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New recyclable catalysts for the formations of

carbon-carbon and carbon-nitrogen bonds

Dong Wang

To cite this version:

Dong Wang. New recyclable catalysts for the formations of carbon-carbon and carbon-nitrogen bonds. Organic chemistry. Université de Bordeaux, 2014. English. �NNT : 2014BORD0128�. �tel-01159007�

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THÈSE EN COTUTELLE PRÉSENTÉE

POUR OBTENIR LE GRADE DE

DOCTEUR DE

L’UNIVERSITÉ DE BORDEAUX

ÉCOLE DOCTORALE

SPÉCIALITÉ : Chimie Organique

Par

M. Dong WANG

NOUVEAUX CATALYSEURS RECYCLABLES POUR LES

REACTIONS DE FORMATION DE LIAISONS

CARBONE-CARBONE ET CARBONE-AZOTE

Sous la direction de M. Didier ASTRUC

Soutenue le: 26 Septembre 2014

Membres du jury:

Mme Angela MARINETTI Directeur de recherche au CNRS Rapporteur

M. Noël LUGAN Directeur de recherche au CNRS Rapporteur

M. Jean-François LETARD Directeur de recherche au CNRS Examinateur

M. Lionel SALMON, Chargé de Recherche au CNRS Examinateur

M. Jaime RUIZ Ingénieur contractuel à Université de Bordeaux Membre invité

M. Didier ASTRUC Professeur à l’Université de Bordeaux Directeur de thèse

Logo

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Acknowledgement

This thesis was completed in the Institut des Sciences Moléculaires (ISM), UMR

CNRS N° 5255, Bordeaux University.

I would like to express my gratitude to all those who have helped me during the

writing of this thesis. First of all, I would like to express my sincerest gratitude to my

supervisor Prof. Didier Astruc, for his inspiring, patient instruction, insightful

criticism and expert guidance on my thesis. Without his consistent and illuminating

instruction, this thesis could not have reached its present form. His profound

knowledge of chemistry triggers my lover for this area, his earnest attitude tells me

how to be an eligible chemist. I am also deeply grateful for his kind help in daily life.

All help from him will be always engraved on my mind.

I am also greatly indebted to the two reporters for the thesis, Angela Marinetti, and

Mr. Noël Lugan, and the other external jury members Jean-François Létard, and

Lionel Salmon CNRS Director of Research for their time and energy in serving as

referees and examinators of the PhD.

I am also deeply grateful to the engineer of our research group, Dr. Jaime Ruiz, for

his patient guidance on experiment operation and excellent work on cyclic

voltammetry. High tribute shall be paid to Lionel Salmon, Sergio Moya, Dominique

Denux, Mrs. Christine Labrugère, and Laetitia Etienne for their excellent analyses

on several samples.

My sincere gratitude also go to my former and current colleagues, including

Amalia Rapakousiou, Yanlan Wang, Liyuan Liang, Christophe Deraedt,

Pengxiang Zhao, Haibin Gu, Changlong Wang, Sylvain Gatard, Roberto

Ciganda and

Martin d’Hallui

n, who kindly gave me invaluable advises and help to

solve various problems in both study and life.

Last but not the least, my gratitude also extends to my family who have been

assisting, supporting and caring for me all of my life. Special thanks should go to my

wife Na Li who give me continuous support and encouragement during my thesis.

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Table of Content

General Introduction

………...

1

Chapter 1

Overview on Dendritic and Magnetic Catalysts

………

5

1.1 Introduction

………

6

1.2 Dendritic Catalysis – Basic Concepts and Recent Trends

...

7

1.3 Fast-Growing Field of Magnetically Recyclable Nanocatalysts

...

26

Chapter 2

Iron Oxide Magnetic Nanoparticle-Immobilized Ru Catalyst

...

62

2.1 Introduction

...

63

2.2 Magnetically Recoverable Ruthenium Catalysts in Organic Synthesis

...

64

2.3 A recyclable Ruthenium(II) Complex Supported on Magnetic Nanoparticles:

A Regioselective Catalyst for Alkyne–Azide Cycloaddition

...

83

Chapter3

Magnetic Nanoparticle-Immobilized Tris(triazolyl) Cu(I) Catalyst for the

Copper-catalyzed Alkyne Azide (CuAAC) "Click" Reaction

………...

86

3.1 Introduction

………...

87

3.2 A Highly Active and Magnetically Recoverable Tris(triazolyl) Cu(I) Catalyst

for “Click” Alkyne-Azide Cycloaddition Reaction

………..………

88

Chapter 4

Magnetically Recyclable Palladium Nanoparticles in C-C Coupling Reactions

..

96

4.1 Introduction

……….……...

97

4.2 Highly Efficient and Magnetically Recoverable “Click” PEGylated γ-Fe

2

O

3

-Pd

Nanoparticle Catalysts for Suzuki-Miyaura, Sonogashira, and Heck Reactions

…..

99

4.3 Impregnation of Dendritically Preformed Pd Nanoparticles on Magnetic

Nanoparticles for Improved Catalyst Robustness, Efficiency and Recyclability.

.

131

Chapter 5

Mono-

and

Polymetallic

Palladium

Complexes

Containing

2-Pyridyl-1,2,3-triazole Ligand or Nonabranch-derived Ligand

……….…

143

5.1 Introduction

……….….

144

5.2 The Clicked Pyridyl-Triazole Ligand: From Homogeneous to Robust,

Reclyclable Heterogeneous Mono- and Polymetallic Palladium Catalysts for

Efficient Suzuki-Miyaura, Sonogashira, and Heck Reactions

………..………..

146

Conclusion and Perspective

………...

160

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General Introduction

Increasing environmental concerns have pushed chemists to turn their attention from

traditional concepts of process efficiency to “green” and sustainable chemistry that

assign minimization of waste generation and avoid the use of toxic and/or hazardous

substances.

1,2,3

Specifically, the guiding principle of green chemistry can be

paraphrased as: waste prevention instead of remediation, atom efficiency, less

hazardous/toxic chemicals, safer products by design, innocuous solvents and

auxiliaries, energy efficient by design, preferably renewable raw materials, shorter

syntheses (avoid derivatization), catalytic rather than stoichiometric reagents, design

products for degradation, analytical methodologies for pollution prevention and

inherently safer processes.

4

Green catalysis, a key component of these principles, is extremely important in the

modern development of green chemistry.

5,6,7

A green catalyst must possess specific

features including low preparation cost, high activity, great selectivity, high stability,

efficient recovery, and good recyclability.

8

To date, several effective strategies

resulting in green catalysis have been discovered such as the recovery of catalyst,

cascade reaction protocol, the use of “green” solvents (neat condition, water, ethanol,

ionic liquids, supercritical liquids), flow conditions, photocatalysis and so on. Design

and use of recoverable catalysts are the most promising and straight way to green

catalysis, because the recovery of catalyst is not only a task of great economic and

environmental importance in catalysis science, but also overcome the problem of

metal contamination in products.

Catalyst recovery can be done by the experimental manipulations of precipitation,

traditional filtration, nanofiltration with membranes, centrifugation, extraction and

magnetic separation.

5

In general, to achieve these processes, organic and inorganic

supports (including polymers, dendrimers, metal oxides, alumina, fluorous tag,

zeolites, carbon nanotube, graphene, active carbon, silica, metal nanoparticles, ionic

liquids, and so on) are needed for immobilizing free catalytic species forming

heterogeneous or homogeneous catalysts.

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We have long been interested in catalyst recovery, especially for dendrimer

catalysts and magnetic nanoparticles-immobilized catalysts. Dendrimers are a family

of nanosized, branched three-dimensional supramolecular, and possess monodisperse

nature which retains the advantage of homogeneous catalysts in terms of showing fast

kinetic behavior, easy tenability and rationalization.

9-13

Moreover, dendrimer catalysts

can easily be removed from the reaction mixture by precipitation, traditional filtration,

or nanofiltration techniques because of their large size compared with the products.

11

Magnetic nanoparticles (MNPs) have attracted considerable interest as ideal

supports, and the study in this field has been undergoing an explosive development.

14

Indeed, magnetic nanoparticles (MNPs) perfectly bridge the gap between catalytic

activity and catalyst separation. Magnetically recyclable catalysts have the potential to

approach catalysts benefiting from high activity, high selectivity, high stability, and

easy separation, because MNPs-immobilized catalysts combine the advantages of

nanocatalysts

15,16

with

their

inherent

properties

including

non-toxicity,

biocompatibility, facile assembling, and high accessibility of reusability through

magnetic attraction.

As mentioned above, dendrimer catalytic and magnetic catalysts are two important

modes of catalyst recovery. Their comparison should be deeply significant and useful

in catalyst recovery science. Therefore, we reviewed both subjects and present these

overviews in the first chapter.

