chemistry in polymer and material
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‘Click’ Chemistry in Polymer and Material
Science: An Update
Wolfgang H. Binder,* Robert Sachsenhofer
Introduction
Who will be reading a review on a topic that was reviewed
only 15 months previously[1] by the very same author?
According to a SciFinder search in January 2008, the azide/
alkyne ‘click’ reaction (also termed CuAAc) has had
enormous impact within the field of polymer science.
Thus, 220 original papers have been published in the
context of click chemistry and polymer science, more than
20 reviews and at least 10 patents have appeared,
altogether stressing the importance of this reaction. Given
the short timeline for discovery of CuI catalysis
(2001–2002 by Meldal et al.[2,3] and 2002 by Sharpless
et al.[4]) and the first published applications in polymer
science (2004),[5–10] someone may ask the question
‘where does it stem from’, and - in the same line - find a
quick answer: a high efficiency reaction, coupled with a
high functional group tolerance and solvent insensitivity
(also highly active in water), working equally well under
homogeneous and heterogeneous conditions certainlyranks high on the polymer scientists’ wish list. Therefore,
this reaction is a solution to many problems that have
been encountered in polymer science for a long time, such
as: a) a poor degree of functionalization with many
conventional methods, especially when involvingmultiple
functional groups (i.e.: at graft-, star-, and block copoly-
mers, dendrimers, as well as on densely packed surfaces
and interfaces); b) purification problems associated with
the often emerging partially functionalized mixtures; c)
incomplete reaction on surfaces and interfaces; and d)
harsh reaction conditions of conventional methods, which
often lead to the break-up of associates and assemblies, in
particular in the newly emerging supramolecular sciences.
As a main surplus, the click reaction combines excellently
with many controlled polymerization reactions developed
during the past decades,[11] thus opening the way to a
nearly unlimited investigation of new functionalized
polymeric architectures, hitherto unreachable by the
polymerization methods themselves. With azide/alkyne
click chemistry in hand, polymer chemistry now approa-
ches the level of small-molecule organic chemistry in
terms of functional broadness, structural integrity, and
molecular addressability.
Review
W. H. Binder, R. Sachsenhofer
Martin-Luther University Halle-Wittenberg, Faculty of Natural
Sciences II (Chemistry and Physics), Institute of Chemistry/
Division Technical and Macromolecular Chemistry, Heinrich-
Damerowstr. 4/12; 06120 Halle (Saale), Germany
E-mail: [email protected]
The metal catalyzed azide/alkyne ‘click’ reaction (a variation of the Huisgen 1,3-dipolarcycloaddition reaction between terminal acetylenes and azides) has vastly increased inbroadness and application in the field of polymer science. Thus, this reaction representsone of the few universal, highly efficient functionalization reactions, which combines bothhigh efficiency with an enormously high tolerance of functional groups and solvents underhighly moderate reaction temperatures
(25–70 8C). The present review assembles anupdate of this reaction in the field of polymerscience (linear polymers, surfaces) with a focus onthe synthesis of functionalized polymeric archi-tectures and surfaces.
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Briefly, the azide/alkyne click reaction[12–14] represents a
metal-catalyzed variant of the Huisgen 1,3-dipolar
cycloaddition reaction[15,16] between C–C triple, C –N triple
bonds[17] and alkyl-/aryl-/sulfonyl azides. The relevant
outcomes of this reaction are a) tetrazoles, [13,18] b) 1,2,3-
triazoles,[2–4,19] or c) 1,2-oxazoles, respectively. In addition,classical Diels–Alder-type reactions have been used
extensively for the functionalization of polymeric materi-
als[20] and surfaces.[21] According to the definition of
Sharpless et al.,[12] a ‘click reaction’ is defined by a gain of
thermodynamic enthalpy of at least 20 kcal mol1, thus
opening the way to a high yielding and thus nearly
substrate-insensitive reaction. The present review focuses
entirely on the azide/alkyne reaction catalyzed by CuI
species, and the now more widely used purely thermal
(‘Huisgen-type’) processes in polymer science and on
surfaces. A survey of the most recent literature related to
the polymer science and materials field in the years 2006to 2008 (deadline: 15th March 2008) will draw a line to a
previous review in this journal[1] and other reviews
describing the azide/alkyne click reaction in general,[12,22]
for application in polymer chemistry,[1,23–28] dendri-
mers,[25,29] carbohydrate chemistry,[30–32] materials chem-
istry,[1] and organic chemistry,[28,33] as well as for
peptides[34] and drug discovery.[35] In addition, this whole
special issue of Macromolecular Rapid Commununication
is dedicated to this topic, including many more specialized
reviews and original papers. Thus special reviews will
cover topics such as the role of the copper species on
polymer ‘clicking’ (by M. Meldal), the generation of
polymeric architectures (by Turro et al.), the combination
of biodegradable polymers and azide/alkyne click reac-
tions (by R. Jerome et al.); the synthesis of multistep
reactions in combination with azide/alkyne click reactions
(by M. Malkoch et al.); click chemistry for the synthesis of
macromolecular chimeras (polymer/biopolymer hybrids,
by K. Velonia); and reversible addition fragmentation
transfer (RAFT) from silica nanoparticles (by W. Brittain
et al.). The present review will briefly and concisely update
the topic azide/alkyne click chemistry in polymer science,
including literature up to March 2008.
