N
N
t-Bu
92: 69%
O
n-Hex
Scheme 3.39 Synthesis of highly functionalized polymers and oligomers.
R
t-Bu
t-Bu
O
t-Bu
N
N
t-Bu
n-Hex
O
t-Bu
t-Bu
91 (3 fold excess)
Pd(PPh 3) 4, Na 2CO 3
toluene, heating
O
n-Hex
N
t-Bu
t-Bu
N
O
n-Hex
O
B
O
t-Bu
R