The second chapter concerns magnetically recyclable Ru catalysts. First of all, the

history, trends and prospects of MNPs-immobilized Ru catalysts involving the related

design, synthesis and catalytic application are briefly described. This overview was

published in the journal “Molecules”. The second subsection is an experimental study

that

mainly

focuses

on

the

immobilization

of

pre-synthesized

pentamethylcyclopentadienyl ruthenium complexes on iron oxide nanoparticles and

its catalytic test in alkyne-azide cycloaddition regioselectively producing

1,5-disubstituted 1,2,3-triazoles.

The third chapter demonstrates that the versatile tris(triazolyl) ligand is readily

deposited on MNPs, and subsequent complexation with CuBr salt generates a novel

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MNPs-supported tris(triazolyl)–CuBr catalyst. This catalyst shows a high activity for

Cu(I)-catalyzed alkyne-azide cycloaddition (CuAAC “click” reaction) in aqueous

solution at room temperature, and more importantly copper recovery is achieved.

The fourth chapter provides a description of MNPs-anchored Pd nanoparticles

(PdNPs). The

efficiency

of triethylene

glycol (TEG)-terminated “click”

dendrimers-stabilized metal NPs has been testified by our previous research.

17,18

Based on this, we turn our attention to the synthesis of MNP-immobilized PdNPs

decorated with dendritic TEG-terminated “click” ligands. The syntheses were carried

out through two strategies: reduction of pre-coordinated Pd salts immobilized on the

MNP support, impregnation of pre-synthesized PdNPs into MNPs. Both kinds of

MNPs-PdNPs

performed

well in

carbon-carbon

coupling reactions, and

unprecedented dendritic effects were observed in various aspects.

The fifth chapter introduces the syntheses of palladium complexes containing

single or nonabranched 2-pyriyl-1,2,3-triazole ligands. When a nonabranched ligand

was used, partly- and fully- metalized Pd complexes showed various state in the given

media. Their catalytic properties were also tested in classic coupling reactions.

At the end of the thesis, the “Conclusion and Perspectives” section summarizes the

progress resulting from the research conducted during this thesis concerning

heterogeneous and abundant catalysts for various classic reactions. In addition,

perspectives are provided, indicating that development of new magnetic plasmonic

photocatalysts based on AuNPs, AgNPs and CuNPs, exploration of magnetic

bimetallic catalysts, and replacement of “noble” metal catalysts by abundant metal

(so-called “biometals”) catalysts should be valuable goals of further work along this

line.

References

1. P. T. Anastas, J. C. Warner, Green Chemistry: Theory and Practice, Oxford

University Press, New York, 1998.

2. M. Doble, A. K. Kruthiventi, Green Chemistry and Engineering, Academic Press,

London, 2007.

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3. S. K. Sharma, A. Mudhoo, Green Chemistry for Environmental Sustainability.

CRC Press, Boca Raton, FL, USA, 2010.

4. R. A. Sheldon, I. Arends, U. Hanefeld, Green Chemistry and Catalysis.

Wiley-VCH, Weinheim, Germany, 2007.

5. G. Ertl, H. Knozinger, J. Weitkamp, Eds. Handbook of Heterogeneous Catalysis.

Wiley-VCH, Weinheim, Germany, 1997.

6. A. Suzuki In. Modern Arene Chemistry. D. Astruc, Ed. Wiley-VCH, Weinheim,

2002.

7. G. A. Somorjai, Introduction to Surface Chemistry and Catalysis. Wiley, New

York, 1994.

8. S. B. Kalidindi, B. R. Jagirdar, ChemSusChem 2012, 5, 65.

9. G. R. Newkome, E. He, C. N. Moorefield, Chem. Rev. 1999, 99, 1689.

10. G. R. Newkome, C. N. Moorefield, F. Vögtle, Dendrimers and Dendrons:

Con-cepts, Synthesis Applications. Wiley-VCH, Weinheim, 2001

11. D. Astruc, F. Chardac, Chem. Rev. 2001, 101, 2991.

12. L. Gade (Ed.), Dendrimer Catalysis. Springer, Heidelberg, 2006.

13. J. M. J. Fréchet, D. A. Tomalia, Dendrimers and Other Dendritic Polymers.

JohnWiley & Sons, Ltd, 2001.

14. V. Polshettiwar, R. Luque, A. Fihri, H. Zhu, M. Bouhrara, J.-M. Basset,

Magnetically Recoverable Nanocatalysts, Chem. Rev. 2011, 111, 3036–3075.

15. Astruc, D. Ed. Transition-metal Nanoparticles in Catalysis. Wiley-VCH:

Weinheim, 2008.

16. B. D. Chandler, J. D. Gilbertson, In D. Astruc, (ed) Nanoparticles and Catalysis,

Wiley-VCH, Weinheim, 2007.

17. E. Boisselier, A. K. Diallo, L. Salmon, C. Ornelas, J. Ruiz, D. Astruc, J. Am.

Chem. Soc. 2010, 132, 2729.

18. C. Deraedt, L. Salmon, L. Etienne, J. Ruiz, D. Astruc, Chem. Commun. 2013, 49,

8169.

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Chapter 1

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1.1 Introduction

Dendrimer chemistry has attracted considerable interest and driven various promising

applications in drug delivery, materials science and catalysis. This field is also an

important part of the research of our group, and a variety of dendrimers were

specifically prepared and applied therein in biology, catalysis, sensing and

nanotechnology.

Since 2001, our group has published several review articles or overviews on the

development of dendrimer chemistry. For example, in 2010, our group published a

comprehensive review entitled “Dendrimers Designed for Functions: From Physical,

Photophysical, and Supramolecular Properties to Applications in Sensing, Catalysis,

Molecular Electronics, Photonics, and Nanomedicine”.

1

In 2012, a review on

electron-transfer processes in dendrimers and applications was published.

2

Here, our

attention is mainly focused on the developments and trend of dendrimers in

catalysis.

3-5

Dendrimer chemistry is still promising in catalysis, and many publications on

dendritic catalysis

emerged in the last few years. Thus it appeared necessary to write a

new updated review on the recent breakthroughs and trends in this area.

In recent years, the development of magnetic catalysts is enormously accelerating.

7

A large number of new reactions, nanocatalysts, systems, and trends are appearing at a

fast rate, and more than 400 publications have appeared in the last 2 years. Thus, in

this chapter, we also summarize the basic concepts, seminal studies, new

breakthroughs of magnetically recoverable catalysts.

References:

1. D. Astruc, E. Boisselier, C. Ornelas, Chem. Rev. 2010, 110, 1857.

2. D. Astruc, Nat. Chem. 2012, 4, 255.

3. D. Astruc, F. Chardac, Chem. Rev. 2001, 101, 2991.

4. D. Astyuc, Tetrahedron Asymm. 2010, 21, 1041 (Henri Kagan issue).

5. V. Polshettiwar, R. Luque, A. Fihri, H. Zhu, M. Bouhrara, J.-M. Basset,

Magnetically Recoverable Nanocatalysts, Chem. Rev. 2011, 111, 3036–3075.

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ContentslistsavailableatSciVerseScienceDirect

Coordination

Chemistry

Reviews

j ou rn a l h om ep a g e :w w w . e l s e v i e r . c o m / l o c a t e / c c r

Review

Dendritic

catalysis—Basic

concepts

and

recent

trends

DongWang,DidierAstruc∗

ISM,Univ.Bordeaux,351CoursdelaLibération,33405TalenceCedex,France

Contents

1. Introduction... 2317

2. Basicconceptsandseminalstudies ... 2319

3. Recentadvancesandtrends... 2321

3.1. Metallodendriticcatalysts... 2321

3.1.1. Suzuki–Miyaurareaction... 2321

3.1.2. Mizoroki–Heckreaction... 2322

3.1.3. Cu-catalyzedalkyne-azide(CuAAC)reaction... 2323

3.1.4. Hydrogenation... 2324

3.1.5. Carbonylationandhydroformylationreactions ... 2327

3.1.6. Oxidationreaction... 2327

3.1.7. Polymerizationandoligomerization... 2327

3.1.8. Arylationandalkylationreactions... 2327

3.1.9. Asymmetricsynthesis... 2328

3.1.10. Otherreactions... 2328

3.2. Dendriticorganocatalysts... 2330

4. Conclusionandoutlook... 2332

Acknowledgments... 2332 References... 2332 a r t i c l e i n f o Articlehistory: Received5March2013 Accepted28March2013 Available online xxx Keywords: Dendrimer Metallodendriticcatalysts Catalysis Organocatalysts Nanoparticlecatalysts a b s t r a c t

Inthisreview,attentionisfocusedonbrieflysummarizingthemainconceptsofdendrimersincatalysis andessentiallyreviewingnewbreakthroughsandtrendsinthisareathathaveappearedduringthelast fewyears.Dendrimershavebeenproposedtobridgethegapbetweenhomogeneousandheterogeneous catalysis,anddendriticcatalystshavethepotentialtoapproachcatalystsbenefitingfromhighactivity, highselectivity,highstability,andeasyseparation.

© 2013 Published by Elsevier B.V.