Mechanistic Details/Catalysts
Briefly, the basic process of the Huisgen 1,3-dipolar
cycloaddition[2,10,11] generates 1,4- and 1,5-triazoles
respectively (Scheme 1). Nearly all functional groups are
compatible with this process, except those that are a) eitherself reactive or b) able to yield stable complexes with
the CuI metal under catalyst deactivation. Main interfering
functional groups are terminal azides and alkynes,[36]
strongly activated cyanides,[13,14,18] free (accessible) thiol-
moieties (R–SH) via the Staudinger reaction, as well as
strained or electronically activated alkenes.[16,37] However,
the possibility to use free-thiols prior to an azide/alkyne
click reaction has been demonstrated recently on poly-
mers[38] and surfaces,[39] thus enabling the use of free
thiols despite the often interfering azide/amine reduction
by the free thio-moiety.
In addition to the use of CuI
salts (amounts of approx.0.25–2 mol-%, also coupled to regenerative systems with
ascorbic acid), copper clusters (Cu/Cu-oxide nanoparticles,
sized 7–10 nm[40] or4 nm[41]), metallic Cu0 clusters [41–43])
as well as copper/charcoal[44] have been described. A new
and highly innovative approach towards a polymeric-
bound CuI catalyst has been described by Bergbreiter
et al.,[45] attaching a bipyridyl ligand to a polyisobutylene,
subsequently ligating the CuI species to the polymer. This
generates a CuI species with a high solubility in hexane
solvents for catalytic applications. Recently, the use of
a CuI-free variant using the ring-strain of substituted
cyclooctynes to promote the dipolar cycloaddition process
‘Click’ Chemistry in Polymer and Material Science: An Update
Wolfgang H. Binder is currently full professor of Macromolecular Chemistry at the Martin–Luther University Halle–
Wittenberg. He studied chemistry at the University of Vienna and received a Ph.D. in organic chemistry (University of
Vienna, 1995). Postdoctoral studies (1995–1997) with Prof. F. M. Menger at Emory University, Atlanta, USA, and with Prof.
Mulzer (Vienna, Austria) completed his education. After Habilitation at the Vienna University of Technology (TU-Wien,
2004) and acting as an Associate Professor of Macromolecular Chemistry (TU-Wien, 2004–2007), he became full professor
at the University Halle-Wittenberg (MLU) in 2007. His research interests include polymer synthesis, supramolecular
chemistry, and nanotechnology
Robert Sachsenhofer is currently a Ph.D. student at the Martin–Luther University Halle–Wittenberg, Germany, in the group
of Prof. W. H. Binder. After finishing a diploma thesis under the supervision of Prof. Binder on the surface modification of
luminescent cadmium selenide nanoparticles by ‘click’-type reactions at the Vienna University of Technology, Austria, he
joined the group of Prof. Binder for his Ph.D. in the field of self-assembly of amphiphilic block copolymer.
Scheme 1. Azide/alkyne - ‘‘click’’ - reaction.
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has been described, enabling mild reactions on living
(cellular) systems.[46,47]
Most known solvents and biphasic reaction systems
(mixtures of water/alcohol to water/toluene) can be
applied with excellent results. Cocatalytic systems[48]
often used include amino bases,[49]
(triethylamine (TEA),2,6-lutidine, N , N -diisopropylethylamine (DIPEA), N , N , N 0, N 0,
N 00-pentamethylethylenetetramine (PMDETA), hexame-
thyltriethylenetetramine (HMTETA), tris[(2-pyridyl)-
methyl]amine (TPMA), tris[(2-dimethylamino)ethyl]amine
(Me6TREN), 2,20-bipyridines (bpy), 2,20:20,600-terpyridine
(tpy), ammonium salts,[42] and mono- and multivalent
triazoles[49]) but also phosphines such as tris(carboxy-
ethyl)phosphine (TCPE). A detailed investigation[50] of
several amines has demonstrated a relative kinetic effect
of the added ligands in the order: PMDETA (230)>
HMTETA (55)>Me6-TREN (50)> tpy (8.6)> TPMA
(1.7)>no ligand>bpy (0.43). The increase in reaction rate
is mostly explained by promoting the formation of
the CuI-acetylide, reducing the oxidation of the CuI-
species, but also by preventing side reactions of the
acetylenes (Ullman couplings, Cadiot–Chodkiewizc cou-
plings) or dimerization reactions of the finally formed
triazoles.[51] The latter dimerization reaction is a very
important one, generating 5,50-coupled dimeric triazoles
when using carbonates as bases instead of the usual amine
bases. Moreover, the copper-catalyzed hydrolysis of
O-propargylic-carbamates has recently been described.[52]
Besides copper, other metals employed include Rucomplexes[53,54] such as (CpRuCl(PPh3), [Cp
RuCl2]2,
CpRuCl(NBD), and CpRuCl(COD) favoring not only the
formation of 1,4-addition (e.g., with Ru(OAc)2(PPh3)2), but
also the formation of 1,5-adducts by other Ru catalysts. In
addition, the use of AuI-,[55] Ni-, Pd-,[56] and Pt-salts, has
been described, although with significantly less catalytic
activity.[50]
Strong effects of alternative synthetic methodologies
have been observed under microwave irradiation.[57–62] As
it turns out, the click reaction can be strongly accelerated
under microwave irradiation, however, favoring both the
1,4-adduction as well as the side reactions.
The mechanism (first experimentally proposed by
Sharpless et al.[4] and changed by Finn et al.,[63,64] deter-
mined by computational methods,[65,66] and finally revised
by Bock et al.[22]) involves the following main features
(Scheme 2): a) up to a 105 rate acceleration and an
W. H. Binder, R. Sachsenhofer
Scheme 2. Proposed mechanism of the azide/alkyne - ‘‘click’’ - reaction.
