Synthesis of Dendronized Poly(fluorene)s with Peripheral Carbazole - - PowerPoint PPT Presentation

Synthesis of Dendronized Poly(fluorene)s with Peripheral Carbazole Groups

LI Yi

Introduction Methodology Synthesis Characterization References

Outline

Introduction Methodology Growth Strategies Palladium Catalyzed Cross-coupling Palladium Catalyzed Suzuki Cross-coupling Synthesis Dendrons Monomers Suzuki Polycondensation (SPC) Characterization References

Introduction Methodology Synthesis Characterization References

Introduction

dendrimer = dendros + meros[1] ↓ ↓ tree part

Introduction Methodology Synthesis Characterization References

Growth Strategies (I)

• Divergent[2]
• Convergent[3]

Introduction Methodology Synthesis Characterization References

Growth Strategies (II)

• Double exponential[4]
• Hyperbranched etc.

Introduction Methodology Synthesis Characterization References

Palladium Catalyzed Cross-coupling: Reactions

X + [Pd] R B ( O H )

2

RZnBr R R RSiMe3 R R M g B r R R R2N R R R S n

i

B u Suzuki Negishi Hiyama Kumada Buchwald-Hartwig Heck Sonogashira Stille R R N H R2

Figure: Palladium Catalyzed Cross-coupling Reactions[5]

Introduction Methodology Synthesis Characterization References

Palladium Catalyzed Cross-coupling: Mechanism

Pd L X R L Pd R' L R L Pd L L Pd(II)Ln Pd L R' R L R' R R X R' M X Oxidation Transmetallation cis-trans-Isomerization Reductive Elimination M = SnR3 B(OH)2 ZnX MgBr M

Figure: Palladium Catalyzed Cross-coupling Mechanism

Introduction Methodology Synthesis Characterization References

Palladium Catalyzed Suzuki Cross-coupling (I)

X (HO)2B +

R R' R R'

[Pd], Base Solvent, T

Table: Reaction Conditions[6]

X Catalysts Bases / solvents

• Temp. / °

C References I, Br Pd(PPh3)4 NaHCO3, Na2CO3 / DME / H2O reflux JOC, 1997, 62, 7900-7901. JOC, 2000, 65, 3042-3046. I, Br, OTf Pd(PPh3)4 K3PO4•nH2O / dioxane or DMF 80 OL, 2000, 2, 1843-1845. Synlett, 1992, 207-210. JOC, 1993, 58, 2201-2208. I, Br Pd(PPh3)4 CsF / DMF reflux JOC, 1994, 59, 6095-6097. JOC, 1997, 62, 8535-8539. I, Br Pd(PPh3)4 Na2CO3 / MeOH-H2 reflux JACS, 2000, 122, 52-57. JOC, 1996, 61, 1375-1384.

Introduction Methodology Synthesis Characterization References

Palladium Catalyzed Suzuki Cross-coupling (II)

X (HO)2B +

R R' R R'

[Pd], Base Solvent, T X Catalysts Bases / Solvents

• Temp. / °

C References I, Br, OTf Pd(PPh3)4 Na2CO3 or K3PO4 / toluene-H2O 80-100 JACS, 1997, 119, 7281-7290. JACS, 2000, 122, 6935-6949. JOC, 1998, 63, 5675-5679. Synlett, 1999, 966-968. I, Br, OTf Pd(PPh3)4 Ba(OH)2 / DME / H2O reflux Synlett, 1992, 207-210. JOC, 1997, 62, 4943-4948. Br Pd(OAc)2 K2CO3 / t Bu4NBr / H2 70 JOC, 1994, 59, 5034-5037. OL, 1999, 1, 965-967. I Pd(OAc)2 K2CO3 or Cs2CO3 / acetone-H2O reflux JOC, 1997, 62, 7170-7173. JOC, 2000, 65, 2837-2842.

Introduction Methodology Synthesis Characterization References

Palladium Catalyzed Suzuki Cross-coupling (III)

X (HO)2B +

R R' R R'

[Pd], Base Solvent, T X Catalysts Bases / Solvents

• Temp. / °

C References Br Pd2(dba)3 / A K3PO4, toluene 100 JACS, 2002, 124, 1162-1163. Br Pd2(dba)3 / B or C K3PO4, toluene 100 JACS, 2002, 124, 1162-1163. Cl Pd2(dba)3 / t Bu3P Cs2CO3 / dioxane rt ACIEE, 1998, 24, 3387-3388. JACS, 2000, 122, 4020-4028. Pd2(dba)3 / t Bu3PHBF4 KF , THF rt OL, 2001, 3, 4295-4298.