Abbreviations: ARO, asymmetric epoxide ring-opening; BINAP, 2,2-bis(diphenylphosphino)-1,1-binaphthyl; CM, cross metathesis; Cp,

cyclopentadiene; CuAAC, copper-catalyzed alkyne-azide cycloaddition; DENs, dendrimer-encapsulatednanoparticles;DPA,dendriticphenylazomethine;DSNs, dendrimer-stabilizednanoparticles;EYM,enynemetathesis;FTsDPEN,fluorinated dendriticchiralmono-N-tosylated1,2-diphenylethylenediamine;Gn,numberof

dendriticgeneration;HKR,hydrolytickineticresolution;MNP,metalnanoparticle; NBD,norbornadiene;NP,nanoparticle;PAMAM,polyamidoamine;PAMDMAM, polyamidodimethylamine;PdNP,palladiumnanoparticle;POM,polyoxometalate; PPI,polypropyleneimines;PTA,(1,3,5-triaza-7-phosphaadamantane);PPX, poly(p-xylylene);pyta,pyridyltriazole;RCM,ring-closingmetathesis;SILC,supported ionicliquidcatalyst;TEMPO,2,2,6,6-tetramethylpiperidine-N-oxyl.

∗ Correspondingauthor.

E-mailaddress:d.astruc@ism.u-bordeaux1.fr(D.Astruc).

1. Introduction

Dendrimers,dendrons,dendronizedanddendriticand hyper-branched polymersare a family of nanosized, branched three-dimensional molecular frameworks that have attracted the scientificcommunitysincethe1980s[1–7].Essentialand promis-ing applications are in nanomedicine including targeted drug deliveryandimaging, materialssciencewithsensors,light har-vesting devicesand surfaceengineeringandcatalysis[8–23].In thelatterfield,advancestowardsgreenandsustainablechemistry havebeenadrivingforcetooptimizetheuseofmetalcatalystsin termsofefficiency,catalystrecoveryandminimizationof contam-inationbymetalionsandparticles[24–40].Sincethepioneering

0010-8545/$–seefrontmatter © 2013 Published by Elsevier B.V.

http://dx.doi.org/10.1016/j.ccr.2013.03.032

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workoncatalysisof CO/alkenepolymerizationuponcomparing mononuclearandstar-shapedhexaphosphine-palladiumcatalysts wasreportedin1992[41],agreatvarietyofdendriticcatalystshave been developed, and corresponding theoretical knowledge and derivedtechnologiesindendriticcatalysishavebecomemature

[24–40].

Whyisdendriticcatalysissopopular?Whatcandendrimers add to the field of catalysis? Dendritic catalysts exhibit well-defined structures and possess a monodisperse nature which retains the advantage of homogeneous catalysts in terms of showing fast kinetic behavior, easy tenability and rationaliza-tion.Dendriticcatalystscaneasilyberemovedfromthereaction mixturebyprecipitation,membraneornanofiltrationtechniques becauseof theirlargesize compared withtheproducts, which

instills theadvantages of heterogeneous catalysts.Moreover, it is possible to finely tune the catalytic properties of the den-driticcatalysts through the adjustmentof their structure, size, shape, chemical functionality, and solubility. In a few words, dendrimers have been proposed to bridge the gap between homogeneous and heterogeneous catalysis, and dendritic cata-lysts have the potential to approach catalysts benefiting from high activity, high selectively, high stability, and easy separa-tion.

Manyreviewshaveappearedondendrimercatalysissincethe beginningofthe2000s[24–40].Herewewishtobrieflysummarize themainconceptsofdendrimersincatalysisandessentiallyreview newbreakthroughsandtrendsintheareathathaveappeared dur-ingthelast5years.

(a) (b) (c)

(d) (e)

(f) (g)

Fig.1.Structuresofdendrimerscommonlyusedincatalysis:(a)PAMAM;(b)PPI;(c)polybenzylether;(d)polyaliphaticester;(e)polycarbosilane;(f)polyesteramide;and (g)allyl-endedarene-coreddendrimer.

Reprintedwithpermissionfrom[48](Fréchet’sgroup). ©2006Wiley-VCH.

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Fig.2.Mostfrequentlyencounteredlocationsofcatalyticentitiesindendriticmolecules:(a)core;(b)peripherally;and(c)buildingblock. Reprintedwithpermissionfrom[50](Yamamoto’sgroup).

©2006TheChemicalSocietyofJapan.

2. Basicconceptsandseminalstudies

During the past two decades, various dendrimer families have found widespread use as platformsin dendritic catalysis (Fig. 1).Commonly used dendrimers include polyamidoamines (PAMAM)[42],polypropyleneimines(PPI)[43],polybenzylethers (Fréchet-type)[44],polyaliphaticesters[45],polycarbosilanes[46], polyester amides (Newkome-type) [47], and allyl-ended arene-coreddendrimer[48].Theiterativesynthesisofdendrimersallows fortheplacementofcatalyticentitiesatanypointresultingina functionalmacromoleculewithratherwellcharacterizedstructure

[26,49].Mostfrequentlyencounteredlocationsofcatalyticentities inthedendrimermoleculearegiveninFig.2.Asindicatedinthe figure,locationsofcatalyticentitiesincludecore,periphery,and buildingblock(Fig.2).

Thesynthesisofcore-functionalizeddendriticcatalystsisthe sameas for classicaldendrimers but appliedtoa suitably core (Fig.2a).Thestericcrowdingofreactivecoreupondendritic encap-sulationremainsoneofthemorechallengingobstaclestoovercome in catalysis. In general, slower rates of reaction are observed, becausecore-confinedcatalystsaresoisolatedfromthereaction medium,andthecatalystloadingislow(asinglecatalyticsiteper

dendrimer).Ontheotherhand,core-functionalizeddendritic cata-lystscouldbenefitfrommodifiablesurfacegroupsandlocalcatalyst environment. For example, connecting water-solublegroups to peripheryof dendrimerscouldmakedendriticcatalysts“green” andwater-soluble,andthespecificmicro-environmentcreatedby dendriticstructuresshowsgreatsimilaritytobiologicalsystems suchasenzymes[50].Core-functionalizeddendriticcatalystswere firstestablishedin1994(“dendrizymes”)[51],andtheinfluence ofachiraldendriticperipheryontheperformanceofasymmetric cyclopropanationcatalystswasinvestigated.

Graftingcatalyticsitesontheperipheryofdendrimers isthe moststraightforwardandpioneeringapproachtoconstruct den-dritic catalysts, which offers unprecedented opportunities for establishingactivesitemultivalencyandthushighloading capac-ityandligandconcentrations.Theproximalinteractionsbetween catalyticgroupsandstericcrowdingattheperipheryofdendritic catalystsmayleadtocooperativeeffects anda certain selectiv-ityprofilerespectively,whichcouldfurtherincreasethecatalytic effect.Thefirstexampleofsuchacatalyst(Fig.2b)wasreported withseminalworkontheKaraschreaction[52].Manycatalytic examples with positive “dendritic effect” based on periphery-functionalized dendritic catalysts were disclosed. For example,

Fig.3.Jacobsen’sdendritic[Co(salen)]complexforhydrolytickineticresolution(HKR)ofterminalepoxides. Reprintedwithpermissionfrom[53](Jacobsen’sgroup).

©2000Wiley-VCH.

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Fig.4. Astruc’swater-solublestar-shapedcatalystforcathodicreductionofnitrates andnitritestoammoniashowingnokineticdropfromthemonometallictothe star-shapedcatalyst[55].

hydrolytickinetic resolution (HKR) of terminal epoxides seem-inglyproceedsusingcobalt(salen)complexesascatalysts(Fig.3)

[53].ThecatalyticactivitiesofG1toG3PAMAMdendrimerswith respectively4,8and16catalyticresiduesattheperipherywere superiortothose ofthemonomericand dimericcatalysts, indi-catingapositivedendrimereffect.Thiseffectwasassignedtothe dendriticconfinementoftheCo-salencomplexesatthesurfaceof themacromoleculethatwasclaimedtoreinforcecooperative cat-alyticactivity.Arathergeneraltrendinperiphery-functionalized dendriticcatalystswhicharethemajorityofmetallodendritic cata-lystsreported,isthebulkprovidedattheperipheryuponincreasing thedendrimergeneration,restricting accessof thesubstrateto thecatalytic metalcenter.Therefore,a betterspatialseparation ofcatalyticsitesinthedendrimershouldbearranged.This prob-lemhasbeenrecognized,anditwassuggestedthatstar-shaped structurescontainingcatalystsatthebranchterminishouldnot sufferfromsuchstericconstraints[54].Star-shapedhexanuclear catalystscontainingsixCpFeI(arene) complexes(Fig.4)are

effi-cientredoxcatalystsfornitrateandnitritereductiontoammonia inwaterwithoutkineticlosscomparedwithmonometallic cata-lysts[55].Thisshowsherethelackofstericinhibitionthatisoften encounteredindendriticframeworksloadedwithcatalystsatthe branchtermini(negativedendriticeffect).