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absolute 1,4-regioselectivity of the CuI catalyzed process,
b) a kinetic feature of the reaction that indicates at least
second-order kinetics with respect to the concentration of
the copper species,[64] thus proposing at least two copper
centers involved in this reaction, probably linking two
acetylenes by a m-bridge,[67]
c) a significant autoaccelera-tion if multiple triazoles are formed,[48] which reveals
intermolecular ligand effects, d) a significant rate-
reduction with strongly increasing amount of copper,
and e) the formation of a copper-acetylide, whose primary
structure and, therefore, direct activity within the transi-
tion state cannot be exactly predicted. In particular, the
exact structure of the copper-acetylide is difficult to predict
a) because of the large number of possible interactions
(p-complexation, multiple copper species) and b) because
of the many known (highly different) structures of
copper-acetylides. However, the basic feature (i.e., low-
ering of the p K a value of the Cu-acetylide by up to 9.8 units
as determined[66] by DFT calculations) is the most
important contribution towards the rate acceleration.
If the two reaction partners (azide and alkyne) are
brought into close (enforced) spatial relationship, the
reaction can be fast and efficient, as demonstrated in the
case of proteins and enzymes (affinity based protein
profiling (ABPP)),[19,36,68,69] microcontact printing,[70,71] or
atomic force microscopy (AFM)-based techniques.[72] All
three methods generate a closer-than-usual distance
between the two reaction partners, thus linking reactivity
in this reaction to molecular distance. The absolute value
of the necessary minimal distance at which the azide/
alkyne click reaction occurs spontaneously has, however,not been specified in the literature.
A final remark should be made with respect to the
optimal system for succeeding in an azide/alkyne click
reaction. Honestly spoken, despite reviewing the literature
as well as many of our own experiments[9,39,73–81], I cannot
tell. The number of variables and requirements is simply
too high as to provide a general answer to this
certainly important question. The tables and examples
below may provide a hint and explanation in themselves,
and thus eventually lead to an answer with respect to a
specific system. The only, scientifically unsatisfactory, but
truly honest answer I can provide is: check it out, it’s
simple.
Click Reactions on Linear Polymers
The enormous interest in linear polymers lies primarily in
the combination of click reactions with controlled poly-
merization processes. This chapter lists examples
published till the midst of January 2008, where
known polymerization processes have been combined
with the azide/alkyne processes, mostly relating to the
chemical possibilities and the chemical realization of this
endeavor.
Table 1 lists the known click reactions on various linear-
or graft-polymers, according to the polymerization method
and the final chemical structure of the polymer, either
before the click reaction, or after. Cases are shown in anexemplary manner, as to indicate the chemistry required
in order to conduct a click reaction within or after a specific
polymerization process. In general, as shown in Table 1,
more than 60 entries are described, which indicates the
enormous broadness of the investigations. For an example
of click chemistry in conjunction with free-radical poly-
merization see ref.[82].
Atom Transfer Radical Polymerization (ATRP)
As indicated in Table 1 (entries 1–18), a variety of click
reactions in conjunction with ATRP have beendescribed.[45,50,83–115] The reaction has been investigated
with polymers such as polystyrene, various polyacrylates
and polymethacrylates, polyacrylnitrile, and poly(ethy-
lene oxides). As the main methods for conducting ATRP
and click reactions has been described in the previous
review,[1] this issue will not be discussed here in more
detail. In principle the following strategies can be applied
to achieve a combination between the click reaction and
ATRP:
The initiator approach,[85,89,91,103,106,110] which relies on
the use of an alkyne-functionalized initiator or azide-functionalized initiator[115] as shown in Table 1, entries
6, 7, 8, 14 or 2. Relevant to this point is the fact that the
acetylenic/azido initiator-moiety is not cross-reactive
within the subsequent ATRP process.
The Br /N 3 approach[84,85,88,90,94,102,103,107–109,113,114,116]
takes advantage of the terminal bromine-moiety, inher-
ently present within the ATRP reaction. A final Br/
N3 -nucleophilic reaction (usually performed in NaN3/
N , N -dimethylformamide (DMF)) then completes the intro-
duction of an azido-moiety to the terminus of the polymer
(see Table 1, entries 3, 5, 6, 8, 10, 11, 12, 16, and 18). The full
conversion of this reaction has been demonstrated by
NMR methods and subsequent characterization by
matrix-assisted laser desorption ionization mass spec-
trometry (MALDI MS) experiments of the final ‘clicked’
products.
Side-chain modified polymers [86,92,93,97,102,109,111] with
pendant azido- or acetylenic moieties for the generation of
graft-polymers (e.g., Table 1, entry 1, 10, 13, 17a, and 17b)
have been reported. Again, the full compatibility of the
terminal azido or acetylenic moieties with the ATRP reac-
tion is observed, which leads to a high density of func-
tional side chains within the main-chain polymer.
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W. H. Binder, R. Sachsenhofer
Table 1. Overview of ‘click’-reactions with linear- or graft-polymers.
Entry Polymer/substrate Polymerization
method
Catalyst/
conditions
Ref.
