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 meros [1] dendrimer dendros = + ↓ ↓ 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 R 2 N R Suzuki Buchwald-Hartwig 2 ) H N O H ( R 2 B R R R R RZnBr Negishi Heck X + [Pd] R R RSiMe 3 R u R B i M n S g Hiyama B R Sonogashira r R R Kumada Stille Figure: Palladium Catalyzed Cross-coupling Reactions [5]
Introduction Methodology Synthesis Characterization References Palladium Catalyzed Cross-coupling: Mechanism Pd(II)L n R X R' R L Pd L Reductive Elimination Oxidation R' L L X Pd Pd R L R L L R' R' M cis - trans -Isomerization Transmetallation Pd M = SnR 3 M X B(OH) 2 R L ZnX MgBr Figure: Palladium Catalyzed Cross-coupling Mechanism
Introduction Methodology Synthesis Characterization References Palladium Catalyzed Suzuki Cross-coupling (I) [Pd], Base + X (HO) 2 B R R R' Solvent, T R' Table: Reaction Conditions [6] X Catalysts Bases / solvents Temp. / ° C References I, Br Pd(PPh 3 ) 4 NaHCO 3 , Na 2 CO 3 / DME / H 2 O reflux JOC , 1997 , 62 , 7900-7901. JOC , 2000 , 65 , 3042-3046. I, Br, OTf Pd(PPh 3 ) 4 K 3 PO 4 • n H 2 O / dioxane or DMF 80 OL , 2000 , 2 , 1843-1845. Synlett , 1992 , 207-210. JOC , 1993 , 58 , 2201-2208. I, Br Pd(PPh 3 ) 4 CsF / DMF reflux JOC , 1994 , 59 , 6095-6097. JOC , 1997 , 62 , 8535-8539. I, Br Pd(PPh 3 ) 4 Na 2 CO 3 / MeOH-H 2 reflux JACS , 2000 , 122 , 52-57. JOC , 1996 , 61 , 1375-1384.
Introduction Methodology Synthesis Characterization References Palladium Catalyzed Suzuki Cross-coupling (II) [Pd], Base X + (HO) 2 B R Solvent, T R R' R' X Catalysts Bases / Solvents Temp. / ° C References I, Br, OTf Pd(PPh 3 ) 4 Na 2 CO 3 or K 3 PO 4 / toluene-H 2 O 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(PPh 3 ) 4 Ba(OH) 2 / DME / H 2 O reflux Synlett , 1992 , 207-210. JOC , 1997 , 62 , 4943-4948. K 2 CO 3 / t Bu 4 NBr / H 2 Br Pd(OAc) 2 70 JOC , 1994 , 59 , 5034-5037. OL , 1999 , 1 , 965-967. I Pd(OAc) 2 K 2 CO 3 or Cs 2 CO 3 / acetone-H 2 O reflux JOC , 1997 , 62 , 7170-7173. JOC , 2000 , 65 , 2837-2842.
Introduction Methodology Synthesis Characterization References Palladium Catalyzed Suzuki Cross-coupling (III) [Pd], Base X + (HO) 2 B R R' Solvent, T R R' X Catalysts Bases / Solvents Temp. / ° C References Br Pd 2 (dba) 3 / A K 3 PO 4 , toluene 100 JACS , 2002 , 124 , 1162-1163. Br Pd 2 (dba) 3 / B or C K 3 PO 4 , toluene 100 JACS , 2002 , 124 , 1162-1163. Pd 2 (dba) 3 / t Bu 3 P Cl Cs 2 CO 3 / dioxane rt ACIEE , 1998 , 24 , 3387-3388. JACS , 2000 , 122 , 4020-4028. Pd 2 (dba) 3 / t Bu 3 PHBF 4 KF , THF rt OL , 2001 , 3 , 4295-4298. PCy 2 PPh 2 PCy 2 NMe 2 A B C
Introduction Methodology Synthesis Characterization References Palladium Catalyzed Suzuki Cross-coupling (IV) [Pd], Base X + (HO) 2 B R Solvent, T R R' R' X Catalysts Bases / Solvents Temp. / ° C References Cl Pd 2 (dba) 3 / D K 3 PO 4 , toluene 80-100 Om , 1993 , 12 , 1665-1667. JACS , 1998 , 118 , 9722-9723. JACS , 1999 , 119 , 9550-9557. Pd 2 (dba) 3 / E KF , THF rt JACS , 1999 , 119 , 9550-9557. Pd 2 (dba) 3 / F CsF or K 3 PO 4 , toluene or dioxane 100 JOC , 1999 , 64 , 6797-6803. Pd 2 (dba) 3 / G Cs 2 CO 3 , dioxane 80 JOC , 1999 , 64 , 3804-3805. Pd 2 (dba) 3 / H K 3 PO 4 , toluene 100 CC , 2001 , 2408-2409. PR 3 PPh 2 Me O TMS N N Fe Me Me O Me Me PCy 2 Me D : R=Cy F G E : R= t -Bu H
Introduction Methodology Synthesis Characterization References Dendrons (I) N N N N N N O O O O N O O O O * * *
Introduction Methodology Synthesis Characterization References Dendrons (II) N N N N O O O N N O O O O O N N O O O O O O *
Introduction Methodology Synthesis Characterization References Monomers [G-x] [G-x] [G-x] [G-x] [G-x] [G-x] HO OH O O O O O O [G-x]-Br CBr 4 / PPh 3 LAH / THF K 2 CO 3 and a , N 2 N 2 N 2 , reflux, 48h O OMe O OMe OH Br 4 3 1 2 x = 0, a = n -Butanone [G-x] O x = 1, 2, a = 18-Crown-6, Acetone * = [G-(x+1)]-* * = [G-0]-* N [G-x] O (x = 0, 1, 2) [G-x] [G-x] [G-x]-Br Br Br Br Br DMSO/NaOH TEBAB 5 6 n -C 8 H 17 Br, t -BuOK, THF, N 2 n -C 8 H 17 n -C 8 H 17 n -C 8 H 17 n -C 8 H 17 Mg, I 2 , THF Br Br BrMg MgBr 7 8
Introduction Methodology Synthesis Characterization References Suzuki Polycondensation (SPC) HO OH O O B(OMe) 3 HO OH BrMg MgBr B B B B H 2 O HO OH toluene O O reflux, 3h 8 9 10 [G-x] [G-x] O O [Pd] Br Br + B B * * O O [G-x] [G-x] n 10 11 6 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] Φ F Polymers M n P n M w P w M w / M n T G 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)
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