Thebuildingblock(backbone) regionsof a dendrimercould providealocalizedenvironmentsuitableforbindingandcatalysis (Fig.2c).Thecatalyticsiteconcentrationofthisattachmentstyle isveryhigh,whichmightresultinhighreactionrates.Aneffective approachforthesynthesisofthisshapeofdendriticcatalystsisthat usingionicbondsinconnectionwithhydrogenbondstoattach thecatalysttothebuildingblockofdendrimers[56,57].Another approachinattachingcatalyticsitesatdendriticbuildingblocks wasprovided [58].Thus phosphineligandsofthecatalystwere locatedatthebranchingpointsallalongthedendriticconstruction. Metalnanoparticles(MNPs)areamongthemostefficientand selectivecatalysts[59–67].Theyareusuallysynthesizedby reduc-tionofatransition-metalsalt,andthegeneratedmetal(0)atoms agglomerate;thisagglomerationisstoppedatacertainpointinthe presenceofvariousstabilizerssuchasligands,polymers, surfac-tants,ionicliquidsorsolidsupportssuchasoxides,etc.Aproblem residesinthestabilizationofthenanoparticle(NP)surfacewithout blockingaccessofsubstratestothissurface,however,thusafine balancebetweenstabilizationandsurfaceaccessmustbetargeted. LocalizationofaNPinside adendrimerbringsaboutanelegant solutiontothisproblem.Anotherimportantaspectisthecontrolof thesizeandshapeoftheNPsthatisbestaccessibleupon encapsula-tioninsidedendrimers.Dendrimer-stabilizednanoparticles(DSNs)

[68,69]anddendrimer-encapsulatednanoparticles(DENs)[70]can

beusedfor varioustypesofcatalysisaswellasmolecular den-driticcatalysts.CatalysiswithDENswaspioneeredin1999with Gn-OHPAMAMPdandPtDENs(n=4–8)forthehydrogenationof allylicalcoholandN-isopropylacrylamideinwater[71,72].Another promising areawas that of dendrimer-encapsulated nanoparti-clesinheterogeneouscatalysis[73,74].ThepowerfulCuI-catalyzed

“click” reaction betweenazido and terminal alkyne derivatives (CuAAC)selectivelyformingdisubstituted1,2,3-triazoleshasbeen usedtostabilizetransition-metalionsincludingPdIIbythe

1,2,3-triazoleligand[75–78]and toform“click”-dendrimer-protected PdnanoparticlesbyreductionofthePdIIspeciestoPdNPeitheras

DENsordendrimer-stabilizedPdNPs(DSNs).SuchPdNPsshowed excellentcatalyticactivitiesinhydrogenation[79,80]andC–Ccross coupling[37,81].

Dendriticcatalysts areseparated from thereaction medium throughprecipitation,membranenanofiltrationbytaking advan-tageof themacromolecularand tunablenatures ofdendrimers. Thetechnologicalimprovements forseparation werepioneered byKraglandReetzintheirseminalstudy[82–84].Subsequently, cationicdendrimerordendron-protectedpolyoxometallate cata-lystswererecycledbyprecipitationuponadditionofetherfrom biphasicCDCl3/aqueousmixturesafterolefinepoxidationorsulfide

oxidationtosulfonesandsecondaryalcoholstoketones.Both fam-iliesofmetallodendrimersanddendron-protectedcatalystscould beusedmanytimeswithoutlossofactivity,althoughtheactivity ofthedendron-protectedcatalystsdecreaseduponincreasingthe dendrongenerationandbulk[85–87].Recently,dendriticcopper(I) (hexabenzyl)trencomplexthatwereactivefor“click”reactions betweenazidesandalkynesintolueneorwaterwererechargedat least10timesthroughcompleteprecipitationoftheproductfrom thereactionmediumat−18◦C[88].Silicagel-supported

metallo-dendroniccatalysisofolefinhydroformylationwithRhIprovided

anotherapproachforrecyclingdendriticcatalystsupon engineer-ingheterogeneous solidsupport-bound dendritic catalysts[89]. Subsequenttothisseminalwork,manystudieshave been con-ductedbydifferentgroupsinwhichtheinfluenceofthegeneration oncatalyticeffects, solidsupport,and backbonestructurewere investigated.

Asymmetriccatalysisisanessentialbranchofcatalysisresearch. In 1990s, the first example of dendritic asymmetric catalysis wasreported [51,90], in which a chiral dendron bearing phos-phinesatitscorewassynthesized,therebyestablishingthecrucial “dendrizyme”concept.Anumberofreportsthenfollowedon asym-metric catalysis by dendritic chiral metal complexes. The first asymmetricrhodium-catalyzedhydrogenationofprochiralolefins indendrimercatalysisandshoweda slightlynegativedendritic effectonselectivityupon increasinggenerationwasreportedin 1998[91,92]. Astronglypositive dendriticeffectinasymmetric catalysis was demonstrated [93] whereby the ee for pyrphos-Pd-functionalizedPPI and PAMAMdendrimers-catalyzed allylic aminationof 1,3-diphenyl-1-acetoxypropene increasedfrom9% forthemononuclearreference[(Boc-Pyrphos)PdCl2] to69%for

thePd64-PAMAM-dendrimer[94].Dendriticasymmetriccatalysts

have been appliedto several important organicreactions such asMannich-type,Diels–Alder,Wittigreaction,Michaeladdition, asymmetricepoxidering-opening,asymmetrichydrogenationand asymmetric epoxidation. Recent reviews have emphasized the importanceofdendriticasymmetriccatalysts[95,96].

Organocatalysis dates back more than 150 years. Since the beginning of the 21st century, dendritic organocatalysis has attracted considerable attention. Until now, most dendrimers (especially for PAMAM and PPI dendrimers) have been modi-fiedwithorganocatalytic moietiesforuseassupportinvarious organocatalyzedreactionsincludingformationofC–Cbonds, cleav-ageof estersbonds,oxidationandreduction reactions[37].The hydrolysisofestersusingpeptidicdendrimershasbeenexamined

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Fig.5.Exampleofapeptidedendrimerusedforcatalyzingthehydrolysisofesters. Reprintedwithpermissionfrom[97](Reymond’sgroup).

©2004AmericanChemicalSociety.

withtheviewtomimictheefficiencyofenzymes.Aseriesof pep-tidedendrimershavingdiaminoacidor3,5-diaminobenzoicacid asbranchingunits,bearinghistidine,aspartate andserinewere usedtocatalyzethehydrolysisof7-hydroxy-N-methylquinolinium estersand8-hydroxypyrene-1,3,6-trisulfonateesters.1-G2(Fig.5)

isoneofthesepeptidedendrimersthatwasusedforthe hydrol-ysisofquinoliniumesters[97].Thenumberofhistidineresidues per dendrimers was thecrucial factor influencing the catalytic rateconstants.Indeed,theG4dendrimerwas140000-foldmore efficientthan 4-methylimidazoleas a referencecatalyst forthe hydrolysisofthenonanoylesterofpyrene[98].

3. Recentadvancesandtrends

3.1. Metallodendriticcatalysts 3.1.1. Suzuki–Miyaurareaction

The first three generations of dendritic bis(dicyclohexyl-phosphanylmethyl)amine-functionalized palladium catalysts (Fig.6)havebeenusedintheSuzukicouplingreaction[99,100]of halogenoarenes,includingchloroareneswithphenylboronicacid

[101].TheG1dendrimergaveyieldscomparabletothoseobtained withthemononuclearcomplex,but aclearnegativeeffectwas observedwithanincreaseofthegeneration.Thedendritic com-poundswererecoveredbyprecipitationwithpentaneandreused forthreecycles.

Recently,theactivityofPdcomplexesofthecore-functionalized dendriphos ligands has been examined in the Suzuki–Miyaura cross-couplingreaction[102,103]. Aseries oftriarylphosphanes containing dendritically-arranged tetraethylene glycol moieties at the periphery were synthesized (Fig. 7), and the combina-tionof[PdCl2(PhCN)2]andsecondgenerationdendriticderivative

2a2 with the TEG chains led to a highly active catalytic

sys-tem:downto0.1mol%catalyst loadingyielded93%conversion,

when nonactivatedaryl chloridewasemployed. Haagdesigned ahyperbranchedwater-solublepolyglycerolderivative function-alized with N-heterocyclic carbene palladium complexes, and applieditascatalystforSuzukicross-couplingreactionsinwater. Turnover frequencies ofupto2586h−1 at 80◦C wereobserved withthedendriticcatalystalongwithturnovernumbersofupto 59000,whichareamongthehighestturnovernumbersreported forpolymer-supportedcatalystsinneatwater.Thedendritic cat-alystcouldbereusedinfiveconsecutivereactionswithoutloss inactivity[104].Apseudo-homogeneousheterogenizedcatalyst was synthesizedthrough noncovalently immobilized palladium acetateasasupportedionicliquidcatalyst(SILC)inananosilica dendrimerPAMDMAM[105].Thesupporteddendriticcatalystwas effective for Suzuki–Miyaurareactionsof ortho-substitutedaryl bromidesoraryltriflateswithoutaligandin50%aqueousethanol inairatroomtemperature.Thecatalystcouldbereuseduptofive timesin93%averageyieldaftersimplecentrifugation,andtheTON reached176000.Theefficientuseofa“click”dendritic monoden-tatephosphineligandinthePd-catalyzedSuzuki–Miyauracoupling wasreported. The dendriticcomplex waseasily removed from thereactionmixturebynanofiltrationusingceramicnanofiltration membranes[106].