1 ATRP CuBr/r.t. [86]
2 ATRP N -alkyl-2-
pyridylmethanimine-
CuBr/70 -C
[115]
3 ATRP CuBr/THF/r.t. 4,4(-
di(5-nonyl:)-
2,2(-bipyridine
[84,90]
4a ATRP NaN3/ZnCl2/120-C [10]
4b ATRP NaN3/ZnCl2/120 -C [10]
5 ATRP CuBr/PMDETA/r.t. [107]
6 ATRP CuBr/DMF/r.t. [106]
7 ATRP CuI/DBN/THF/35 -C [85]
8 ATRP CuBr/PMDETA/THF/
35 -C
[108]
9 ATRP CuBr/PMDETA [103]
10 ATRP CuBr/DMF/r.t [102]
( Continued )
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‘Click’ Chemistry in Polymer and Material Science: An Update
Entry Polymer/substrate Polymerization
method
Catalyst/
conditions
Ref.
11 ATRP CuBr/PMDETA/r.t [94]
12 ATRP CuBr/PMDETA/50 -C [98]
13 ATRP CuBr/DMF [97]
14 ATRP CuBr/bipyridine/DMF/120 -C
[89]
15 ATRP Cu0/CuBr or CuBr/
PMDETA/DMF/r.t.
[87]
16 ATRP CuBr/PMDETA/sodium
ascorbate/DMF
[88]
17a ATRP Cu(PPh3)3Br/DIPEA [109]
17b ATRP Cu(PPh3)3Br/DIPEA [109]
18 ATRP CuBr/bipyridine/
THF/r.t.
[113]
19 NMP NaN3/ZnCl2/DMF/
120 -C
[119]
Table 1. (Continued)
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W. H. Binder, R. Sachsenhofer
Entry Polymer/substrate Polymerization
method
Catalyst/
conditions
Ref.
20 NMP Cu(PPh3)3Br/DIPEA/
dioxane
[120]
21 NMP Cu(PPh3)3Br/DIPEA/
THF
[123]
22 NMP [(CH3CN)4Cu]PF6/
TBTA/DIPEA/DMF
[81]
23 NMP CuBr/PMDETA/
DMF/r.t.
[96]
24 NMP Cu(PPh3)3Br/DIPEA [122]
25 NMP toluene [121]
( Continued )
Table 1. (Continued)
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‘Click’ Chemistry in Polymer and Material Science: An Update
Entry Polymer/substrate Polymerization
method
Catalyst/
conditions
Ref.
26 free radical CuSO4 5H2O/
sodium ascorbate/
H2O/DMSO
[82]
27 RAFTRNMP Cu(PPh3)3Br/DIPEA/
THF/H2O/r.t./3d
[118]
28 RAFT CuI/DBU/DMAc/40 -C [129]
29 RAFT CuBr/PMDETA/
DMF/r.t
[130]
30 RAFT CuSO4/sodium
ascorbate/
H2O/t BuOH
[128]
31 ATRP CuBr/bipyridine/
120 -C
[104]
32 RAFT CuSO4/sodium
ascorbate/H2O
[117]
33 RAFT CuSO4 5H2O/sodium
ascorbate/DMSO/50-C
[101]
Table 1. (Continued)
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W. H. Binder, R. Sachsenhofer
Entry Polymer/substrate Polymerization
method
Catalyst/
conditions
Ref.
34 RAFT Cu(PPh3)3/DIPEA/
DMF/r.t.
[132]
35 RAFT CuBr/PMDETA/
DMF/r.t.
[127]
36 RAFT Cu(PPh3)3Br/DIPEA/
THF/H2O
[133]
37 RAFT CuI/DBU/THF [131]
38 RAFT [134]
39 RAFT CuI/DBU/THF/40 -C [135]
( Continued )
Table 1. (Continued)
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‘Click’ Chemistry in Polymer and Material Science: An Update
Entry Polymer/substrate Polymerization
method
Catalyst/
conditions
Ref.
40 ROMP Cu(I)/DIPEA/DMF/
toluene/H2O
[76]
41 ROMP Cu(PPh3)3Br/DIPEA/
DMF/50 -C
[9,75]
[74]
42 ROMP [137]
43 ROMP CuBr/PMDETA/
DMF/50 -C
[136]
44 [150]
45 living anionic [38]
46 living cationic
ring opening
CuSO4 5H2O/
water/t BuOH
[145]
47 living cationic
polymerization
of isobutene
Cu(PPh3)3Br/DIPEA/
toluene
[77]
48 living anionic
polymerization
CuBr/DMF/60 -C [149]
Table 1. (Continued)
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W. H. Binder, R. Sachsenhofer
Entry Polymer/substrate Polymerization
method
Catalyst/
conditions
Ref.
49 polyaddition Cu(I) [153,152]
50 polyaddition 100 -C [154]
51 polyaddition CuSO4.5H2O/
sodium ascorbate/
H2O/tBuOH
[155]
52 polyaddition CuSO4.5H2O/
sodium ascorbate/H2O/
tBuOH
[156]
53 polyaddition [151]
54 polyaddition CuSO4 5H2O/sodium
ascorbate H2O:t BuOH (1: 1)/r.t.
[6]
55 polyaddition Cu/Cu(OAc)2/
TBTA THF/
CH3CN
[161]
56 polyaddition CuSO4 5H2O/sodium
ascorbate
[157]
57 CVD CuSO4 5H2O/sodium
ascorbate H2O:tBuOH (2: 1)
[70]
( Continued )
Table 1. (Continued)
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As the main structural issues are solved within the
combination of click reactions and ATRP, this method is
a fully established reaction sequence that leads to all
kinds of chain-end, head-end, and side-chain modified
polymers by the ATRP process.
