Suzuki ReactionReporter: Yu Ting Huang

Advising Prof: Ru Jong Jeng

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OutlineIntroductionChemistry of Suzuki ReactionReaction mechanismBoron reagents

Recent development of Suzuki ReactionConjugated microporous polymersLight-emitting diodesOrganic Solar cell

Polymer-bound palladium catalyst in Suzuki Reaction

Conclusions2

IntroductionThe Suzuki reaction is the organic reaction that is

classified as a coupling reaction where the coupling partners are a boronic acid with a halide catalyzed by a palladium(0) complex

It was first published in 1979 by Akira Suzuki and he shared the 2010 Nobel Prize in Chemistry with Richard F. Heck and Ei-ichi Negishi for their effort for discovery and development of palladium-catalyzed cross couplings in organic synthesis.

3Richard F. Heck Akira SuzukiEi-ichi Negishi

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Suzuki Reaction and Stille Reaction

Ar: the relative reactivity appears to be PhI >p-ClC,H,Br > PhBr > o-MeC,H,Br > o-MeOC,H,Br.

 A. Suzuki,  Chem. Commun. 1979, 866.

Stille Reaction

  J. K. Stille,  Angew. Chem. Int. Ed. Engl. 1986, 25, 508

R1 Sn(Alkyl)3 + R2 XPd0(catalytic)Lidand Set

R1 R2 X Sn(Alkyl)

R1, R2 =sp2 hybridized C(allyl, alkenyl, aryl); X=halides(Cl, Br, I), pseudohalides(OTf, OSO2CF3, OPO(OR)2)

+

OutlineIntroductionChemistry of Suzuki ReactionReaction mechanismBoron reagents

Recent development of Suzuki ReactionConjugated microporous polymersLight-emitting diodesOrganic Solar cell

Polymer-bound palladium catalyst in Suzuki Reaction

Conclusions5

Reaction mechanism

6Guy C. Lloyd-Jones., et al, Chem. Soc. Rev., 2014, 43, 412

Boron reagents

7Guy C. Lloyd-Jones., et al, Chem. Soc. Rev., 2014, 43, 412

8Guy C. Lloyd-Jones., et al, Chem. Soc. Rev., 2014, 43, 412

OutlineIntroductionChemistry of Suzuki ReactionReaction mechanismBoron reagents

Recent development of Suzuki ReactionConjugated microporous polymers Organic light-emitting diodesOrganic Solar cell

Polymer-bound palladium catalyst in Suzuki Reaction

Conclusions9

Conjugated microporous polymers

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A. I. Cooper, et al, Angew. Chem., Int. Ed., 2012, 51, 12727–12731.

Subi J. George, et al, J. Mater. Chem., 2011, 21, 12958

Han, B.-H., et al, Macromolecules, 2011, 44, 5573.

Organic light-emitting diodes

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T. Yokozawa, et al, J. AM. CHEM. SOC. 2007, 129, 7236

Polyfluorene

Polyfluorenes are an important class of polymers which have the potential to act as both electroactive and photoactive materials.

Hyperbranched polyfluorenes

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W. Huang, et al, Macromolecules, 2005, 38, 6755

Organic Solar cell

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Z. K. Chen, et al, J. Polym. Sci., Part A: Polym. Chem. 2007, 45, 5266.

OutlineIntroductionChemistry of Suzuki ReactionReaction mechanismBoron reagents

Recent development of Suzuki ReactionConjugated microporous polymersLight-emitting diodesOrganic Solar cell

Polymer-bound palladium catalyst in Suzuki Reaction

Conclusions14

Polymer-bound palladium catalyst

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C. Le Drian, et al, Tetrahedron Lett. 1998, 39, 4287

W.-C. Shieh, et al, Synth. Commun. 2002, 32, 1059.

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S. Ikegami, et al, Org. Lett. 2002, 4, 3371.

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SCHEME 1. Schematic Representation of Magnetic Nanoparticle Facilitated Solid-Phase Suzuki Cross Coupling Reactions

SCHEME 2. Immobilization of Pd-NHC Complexes ontothe Surface of Iron Oxide Nanoparticles

Gao, Y. J. Org. Chem.2006, 71, 537.

OutlineIntroductionChemistry of Suzuki ReactionReaction mechanismBoron reagents

Recent development of Suzuki ReactionConjugated microporous polymersLight-emitting diodesOrganic Solar cell

Polymer-bound palladium catalyst in Suzuki Reaction

Conclusions18

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ConclusionsWe can use different boron reagent for different kinds of

suzuki reaction.Suzuki reaction is a good way to prepare conjugated

polymer. In green chemistry, the catalyst can be recycled is a better

choice.