Mono- and polymetallic palladium complexes containing a 2-pyridyl-1,2,3-triazole (pyta) ligand or a nonabranch-derived (nonapyta) ligand have been synthesized by reaction of pal-ladium acetate with these ligands and used as catalysts for Suzuki–Miyaura,SonogashiraandHeckreactions(Fig.8)[107].The unsubstituted monopalladium 1 and nonapalladium complexes

29 wereinsoluble in all the reaction media; whereas, tri- and

tetranuclarpalladiumcomplexes(23and24)weresoluble,which

allowedconductingcatalysisundereitherhomogeneousor het-erogeneousconditions.Bothtypesofcatalystsshowedexcellent activityforSuzuki–Miyaura,Sonogashiraand Heckreactions. In addition,therecyclablefeatureofheterogeneouscatalystswas ver-ifiedintheexampleofHeckreaction.

In many cases,theproblemof metalleaching restricted the applicationofdendriticcatalysisinthepharmaceuticalindustry. Theuseofphosphorusdendrimerspartiallyaddressedtheproblem. Phosphorusdendrimers(G0andG3)functionalizedwiththiazolyl phosphinesshowedhighactivityinPd-catalyzedSuzukireactions even undermildconditions, andthecatalytic systemscouldbe successfully recovered and reusedat least five times [108]. In addition,palladiumleachingindendriticcatalysisdecreased com-pared with monomeric catalysis. Only trace amounts of metal (<0.55ppm) were found in the product before purification by colummchromatography,andtheproductmetthespecification limitsforresiduesofmetalcatalystsinthepharmaceutical indus-try[109].Pyrene-taggeddendriticPd-phosphinecatalystsgrafted withmagneticCo/Cnanoparticleswerepreparedandusedas cata-lystsintheSuzuki–Miyaurareactionswithhighefficiency[110]. Attaching a dendriticligandontothe NPsurface allowedup to fivetimeshigherloading(0.5mmolg−1activesites)thanthe pre-viouslyreporteddirectfunctionalizationofcatalystsontotheNP

[111].Moreover,theuseofamagneticsupportmadethecatalysts moreeasytoremovefromthereactionmixturebysimply apply-inganexternalmagneticfield.Itcouldbereusedatleast12times withoutlossinactivity.Remarkably,Felbinac,whichisa commer-ciallyavailabledrugofgreatindustrialinterest,canbeprepared in multiplerunsusing thiscatalyst withspecification limitsfor residuesofmetalcatalystsinpharmaceuticalindustry(<5ppmPd) andwithouttediouspurification.

A series of “click”-ferrocenyl dendrimer-encapsulated and stabilized Pd nanoparticle pre-catalysts were synthesized with various generations of 1,2,3-triazolyldendrimers (G1-27, G2-81

forDENs,G0-9forDSNs)(Fig.9).WiththesePdNPs,catalysisof

Suzuki–MiyauraC–C coupling[112]betweenPhIand PhB(OH)2

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Fig.6. DendriticdiphosphinoPd(II)complexes. Reprintedwithpermissionfrom[101](Astruc’sgroup).

©2005AmericanChemicalSociety.

was carried out at room temperature and did not depend on thePdNPsizeandwhetheritsstabilizationisintra-or interden-dritic.Thisindicatedthatthedendrimerwasnotinvolvedinthe rate-limitingstepofthereaction.Thedendrimer-stabilizedPdNPs workedidentically whatevertheirsize,and theTONsincreased upondecreasingtheamountofcatalystfrom1%downto1ppmor upondilutionofthereactionsolution.Thus,theefficiencyofthe cat-alystwasremarkableinhomeopathicamounts(54%yieldat25◦C with1ppmequivalentofPdatom,i.e.TON=540000).A quantita-tiveyieldwasnotevenreached(75%yield)with1%equivalentPd atom[81],which,however,confirmedthehypothesisofa “home-opathic”catalyticmechanism.The“homeopathic”mechanismwas alreadyobservedfortheHeckreactionat150◦Candwas rational-izedaccordingtoaleachingmechanisminvolvingdetachmentof PdatomsfromthePdNPsubsequenttooxidativeadditionofthe organichalidePhIonthePdNPsurface[113–117].Thismechanism wasestablishedforhigh-temperaturereactionsdueto decomposi-tionofthePdcatalysttonakedPdNPs,butitwaslessexpectedfor aroom-temperaturereaction.Theeaseoftheroom-temperature reactionmusthavebeendue,however,tothelackofligationonto thedendrimer-stabilizedPdNPsthatthereforecouldeasilyundergo

oxidativeadditionofPhIattheirsurface,whichprovokedleaching ofPdatoms.TheseisolatedPdatomsareapparentlyextraordinarily reactiveinsolution,becausetheydonotbearligandsotherthanthe veryweaklycoordinatingsolventmolecules.Thelimitintheir effi-ciencyisreachedwhentheseatomsorsmallclustersaretrapped bytheirmotherNP,ifthesolutionismoderatelyconcentrated.This trappingmechanismthatinhibitscatalysisisalwayslessefficient astheconcentrationofcatalystinthesolutionislowered. There-foreitisnotefficientunderextremelydilutedsolutions,whereas itstronglyinhibitscatalysisatrelativelyhighconcentrations.Itis likelythatthisconceptcanbeextendedtootherPdNP-catalyzed C–Cbondformationreactions(Fig.10).

3.1.2. Mizoroki–Heckreaction

Thefirstexampleofcatalystrecoveryandapositivedendritic effectincatalysiswithmetaldendrimerswasreportedin1997[82], in which poly(propylene imine)dendrimer modified palladium complexeswithdiphenylphosphanylmethylend-groupsshowed significantlyhigheractivitythanthemononuclearcomplexinHeck reaction[118],probablyduetoitsreducedtendencytodecompose

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Fig.7. Novelphosphaneligandsbearingtetraethyleneglycolorn-C12moieties. Reprintedwithpermissionfrom[103](Tsuji’sgroup).

©2008Wiley-VCH.

thermallytometallicPd.Thedendriticcatalystwasrecoveredby precipitationwithdiethylether.

Recently,studiesontheefficaciesofmultivalentvs. monova-lent dendriticcatalyststhroughcomparativeresearchwithinor acrossthedendrimergenerationsbasedonC–Cbond-forming reac-tions(especially ofHeck reaction)werepublished[119,120]. A seriesofpartiallyandfullyphosphine–Pdcomplexes functional-izedpoly(etherimine)dendrimerscatalystsweresynthesized,and thecomparativeanalysesshowedthatanindividualcatalyticsite wasfarmoreeffectiveinitscatalyticactivitywhenpresentedin multiplenumbers,i.e.,inamultivalentdendriticsystem,thanasa singleunitwithinthesamegeneration;andthathigherclustering ofcatalyticmoietiesismoreeffectivethanalessernumber.The studyverifiesthepositiveeffectsofthemultivalentpresentation ofthecatalyticmoieties.

Amidoamine-based dendrimers with end-grafted 1–5 Pd–Fe units were designed (Fig. 11), and these bimetal complexes exhibited catalytic activity for the Heck cross coupling of iodobenzene with tert-butyl acrylate [121]. The comparison of catalytic performance among these dendritic catalysts con-firmed a positive cooperative effect. In another example of positivecooperativeeffect[122],thesynthesesoffirstgeneration dendriticcompoundsbearing 1,1-alkane-1,1-diylbis(4-butyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene) palladium(II) dibromide on theperipheryweredescribed.Thedendriticcomplexwasmore activethanthecorrespondingnon-dendriticmononuclearspecies intheHeckreaction,whichwasindicativeofapositivecooperative effect.Howeveringeneralthecatalyticactivitiesofallthese com-plexesweremoderate.Incontrast,anegativedendriticeffectwas foundwhenPdcomplexesofbidentatephosphinesonapolyether dendronssupportwereused.Thisobservationwasexplainedby thefactthat,inthecaseofbidentatephosphineligands,thehigh localdensityofphosphinesdictatedbythedendriticarchitecture wasadisadvantagefortheHeckreaction[123].

Theuseofsolublepolysiloxaneswithlinear,star-shapedand hyperbranched architectures havingvinyl, 2-butylthioethyl and

Scheme1.Cu(I)loadedPAMAMdendrimerfor“click”reaction. Reprintedwithpermissionfrom[130](Voelcker’sgroup).©2011Elsevier.