An important point concerns the formation of macro-
cyclic polymers by click reactions,[89] which was first
described by Grayson et al. (Table 1, entry 14) with an a ,v-
bifunctional polystyrene, and has now been extended to
the generation of cyclic poly( N -isopropylacrylamides)[104]
(Table 1, entry 31) in yields that range from 60 to 80%. This
verifies the prediction made in the previous review, [1] that
the click reaction will be an efficient tool for the generation
of polymeric macrocycles in the near future. In a similar
‘Click’ Chemistry in Polymer and Material Science: An Update
Entry Polymer/substrate Polymerization
method
Catalyst/
conditions
Ref.
58 topological CuI/CH3CN [164]
59a/b polyaddition CuSO4 5H2O/H2O:tBuOH (2: 1)
[163]
60 anionic ring
opening
CuSO4 5H2O/sodium
ascorbate/100 -C
[143,141]
[140]
61 ROP CuSO4 5H2O/Cu wire/
37 -C
[146]
62 sequential
stepwise
solid phase
synthesis
CuI/ascorbic acid/
DIPEA butan-2-ol/
DMF/pyridine
[172]
63 CuIIBr/ascorbic acid/
propylamine DMSO/r.t.
[176]
64 DNA-synthesis DMSO/H2O/80 -C/72 h (no CuI!!) [188]
65 solid phase synthesis or
DNA-polymerase
CuI [186]
66 solid phase synthesis CuSO4 5H2O, sodium
ascorbate H2O/MeOH
[61,182]
Table 1. (Continued)
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manner (see Table 1, entry 32) the generation of cyclic
poly( N -isopropylacrylamides) by RAFT/click methods has
been described in high yields.[117]
Nitroxide-Mediated Polymerization (NMP)As time has gone by, many NMP methods have been
conducted in junction with the click reaction.[81,96,118–125]
As with ATRP, the polymerization of side-chain function-
alized monomers bearing azido-moieties is simple, and
leads to copolymers onto which additional functional
groups can be easily attached. Thus photolabile moieties
(entry 20)[120] or potential crosslinking sites (entry 24)
can be introduced by the corresponding acetylenes or
azides.[124] The initiator approach (Table 1, entries 21–23)
has been tested using an azide/alkyne-modified Hawker-
type nitroxide to initiate the polymerization of sty-
renes,[96,123]
acrylates,[81,96]
and N -isopropylacrylamide.[81]
The attachment site can be easily functionalized by the
azide/alkyne click reaction, to furnish the corresponding
monofunctionalized, telechelic polymers. Furthermore, the
simplicicity of the generation of a large structural variety
of Hawker-type nitroxide initiators could be used to
demonstrate remote effects between the end-group on the
nitroxide and the growing radical.[81] A very fine example
of a combination of a modified NMP initiator (prepared by
the click approach) and ATRP has been reported (Table 1,
entry 23).[96,126] Besides the nitroxide moiety, an ATRP-
initiating site as well as a terminal alkyne moiety are
bound to the initiator, which generates three possible
sites for the attachment of three different polymers:
initiation of polystyrene by the NMP method, followed by
the attachment of poly(ethylene glycol) (PEG)- N 3 through
the terminal alkyne, followed by ATRP of methyl
methacrylate (MMA) was used to generate multivalent,
three-arm star polymers with three different polymers on
each arm.
Reversible Addition Fragmentation Transfer (RAFT)
Since the last review, an enormous increase in publications
combining RAFT with the azide/alkyne click reaction have
been described.[25,101,105,117,118,127–135] As many monomers
(such as N -isopropylacrylamides,[117,130] substituted sty-
renes,[118] hydroxylated methacrylates,[132] and glycosy-
lated methacrylates[129]) are easier to combine with RAFT
than with ATRP or NMP, the RAFT/click methodology
seems to be the method of choice for several polymers in
this context.
As in the case of ATRP, azido-/alkyne-modified RAFT
initiators [25,101,105,127,129–131,135] as well as side-chain
modified monomers[128,131,133] can be used in this strategy.
Whereas azido-modified RAFT-initiators can be used
without detriment to initiate a living polymerization,
which leads to fully endgroup-functionalized telechelic
polymers (proven by MALDI and NMR experiments), there
is a divergence in the literature concerning the use of
acetylene-RAFT initiators. Some authors definitely claim
the necessity to use trimethylsilyl (TMS)-protected ter-minal acetylenes within the monomers[131,133] or initia-
tors[129] for a successful RAFT polymerization (otherwise
observing crosslinking during the polymerization reaction
with the free acetylenes), some authors use unprotected
RAFT initiators for the polymerization of styrene, [101,135]
acrylamides,[101] and vinylacetate.[135] With azido moieties
within the initiator part, the interference is much
lower, since they can be used both within the initiating
RAFT agent[117,127,130] as well as within the sidechain[128]
of the used monomer. In addition, the use of triazole
units within the monomer, close to the growing radical
centre, leads to good results for the final RAFT polymeri-
zation.[134]
An outstanding example for the generation of cyclic
poly( N -isopropylacrylamides) by RAFT/click methods has
been described in high yields (see Table 1, entry 32). [117]
The use of an azido-modified RAFT initiator, subsequent
polymerization of N -isopropylacrylamide, and final trans-
formation of the terminal isobutylsulfanylthiocarbonyl-
sulfanyl moiety into the propargylic moiety by a one-pot
aminolysis/Michael addition sequence is reported.
Although no yield was provided, the publication repre-
sents the first example for the preparation of cyclic
poly( N -isopropylacrylamide).