PCy2 NMe2 A

PCy2 B PPh2 C

Introduction Methodology Synthesis Characterization References

Palladium Catalyzed Suzuki Cross-coupling (IV)

X (HO)2B +

R R' R R'

[Pd], Base Solvent, T X Catalysts Bases / Solvents

• Temp. / °

C References Cl Pd2(dba)3 / D K3PO4, toluene 80-100 Om, 1993, 12, 1665-1667. JACS, 1998, 118, 9722-9723. JACS, 1999, 119, 9550-9557. Pd2(dba)3 / E KF , THF rt JACS, 1999, 119, 9550-9557. Pd2(dba)3 / F CsF or K3PO4, toluene or dioxane 100 JOC, 1999, 64, 6797-6803. Pd2(dba)3 / G Cs2CO3, dioxane 80 JOC, 1999, 64, 3804-3805. Pd2(dba)3 / H K3PO4, toluene 100 CC, 2001, 2408-2409.

PR3 D: R=Cy E: R=t-Bu O O PCy2 Me F N N G Fe Me Me Me Me Me TMS PPh2 H

Introduction Methodology Synthesis Characterization References

Dendrons (I)

N

*

O O N N

*

O O N N O O N N O O

*

Introduction Methodology Synthesis Characterization References

Dendrons (II)

O O N N O O N N O O O O N N O O N N O O O O

*

Introduction Methodology Synthesis Characterization References

Monomers

O O [G-x] [G-x] OMe O O O [G-x] [G-x] OH O O [G-x] [G-x] Br LAH / THF N2 CBr4 / PPh3 N2 N * = [G-0]-* (x = 0, 1, 2) O O [G-x] [G-x] * = [G-(x+1)]-* [G-x]-Br HO OH OMe O Br Br [G-x] [G-x] Br Br [G-x]-Br n-C8H17Br, t-BuOK, THF, N2 Br Br n-C8H17 n-C8H17 Mg, I2, THF BrMg MgBr n-C8H17 n-C8H17 x = 0, a = n-Butanone x = 1, 2, a = 18-Crown-6, Acetone K2CO3 and a, N2, reflux, 48h 1 2 3 4 5 6 7 8 DMSO/NaOH TEBAB

Introduction Methodology Synthesis Characterization References

Suzuki Polycondensation (SPC)

MgBr BrMg B B HO HO OH OH B(OMe)3 [G-x] [G-x] Br Br + B B O O O O [Pd] * [G-x] [G-x] * n H2O B B O O O O toluene reflux, 3h OH HO 8 9 10 6 10 11 11a: x=0 11b: x=1 11c: x=2

Introduction Methodology Synthesis Characterization References

Characterization (I)

GPC[7] TGA[7] DSC[7] UV-vis and PL[7]

Introduction Methodology Synthesis Characterization References

Characterization (II)

Table: Molecular Weights, Thermal Properties, and the Flurenscene Quantum Yields of the Dendronized Polymers (in THF and as Films)[7]

Polymers Mn Pn Mw Pw Mw / Mn TG ΦF in solution films 11a 46 700 47 104 000 104 2.21 103 0.93 0.29 11b 131 000 78 157 000 93 1.20 73 0.96 0.55 11c 143 000 47 171 000 60 1.19 73 0.86 0.64

Introduction Methodology Synthesis Characterization References

References

[1]

• A. D. Schl¨

uter, Top. Curr. Chem. 197, 165-191. (1998) [2]

• D. A. Tomalia, et al., Polymer J. 17, 117-132. (1985)

[3]

• C. J. Hawker, et al., JACS 112, 7638-7647. (1990)

[4]

• T. Kawaguchi, et al., JACS 117, 2159-2165. (1995)

[5]

• N. Miyaura, Top. Curr. Chem. 219, 1-9. (2002)

[6]

• A. B. Charette, CHM6315, U. Montr`

eal (2004) [7]

• Y. Fu, et al., Macromolecules 37, 6395-6400. (2004)

Thank you !