2-diphenylphosphinoethyl side groups as supports for palla-dium(II) catalysts in Heck reactions has been reported [124]. Polysiloxane-supportedcatalystsdidnotprovideanegativeeffect on conversion compared with PdCl2(PhCN)2, but showed good

stability and could be reused several times. Linear polymers-supported catalystsexhibited both bettercatalytic activity and betterstabilitythanthatofdendriticcatalysts.

ThecatalysisbyPdDENsofHeckreactionswascarriedoutwith PAMAMandPPIdendrimersbyseveralgroups.PPIPdDENs con-tainingperfluoroethergroupscatalyzedtheHeckreactionbetween iodobenzeneandn-butylacrylatewith100%selectivityat90◦C, which was superior to yields and selectivities obtained with otherPdNPs.Thefluorinatedpony-tailfunctionalizedDENsalso allowedcarryingoutPdNP-catalyzedHeckcouplingbetweenaryl halidesandmethacrylateinsupercriticalCO2.Moreoverthehighly

unfavored methyl2-phenylacrylatewasexclusivelyobtainedat 5000psiand 75◦C, whereastrans-cinnimaldehydewasobtained with97%selectivityotherwise[125].AlthoughG4-OHDENswere morestablethanG2-OHandG3-OHDENs,thelower-generations DENswerealsomoreactivecatalysts[126].Thisobservation dis-closedacrucialproblemincatalysisbyDENs,i.e.thecorrectbalance betweencatalyticefficiencyandstabilityrequirescarefulsearch fora givendendrimerseries,andit istedious tomaintainboth advantagesofoptimizedefficiencyandstability.

3.1.3. Cu-catalyzedalkyne-azide(CuAAC)reaction

Thecopper-catalyzedalkyne-azideHuisgen-typecycloaddition (CuAAC“click”reaction)[127,128]hasappearedasoneofthemost currentlyusedmethodsfor connectingtwofragments together, andhasbeenwidelyappliedinvariousfieldsincludingconstruction ofdendrimers[75,129].Ontheotherhand,somegroupsrecently, alsotriedtodesignefficientdendriticcoppercomplexesfor“click” reaction.

The synthesis and catalytic properties of Cu-loaded poly(amidoamine) (PAMAM) dendrimers towards the Cu(I)-catalyzedazide–alkynecycloaddition(CuAAC)havebeendescribed (Scheme1)[130].Thereactivitywastestedonamodelreaction betweenazidopropanolandpropargylalcoholinaqueous solu-tion.A significantly faster conversionwasfoundusing PAMAM dendrimersasmacromolecularCu(I)ligandscomparedwith tra-ditionalsmallmolecularligandsystems,andthemacromolecular catalystcouldberemovedbyultrafiltration.

Copper(I)(hexabenzyl)trencomplex1anddendriticanalogues with 18 or 54 branch termini (Fig. 12) have been synthesized

[88,77].Bothparentanddendriticcomplexesshowed outstand-ingactivitiesfor“click”reactionswithvarioussubstratesinterms ofyieldsandTONs.Themetallodendrimersalsoprovideda posi-tivedendriticeffect,asshownbycomparingkineticsstudiesofthe “click”reactionbetweenphenylacetyleneandbenzylazideat22◦C intolueneusing0.1%catalysts,whichwasassignedtothedendritic frame bringing about stericprotection against the well-known inner-sphere aerobicoxidation of Cu(I)to bis(␮-oxo)-bis-Cu(II). Water-soluble PEG-modifieddendritic catalyst exhibited inspir-ingperformancefor“click”reactionsofwater-insolublesubstrates inwaterwithoutco-solventunderambientconditions.Moreover,

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Si Si Si Si Si Si Si Si Si N N N N N N N N N N N NN N N N N N N N N N N N N NN N N N N N N N N N Pd OAc OAc Pd Pd OAc OAc Pd OAc OAc AcO OAc Pd AcO OAc Pd AcO AcO Pd AcO AcO Pd OAc AcO Pd AcO OAc Si Si Si Si Si Si Si Si Si N N N N N N N N N N N NN N N N N N N N N N N N N NN N N N N N N N N N Pd OAc OAc Pd AcO OAc Pd AcO AcO Si Si Si Si Si Si Si Si Si N N N N N N N N N N N NN N N N N N N N N N N N N NN N N N N N N N N N Pd OAc OAc Pd AcO OAc Pd AcO OAc Pd AcO AcO 23 24 29 N N N NH Pd O O O O 1

Fig.8. Mono-andpolymetallicpalladiumcomplexescontaining2-pyridyl-1,2,3-triazole(pyta)ligand. Reprintedwithpermissionfrom[107](Astruc’sgroup).

©2013Wiley-VCH.

thesecoppercatalystswereremovedfromthereactionmedium througheasyprecipitationat−18◦Candreusedatleastthreetimes

[88].

3.1.4. Hydrogenation

BothcategoriesofmoleculardendriticcatalystsandDENs pro-videdexcellentperformancesinhydrogenation[131].Diphosphine andmonophosphineunitsareidealbridgebetweendendritic sup-port and metal for grafting dendritic metal complexes, due to theiroutstandingcapabilityofcoordination,stability,andcatalytic performance.Mostdendriticcatalystsforhydrogenationcontain diphosphineormonophosphine[132–134].

Fig.9.DSNformedfromG0;b)DENformedfromG1.[112].

Tripodal-terminated Rh-phosphine dendrimers were effi-cient catalysts for the hydrogenation of styrene and 1-hexene

[135]. In subsequent work, this group immobilized pyrophos-Rh(norbornadiene) at the periphery of PPI, PAMAM and

Fig.10. Leachingmechanisminthe“homeopathic”catalysisofSuzuki–MiyauraC–C couplingatambienttemperaturebetweenPhIandPhB(OH)2by“click”ferrocenyl

dendrimer-stabilizedPdNPs[81].

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Scheme2. Generalsynthesisofthepyrphos-Rh(NBD)complexes,and{G2}-PAMAM-{Glutaroyl-pyrphos-Rh(NBD)BF4}16.

Reprintedwithpermissionfrom[136](Gade’sgroup). ©2009Wiley-VCH.

hyperbranched PEI dendrimers (Scheme 2) [136]. These met-allodendrimershavebeenusedascatalystsforthehydrogenation ofZ-methyl␣-acetamidocinnamate.Anegativedendriticeffectin termsofactivityandselectivitywasobservedwithincreasingsize ofthedendrimersupportswhenthehydrogenationwascarried out in methanol, and a stronger negative effect was detected in terms of catalytic activity,stereoinduction, and recyclability. Moreover,there is nodifference in catalytic behavior between hyperbranchedpolymer-supportedanddendrimers-supportedRh complexesinthishydrogenationreaction.

Chiraldendriticmonodentatephosphoramidite[137,138]and dendritic BINAP (2,2-bis(diphenylphosphino)-1,1-binaphthyl)

[139] bearing different dendritic supports were applied as ligands for Rh or Ir-catalyzed asymmetric hydrogenation of ␣-dehydroamino acid esters, dimethyl itaconate, quinaldine, and methyl 2-acetamidocinnamate. High enantioselectivities (upto 99%ee)andcatalyticactivities(upto4850h−1TOF)wereachieved when these catalytic systems of dendritic ligands and metal complexeswereemployed,andallthecatalyticsystemsprovided positivedendriticeffects.

Theefficiencies ofcatalytic moieties within andacross den-drimergenerationsforpartiallyandfullfunctionalizedpoly(alkyl

arylether)dendrimersrhodium(I)complexesthatweretestedin thehydrogenationofstyrene[140].Significantincreasesof cat-alytic activities (TONs)with increasingthe amountof catalytic residuesdemonstratedpositiveeffectsofthemultivalent formu-lationofthecatalyticmoieties.

A carbosilane dendrimer functionalized with P-stereogenic diphosphineormonophosphinesligandshasbeendesignedand theiractivitiesin theRh-catalyzed hydrogenationof dimethyli-taconate have beenchecked [141,142].A “green” example was reportedthat thefluorinateddendriticchiral mono-N-tosylated 1,2-diphenylethylenediamine (FTsDPEN) was synthesized and appliedintheruthenium(II)complex-catalyzedasymmetric trans-fer hydrogenation of prochiral ketones in aqueous media with excellentenantioselectivity,andunprecedentedrecoveryand recy-clability[143].