Ring-Opening Metathesis Polymerization (ROMP) and
Ring-Opening Polymerization (ROP)
ROMP/click methodologies[9,39,75] (see Table 1, entries
40–43) inherently offer an enormously broad aspect in
polymer chemistry, since ROMP chemistry is a simple
and highly efficient approach towards functionalized
polymers, in particular towards block-copolymers. We
have first developed efficient attachment strategies of
various ligands, in particular of supramolecular receptors
(hydrogen-bonding structures) onto poly(oxynorbor-
nenes).[9,74–76] Using oxynorbornenes with pendant azido
and acetylenic units, the copolymerization into either
homo-,[9] block-,[74,76] and statistical copolymers[75] could
be demonstrated. The important aspect of this synthetic
approach lies in the fact that these polymers represent
universal scaffolds for the attachment of supramolecular
units onto the backbone, which allows modulation of the
density, distribution, and thus stickiness on a molecular
scale. Oxynorbornene monomers are advantageous over
the corresponding norbornenes because of their reduced
ring-strain, thus eliminating the concurring dipolar
W. H. Binder, R. Sachsenhofer
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cycloaddition reaction onto the norbornene ring.[16,37] A
very fine example to generate a three-arm star polymer,
based on ROMP and side-chain liquid-crystalline cyclooc-
tene moieties is provided by ref.[136]. Polymerization using
a bis-bromoalkene initiator furnished the bistelechelic
poly(norbornene). Subsequent exchange against the azideand coupling to a central core yielded the final polymeric
star-architecture. Purely thermal strategies have also been
employed also, e.g., see ref.[137]. Recently, these results
were also demonstrated on other poly(norbornene)s using
the same strategy.[138] In addition, a paper on the
preparation of N -heterocyclic carbenes from poly( p-
azidomethylstyrenes) and click reactions have been
described.[139]
Several ROP/click strategies[113,140–148] (see Table 1, i.e.:
entries 46, 60, and 61) have been described recently, either
using an alkyne moiety[143–145] or an a-chlorocapro-
lacton[140–142] as functional monomers or an appropriate
alkyne endgroup.[147] In this way, functionalized poly-
(glycolides),[148] poly(lactides),[146] poly(caprolac-
tones),[140–144,147] poly(oxazolines),[145] and poly(L-valine)-
block-poly(acrylic acid) copolymers[113] have been
successfully prepared.
Anionic and Cationic Polymerization
Few examples that combine living anionic[38,149] and
cationic[45,73,77,145] polymerization reactions with click
reactions have been described (Table 1, entries 45–48).
As shown in Table 1, entry 45, living anionic polymeriza-tion of ethylene oxide has been combined with subsequent
hydroxyl/mesyl/bromide/azide exchange.[38] Interestingly,
the photochemical addition of 2-mercaptoethylamine
onto an allylic bond is described in the presence of the
azido moiety, which represents one of the examples of
successful thiol chemistry in the presence of the azide
moiety without concomitant reduction. Another example
of living anionic polymerization and click chemistry has
been reported with poly( p-propargyloxy styrenes).[149]
With living cationic polymerization, supramolecular
ligands have been fixed onto mono-,[73] bi-, and trivalent
telechelic poly(isobutylenes), prepared by quasi-living
cationic polymerization ( M n ¼3 100 g mol1, M w= M n ¼
1.10).[77] The reaction has been performed in biphasic
reaction systems, featuring toluene/water solvent mix-
tures and CuIBr as the catalyst with yields above 94%,
which demonstrates the high efficiency in heterogeneous
reaction systems. Poly(1,3-oxazolines) using 2-(pent-4-
ynyl)-2-oxazoline as monomer have also been polymerized
by living cationic polymerization and functionalized
by a subsequent click reaction.[145] Furthermore, the
Ni-catalyzed polymerization of alkyne-functionalized iso-
cyanides has been described.[150]
Polyaddition/Polycondensation
A variety of examples have been reported (see Table 1,
entries 49–59), that demonstrate polyaddition[6,70,151–160]
or polycondensation processes in junction with the azide/
alkyne click reaction. In principle, two approaches should
be discerned: a) chain-growth or network-formation bydirect azide/alkyne click reaction[6,152–156,158,161] or b) the
introduction of azide or alkyne groups into the growing
chains[70,151,157] or endgroups by the respective monomer
units for further attachment. Using strategy ‘a’ a variety of
functional polymers such as high glass transition tem-
perature (T g) polymers,[152] metal adhesive polymers,[6,153]
polymers with optical non-linearity,[154,160] organic semi-
conductors,[158] or high temperature-stable polymers[155]
have been prepared. Strategy ‘b’ has been used to
prepare side-chain-functionalized polyurethanes[151]
poly( p-phenylene vinylenes),[157] poly[(4-ethynyl- p-
xylylene)-co-( p-xylylene)]s,[70]
poly(fluorenes),[160]
andpoly(pyrroles).[162]
Gels and networks[6,82,88,136,152,153,159,163–166] have also
been formed by azide/alkyne click reactions. This strategy
has proven useful as a simple crosslinking strategy, but
also for the formation of highly sensitive gel and network
structures not accessible by other methods.[164] As
supramolecularily preorganized molecules often tend to
disintegrate upon thermal treatment, the azide/alkyne
click reactions represent an important step towards stable
networks of defined crosslinking density, thus ‘freezing-in’
a specific supramolecular structure.[88,166]
Click Reactions on Other Polymers
The field of ‘other’ polymers in click chemistry is large and
can be hardly overseen putting all other polymers not
presented in the previous groups into this category.
Thus azide/alkyne click chemistry has been
described vastly with peptides,[59,64,143,150,167–172] carbohy-
drates,[30,31,34,109,111,137,173–184] cellulose,[185] and oligonu-
cleotides,[61,186–188] Suffice to say that the broadness is
enormous and exceeds the scope of this article. Details will
be partly presented in special reviews within this special
issue.
Complex Polymeric Architectures
The beauty and usefulness of the azide/alkyne click
reaction is best demonstrated in the build-up of larger
polymeric structures, in particular the polymeric archi-
tecture. As already mentioned, the field of dendrimers
has been reviewed recently,[29] therefore putting a focus
on the polymeric architecture itself, mentioning
new publications on azide/alkyne click chemistry on
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W. H. Binder, R. Sachsenhofer
Table 2. Overview of ‘click’-reactions for the synthesis of complex polymer architectures.
Entry Polymer/substrate Type Catalyst/conditions Ref.
1 star polymers CuI/TBTA/DIPEA [77]
2 graft-polymer CuBr/PMDETA/THF/DMF [210]
3 star polymers CuSO4.5H2O/sodium
ascorbate/70 -C
[105]
4 tadpole-shaped
polymers
CuI/N(Et)3/THF/35 -C [142]
5 star polymers CuSO4 5H2O/sodium
ascorbate/H2O/r.t.
[203]
6 graft-polymer CuSO4 5H2O/sodium
ascorbate/H2O/MeOH/60 -C
[211]
( Continued )
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‘Click’ Chemistry in Polymer and Material Science: An Update
Entry Polymer/substrate Type Catalyst/conditions Ref.
7 capsule CuSO4 5H2O/sodium
ascorbate
[225]
8 terpolymers CuBr/Me6TREN/DMF/50 -C [100]
9 copolymer Cu(PPh3)3Br/DIPEA/CH2Cl2 [144]
10 graft-polymer [212]
11 rod-coil block
polymers
CuBr/PMDETA/r.t [171]
12 star polymers CuBr/PMDETA [91]
13 block-copolymer CuBr/bipyridine/NMP/r.t [207]
14 CuSO4 5H2O/sodium
ascorbate/70 -C
[92]
15 triblock copolymers CuBr/PMDETA/
DMF/120 -C
[208]
Table 2. (Continued)
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W. H. Binder, R. Sachsenhofer
Entry Polymer/substrate Type Catalyst/conditions Ref.
16 block-copolymer CuBr/bipyridine/THF/r.t. [209]
17 polymer brushes CuBr/PMDETA/DMF [93]
18 multisegmented
block-copolymers
CuBr/PMDETA/DMF/r.t. [95]
19 graft-polymer CuSO4.5H2O/sodium
ascorbate/H2O/CH2Cl2/r.t.
[213]
20 star polymers CuBr/PMDETA/DMF/r.t. [204]
21 star polymers CuBr/PMDETA/DMF/r.t. [126]
( Continued )
Table 2. (Continued)
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‘Click’ Chemistry in Polymer and Material Science: An Update
Entry Polymer/substrate Type Catalyst/conditions Ref.
22 star polymers CuSO4/sodium ascorbate/
100 -C/mW-irradiation
[147]
23 comb polymers CuBr/PMDETA/THF/r.t. [214]
24 star polymers CuI/PMDETA/DMF/80-C [205]
25 graft polymers CuBr/PMDETA/DMF/r.t. [114]
26 dendrimers CuSO4 5H2O/sodium
ascorbate/H2O/THF (1: 4)/r.t.
[221]
Table 2. (Continued)
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W. H. Binder, R. Sachsenhofer
Entry Polymer/substrate Type Catalyst/conditions Ref.
27 dendrimers CuSO4 5H2O/sodium
ascorbate/H2O/THF (1: 4)/r.t.
[202]
28 hyperbranched
polymers
CuSO4 5H2O/sodium
ascorbate/H2O/t BuOH/
hexane (5: 5: 1)/r.t.
[222]
29 dendrimers Cu/CuSO4/TBTA DMF/r.t [223]
30 graft-polymer CuI/DMF/80 -C [215]
31 dendrimers CuBr/PMDETA/THF/r.t. [99]
32 dendrimers CuSO4 5H2O/sodium
ascorbate/H2O/THF/40 -C
[216]
( Continued )
Table 2. (Continued)
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dendrimers[59,99,112,175,189–202] and hyperbranched poly-
mers[5,7,130]
more on the side.The main polymeric architectures available are shown
in Table 2 (see selected formulas for details within
Table 2). It is clearly visible that quite complex polymeric
structures, which bear a large variety of different func
tional groups, can be accessed easily with azide/alkyne
click chemistry. Thus star-polymers,[77,91,105,106,147,203–206]
(block)-copolymers,[92,100,114,144,207–209] multisegmented
block-copolymers,[95] rod-coil-block copolymers,[171] graft-
polymers,[142,210–215] dendrimers,[1,27,29,31,59,99,112,132,133,175,-
177,189,191,194–196,198–202,216–224] polymer-brushes,[93] and
crosslinked capsules[225,226] can be prepared, relying on
the aforementioned living polymerization methods and
subsequent transformations. Yields are often high, putting
these reactions far above others in terms of yield,
efficiency, and easiness. As can be easily judged, nearly
every polymeric architecture is now available by proper
planning and appropriate manpower.