FollowingseminalresearchonDEN-catalyzedhydrogenation, it wasshowthat thePAMAM G4-OHPd40NP (Fig. 13)is much

moreefficientthantheG6andG8DENsbecausethelatterserve asnanofilters[71,72,144]inhibiting,tosomeextent,the penetra-tionoftheN-isopropylacrylamidesubstratesinsidethedendrimer inwhichthecatalyticallyactiveNPwaslocated.Ontheotherhand, linearalkenespenetratedmoreeasily,resultinginamuchsmaller

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Fig.11.PAMAM-baseddendrimerswithend-graftedfivePd–Feunits. Reprintedwithpermissionfrom[121](Lang’sgroup).©2010Elsevier.

decreaseinactivity.WhenG4-NH2PAMAMdendrimerswere

func-tionalizedwithvariousepoxideterminihavingincreasingsizes,the hydrogenationcatalysisresultsshowedthattheDENs functional-izedwithbulkierepoxideswerelessefficientcatalyststhanthose havinglessbulkyepoxides[145,146].Molecularrulerscontaining

acyclodextrinstopperandallyl groupsspannedbyalkylchains havingdifferentsizeswereusedtoestimatethelengthbetween theDENsurfaceandthedendrimersurface,andforG4-OHPd40

DENssuchalengthwasestimatedtobe0.7±0.2nm[147,148]. TheYamamotoandNishiharagroupspreparedPAMAMG4-OHRh DENsthatcatalyzedolefinandnitroarenehydrogenationwitha metal-ion/dendrimerratioof60[148].TheG1–3 dihydroxybenzyl-alcohol-baseddendrimersstabilized14–35-nmsizedAgDSNsthat catalyzed choloronitrobenzene hydrogenation at 20bar H2 and

140◦C[149].

“Click”-ferrocenyl dendrimer-encapsulated and stabilized Pd nanoparticlepre-catalysts(Fig.9)wereusedtocatalyze hydro-genationreactions. Indeed,selectivehydrogenationofdienesto monoeneswasachievedreadilyunderambientconditionsforsmall dienes [80], but large steroidal dienes remained unreacted, in accordwiththeirlackofabilitytoreachthePdNPsurface.Therates (TOFs)andTONsofhydrogenationwereallthelargerasthePdNPs weresmaller, asexpected frompreviousresultswith polymer-stabilizedPdNPs[150–152]accordingtoamechanismthatinvolves mechanisticstepsofthehydrogenationonthePdNPsurface.

Heterobimetallic DENs are either alloys DENs (noted M1M2

DENs)orcore@shellDENs.TOFsforthehydrogenationofallylic alcoholwithPd-richheterobimetallicPdPtDENsweresignificantly higherthanthose ofphysicalmixtures ofthesingle-metal ana-logueshavingthesamepercentageofthetwometals[153–159]. Thiswasattributedtopositivesynergisticeffects[160].Au@PtNPs stabilizedbyFréchet-typepolyarylesterdendronsshowedhigher catalyticactivityinhydrogenationofnitrotoluenestoanilines com-paredwithmonometallicPtNPsoramixtureofPtandAuNPs, whichwasattributedtothedecreasedelectronicdensityonthe Ptshellarisingfromtheinfluenceof theAucore[161].Similar effectswereinvokedforthebetteractivityofheterobimetallicDEN

Fig.12.Copper(I)(hexabenzyl)trencomplex1andmetallodendriticCu(I)derivativeG1,G2,andwater-solubleG2.

Reprintedwithpermissionfrom[88](Astruc’sgroup). ©2011Wiley-VCH.

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Fig.13.PAMAMG4,G6andG8PdDENsforselectivecatalysis. Reprintedwithpermissionfrom[72](Crook’sgroup).

©2001AmericanChemicalSociety.

catalystscomparedwithmonometallicDENshydrogenationof p-nitrophenol[153],selectivehydrogenationof1,3-cyclooctadiene

[154],hydrodechlorinationof1,2-dichloroethane[155]andCO oxi-dation[156–159].

3.1.5. Carbonylationandhydroformylationreactions

Someremarkableexamplesinvolvingdendriticcatalystsona solidsupportsuchassilicagelhavebeenpublished(Fig.14).The dendriticRhorPdcomplexesonsolidsupportshowedhigh activ-ityforcarbonylationandhydroformylationreactions[89,162–167]. These systems were easily recovered by simple filtration in air and reused without loss of activity. Recyclable palladium-complexeddendrimersonsilicagelwerefirstusedascatalystsin intramolecularcyclocarbonylationreactions. Fromthispowerful approach,aseriesofoxygen-,nitrogen-,orsulfur-containing 12-to18-memberedringfusedheterocyclesweresynthesizedwith goodyields[168].

3.1.6. Oxidationreaction

Polyoxometalates(POMs)[169–171]arealargeclassof inor-ganiccagecomplexeswithveryinterestingpropertiesthatrender

them attractive for potentialapplications in a variety of fields including catalysis. The catalytic properties of dendritic POM hybrids were based on electrostatic bonding between POMs (the most frequent one is Venturello ion [PO4{WO(O2)2}4]3−)

pairedwithdendriticcations.DendriticPOMsbearingVenturello ion exhibited good catalytic activity and recoverability in the oxidationoforganicsubstratessuchasalkenes,alcohols,and sul-fides [85–87,172–174].Zirconium-peroxo-baseddendriticPOMs (Fig. 15) obtained by pairing zirconium-peroxotungstosilicate [Zr2(O2)2(SiW11O39)2]12− with ammonium dendrons provided

homogeneous dendritic counterparts that also were recover-able and reusable catalysts for the oxidation of sulfides in aqueous/CDCl3biphasicmedia[175].

Dendritic pyridine derivatives bearing 2,3,4,5-tetra-phenylphenyl substituent-supported palladium complexes suppresstheformation of Pd blackduring aerobicoxidation of alcohols under commonconditions [176].Heterogeneous man-ganese complexesof polystyrene-supported PAMAMdendrimer showed high stability and catalytic efficiency in oxidation of secondaryalcohols,andcanberecoveredandreusedatleastsix times[177].

3.1.7. Polymerizationandoligomerization

The well-defined hyperbranched structure of metalloden-drimersleadstopossibilityofsiteisolationofcatalyticresidues, which suppress theformation of inactive bis-metal complexes. Thedendrimer-substitutedo-diphenyl-phosphinophenol(Fig.16, left)isfarmoreactivethantheparentligand(Fig.16,right)for the Ni-catalyzed oligomerization of ethylenein toluene, which wastakenintoaccountbythefactthatthedendriticarchitecture suppressedtheformationofbis-(P,O)Nicomplexes [178].When thecomparedanalysiswascarriedoutinmethanol,asimilar cat-alyticresultwasobtained,buttheprocesswasdifferentfromthat observedintoluene:boththedendriticligandandtheparentligand formedbis(P,O)nickelcomplexesinmethanolaccordingtoNMR spectroscopy.However,thedendriticbis(P,O)Nicomplex dissocia-testoamono-ligatedspeciesundercatalyticconditions.

Bothamonometalliccopper(II)complexandabimetallic com-plex assembled with four copper(II) ions and one iron(III) ion bearing a dendritic phenylazomethine (DPAG4, Fig. 17) were used to catalyze the aerobic oxidative polymerization of 2,6-difluorophenol without any base additive [179]. The catalytic efficiency of the bimetallic complex outperforms that of the monometalliccoppercomplex,thatis,theparticipationofthe sec-ondmetal-ionenablesfacilecontrolofthepolymerproductswith exceptionallyhighmolecularmassesandbranching.Thelocation ofthemetalsaltsinDPAG4dendrimerwasradial,resultingfrom stepwisecomplexationasreportedinapreviousstudy[180].The locationsofbimetallicentitiescontainingcopperandironinDPAG4 werealsoinvestigated.Binarytitrationexperimentsshowedthat iron(III) with stronger affinity than copper(II) for thedendritic ligandpreferentiallybindtothe innercoordination sitesof the DPAG4,whichwasconfirmedbyUV–visabsorptionspectrometry. 3.1.8. Arylationandalkylationreactions

Phosphorus dendrimers functionalized with iminopyridine chelating unit (Fig. 18) provided higher yields than with a monomeric ligand for O- and N-arylation and vinylation of phenol and pyrazole [181]. When azabis(oxazoline)-ended phosphorusdendrimerswereevaluatedasligandsfor copper(II)-catalyzed asymmetric benzoylations, a positive dendritic effect in terms of enantioselectivity was observed [182]. The sec-ond generation of 2,9-dimethyl-1,10-phenanthroline grafted dendrimer showed similar catalytic activity to that of the monomer in Cu-catalyzed substitution of 4-iodoanisol to give 1,4-dimethoxybenzene[183].Dendriticpoly(propylenimine)and

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Fig.14.Rh–PPh2–PAMAM–SiO2complexes.

Reprintedwithpermissionfrom[89](Alper’sgroup). ©1999AmericanChemicalSociety.

hyperbranchedpoly(ethylenimine)withP-containing functional groupswere appliedasmultivalentligands inthePd-catalyzed allylicsubstitutionreactions[184].TheG0–G4phosphorus-based dendrimersdecoratedwith␤-diketoneswereusedasligandsfor copperinO-arylationsof 3,5-dimethylphenolby arylbromides. Althoughnodendrimereffectwasobserved,whichresultedfrom thedecompositionofthedendrimerunderthereactionconditions, itisaveryefficientcatalyticsystemfortheO-arylationreaction

[185].

3.1.9. Asymmetricsynthesis

Examples of asymmetric hydrogenation have already been introducedinthe“Hydrogenation”section.Otherrecentadvances inmetallodendriticasymmetricsynthesisincludetheHenry reac-tion, addition of dialkylzinc to aldehyde, asymmetric epoxide ring-openingreaction,Diels–Alderreaction,andthree-component condensation.

A series of well-defined chain-end functionalized carbosi-lanedendrimershavingbis-andtrisoxazolinesdistributedatthe peripheryoftheirhyperbranchedchainendshavebeen synthe-sized[186].Subsequently,dendriticcoppercomplexesthatwere immobilizedinamembranebagwereproduced,then“catalysis in teabag” systems was assessed by studying two benchmark reactions,the ␣-hydrazinationof a ␤-ketoester and theHenry reactionof2-nitrobenzaldehydewithnitromethane(Fig.19).The bisoxazoline-basedcatalystsdisplayedsufficientactivityandcould berecycledwithoutsignificantdecreaseinactivityandselectivity. Moreover,thesimpleoperationofdippingthecatalyst-filled dial-ysisbagsintoreactionvesselscontainingthesubstratewascarried outsuccessfully.

Aseriesofdendriticpolyglycerolsalenligandshavebeen syn-thesized[187].ThecorrespondingdendriticCr(III)catalystswere

usedforasymmetricepoxidering-opening(ARO)reaction.A neg-ativedendritic effectwasshownontheenantioselective ofthe AROreaction,whichresultedfromtheorientationofthe immo-bilized catalytic units with respect toone another. To achieve higherenantioselective,pyrrolidine-modifieddendriticsalen lig-andswereusedandprovidedimprovedcatalyticactivities.

AmethodforDiels–Alderandthree-componentcondensation reactionsusingpoly(arylether)witha2,2-bipyridinecore-based dendritic copper catalyst was described [188]. The Diels–Alder reaction of cyclopentadiene with various dienophiles was per-formedwith10mol%ofthecatalystaffordingthecorresponding adductsin excellent yields; when thedendriticligand wasnot used in the reaction, neat copper catalysts could not provide Diels–Alderadductsbutpromotedthecationicpolymerizationof cyclopentadiene.Thiscatalyst wasalsoemployed for Mannich-type reactions(three-componentcondensation)of analdehyde, o-anisidine.Usingvariousnucleophiles,betteryieldwasobtained with water as solvent than with dichloromethane, which was attributedtothecohesion effectoforganicsubstratesin water. Moreover,thecatalystwasrecoveredandreusedatleastfivetimes withoutlosingitsactivityinallcases.

3.1.10. Otherreactions

Other recent advances in metallodendritic catalysis focused on thermal decomposition of ammonium perchlorate [189], Ru-catalyzed hydration of phenylacetylene and isomerization of 1-octan-3-ol [190,191], Pd-catalyzed auto-tandem reaction

[192,193], Fe-catalyzed alkene epoxidation reactions [194], Cu-catalyzed generation of oxygen radical anions [195], Ru-catalyzed olefin metathesis[196,197], Zn-catalyzed cleavage of the RNA model substrate HPNPP [198,199], Co-catalyzed acti-vation of carbon dioxide [200], co-catalyzed debromination of

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Fig.15.Zirconium-peroxo-baseddendriticPOMs. Reprintedwithpermissionfrom[175](Nlate’sgroup).

©2010Wiley-VCH.

Fig.16.o-Diphenylphosphinophenolligands. Reprintedwithpermissionfrom[178](ReekandvanLeeuwen’sgroup). ©2004AmericanChemicalSociety.

2-phenethylbromide[201],andRh-catalyzed[2+2+2] cycloaddi-tionreacton[202].

Thecombination ofPTA (1,3,5-triaza-7-phosphaadamantane)

[203] and dendrimers might bring about water-soluble organometallic dendritic catalysts. Ruthenium complexes with PTAattheperipheryweresynthesizedandusedascatalystsfor thehydrationofalkynesandtheisomerizationofallylicalcohols to ketones in aqueous media. Positive dendritic effects on the

Scheme3. Conceptof“bottling”dendriticcatalystsinPPXnanotubes. Reprintedwithpermissionfrom[221](Wendorff’sgroup).

©2009Wiley-VCH.

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Fig.17.Structuresofphenylazomethinedendrimer(DPAG4),andtheadditionofCuCl2andFeCl3bydifferentmethods.

Reprintedwithpermissionfrom[179](Yamamoto’sgroup). ©2011JohnWiley&Sons,Ltd.

regioselectivityor conversionwereobserved for bothreactions

[190].Inaddition,thestudyofthe“numberofterminalgroupsvs. dendrimergeneration”wasinvestigatedforthedendriticligand

1-G2ofthefirstgenerationcontaining24PTAgroups,1-G1ofthe

firstgenerationcontaining12PTAgroups,and6-G2ofthesecond

generationcontaining24PTAgroups(Fig.20).Throughcompared analysisofthecatalyticefficiencies,thepositiveinfluenceofthe densityofcatalyticsitesonthesurfaceofthesedendrimersforthe alcoholisomerization reactionin waterhasbeen demonstrated

[191].

Catalysis of ring-closing metathesis(RCM), cross metathesis (CM) and enyne metathesis (EYM) of hydrophobic substrates wasreportedinwaterandairunderambientormildconditions usinglow catalytic amounts (0.08mol%)of a suitably designed “click”dendrimer(Fig.21)thatcan bereusedmany times and

Fig.18.Structureofazabis(oxazoline)-endeddendrimerligandgeneration1. Reprintedwithpermissionfrom[181](Majoral’sgroup).

©2006AmericanChemicalSociety.

verylowamountsofGrubbs’secondgenerationolefin-metathesis catalyst[197,204–206].Thedendrimerplaystheprotectingroleof ananoreactortowardsthecatalyticallyactivespecies,inparticular thesensitiveruthenium-methyleneintermediate,involvedinthe metathesiscatalyticcycle,preventingcatalyst decompositionin thepresenceofanolefinsubstrate.

3.2. Dendriticorganocatalysts

Thenumber ofpublications ondendritic organocatalysishas dramatically increased during the past few years [207–212]. Michaeladdition[213–215],hydrolysisreaction[216,217],model aldolreaction[218],epoxidationofenones[219],hydrogenation

[220], Knoevenagel reactions [221], transamination [222], aldol reactions[223,224],hydrosilylation[225],superoxidedismutation

[226],asymmetricboranereductionofprochiralketones[227],and ring-openingofepoxides[228]havebeenreportedusingdendritic organocatalysts.

Forexample,anovelmethodin whichC16 alkylchainshave

beenattachedtothefifthgenerationofpoly(propyleneimine)(PPI) dendrimerswasreported[207],andthesenewdendrimershave beenusedasefficienttertiaryaminecatalystsforanintramolecular Michaelreactionbasedonsubstrateorientationwithinthe inter-nal dendritic nanocavities. The sterically confined nanocavities consisting of regularly arranged amino groups of thedendritic organocatalyst could accommodate the substrate in a reactive conformationforintramolecularcyclization.Therecyclablechiral 2-trimethylsilanyloxy-methyl-pyrolidine-functionalized den-driticorganocatalyst wassynthesized and used in the Michael

Fig.19.Anenlargedschematicviewofgeneralsetupfortherecyclingusingthe “catalystinateabag”principle.

Reprintedwithpermissionfrom[186](Gade’sgroup). ©2009Wiley-VCH.

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Fig.20.Chemicalstructureofdendrimers1-G1,1-G2,and6-G2,allowingthecomparisonbetweentheirsizeandtheirnumberofterminalgroups.

Reprintedwithpermissionfrom[191](Caminade’sgroup).©2012Elsevier.

addition reaction of various unmodified aldehydes with nitrostyrenes [208]. In this study, the catalyst showed good catalytic activities in terms of yields, enantioselectivities, and diastereoselectivitieswhenaldehydeswithdifferentsubstituents were employed.A series of Wangpolystyrene-supported recy-clable bifunctional dendritic organocatalysts having various numbersofacidicprotonsbasedonchiraldiamineshavebeen syn-thesized[209].Thesemacromoleculeswereevaluatedascatalysts forasymmetricnitro-Michaeladditionofacetonetonitroolefins.

CatalyticresultsshowedthatthenumberofH-bonddonorsofthe catalyst wasa determinantfor the reactivity and enantioselec-tivity.Whenthenumberofacidicprotonsincreasesfromzeroto two,theyieldoftheproductincreases3-fold.However,abetter enantioselectivitywasachievedwithcatalystshavingoneacidic proton.

Poly(p-xylylene) (PPX) nanotubes which can be considered as nanoreactors were prepared in 2009 (Scheme 3) [221]. The PPX nanotubes loadingPAMAMdendrimers showedactivityas

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