Click Reactions on Surfaces
An interesting aspect of the azide/alkyne click reaction lies
in the fact that a reduced or enforced distance between the
reaction partners leads to a strongly enhanced reaction
rate. This effect has been demonstrated in the azide/alkyneclick reaction within the pocket of enzymes (based protein
profiling (ABPP))[19,36,69,227] by direct microcontact print-
ing,[70,71] or by AFM tips,[72] thus opening the chance for a
sufficiently complete reaction at an interface. Moreover,
since surfaces and interfaces are a chronic source of
incomplete or insufficient chemical reactions, the azide/
alkyne click reaction here definitely has changed the world
of the interfacial scientist, enabling easy access to
functionalized surfaces of reliable and reproducible surface
densities. Thus a large variety of click reactions on
self-assembled monolayers (SAMs),[39,80,132,173,174,228–236]
polymeric surfaces,[45,116,162,185,237,238] layer by layer
assemblies,[238,239] block copolymer (BCP) micelles,[124,125]
polymersomes[240–242] and liposomes[243–245] have been
reported (see Table 3). In the case of SAMs the use
of appropriately azide-[39,101,228–231] or alkyne-
functionalized[132,173,174,232–234] surfaces by direct ligand-
adsorption have been described. Alternatively, in-situ
generation of terminal azides by bromide/azide exchange
directly on the v-bromoalkyl-functional monolayer can be
effected,[231,235] which eliminates the pressing instability
of v-azido-1-thioalkanes prior to the SAM-formation
process. Dynamic or labile assembly structures (such as
‘Click’ Chemistry in Polymer and Material Science: An Update
Entry Polymer/substrate Type Catalyst/conditions Ref.
33 dendrimers CuSO4 5H2O/sodium
ascorbate/H2O/THF
[224]
34 dendrimers CuSO4 5H2O/sodium
ascorbate/H2O/THF/r.t.
[189]
35 dendrimers CuBr/PMDETA/DMF/80 -C [112]
36 block-copolymer CuBr/PMDETA/CH2Cl2/r.t. [241]
Table 2. (Continued)
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W. H. Binder, R. Sachsenhofer
Table 3. Overview of ‘click’ reactions on surfaces, nanoparticles, polymersomes, vesicles, micelles, carbon nanotubes, and resins.
Entry Polymer/substrate Surface Catalyst/conditions Ref.
1 SAM on Au/planar CuSO4 5H2O/sodium
ascorbate/H2O/EtOH
[228]
2 SAM on SiO2/planar thermal/70 -C/neat [231]
3 SAM on Au/planar CuSO4 5H2O/sodium
ascorbate/H2O/EtOH
[232]
4 SAM on Au/planar CuSO4 5H2O/sodium
ascorbate and
Cu(Ph3)3Br/H2O/EtOH
[39]
5 SAM on Au/planar CuSO4 5H2O/sodium
ascorbate/H2O/EtOH
and DMSO/H2O
[229]
6 SAM on SiO2/planar no catalyst/r.t./m-contact
printing
[233]
7 SAM on Au/planar TBTA CuBF4/hydroquinone/
DMSO/H2O
[230]
8 porous Si CuSO4/ascorbic acid,MeCN/
tris-buffer/pH 8.0/r.t.
[234]
9 SAM on Au/planar CuSO4/sodium ascorbate/
H2O/EtOH
[174]
10 SAM on glass CuSO4 5H2O/TBTA/TCEP/
PBS-buffer/t BuOH/4 -C
[173]
11 SAM on Au-nanoparticles
1,8W0,4 nm
dioxane/hexane/r.t. [80]
12 SAM on SiO2/planar CuSO4 5H2O/sodium
ascorbate
[235]
13 SAM on SiO2/planar CuSO4 5H2O/sodium
ascorbate/DMSO/50 -C
[101]
14 SAM on Au/planar CuSO4 5H2O/sodium
ascorbate/r.t.
[116]
( Continued )
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‘Click’ Chemistry in Polymer and Material Science: An Update
Entry Polymer/substrate Surface Catalyst/conditions Ref.
15 liposome CuSO4 5H2O/sodium
ascorbate/H2O
[243]
16 polymersomes CuSO4 5H2O/sodium
ascorbate/TBTA
[240]
17 bionanoparticle/virus CuBr/PCDS [257]
18 liposome CuSO4/sodium ascorbate/
HEPES-buffer/pH¼6.5
[245]
19 liposome CuBr/H2O [244]
20 polymer layer AFM-tip/225 -C [237]
21 responsive polymer
click capsules
CuSO4 5H2O/sodium
ascorbate
[238]
22 layer by layer (LbL) film
of polymer
CuSO4 5H2O/sodium
ascorbate/H2O
[239]
Table 3. (Continued)
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W. H. Binder, R. Sachsenhofer
Entry Polymer/substrate Surface Catalyst/conditions Ref.
23 surface-functionalized
micelles
CuSO4.5H2O/sodium
ascorbate/H2O/r.t.
[125,124]
24 CdSe-NP CuBr [80]
25 CdSe-NP CuBr/TBTA/DIPEA or DT [78]
26 Fe2O3-NP DT /toluene [79]
27 Fe2O3-NP CuSO4 [256]
28 SAM on
Au-nanoparticles
dioxane/hexane/r.t. [254]
29 SAM on
Au-nanoparticles
CuI/r.t. [255]
30 Au-nanorods CuSO4/ascorbic acid/4 -C [258]
31 SWNT- nanocomposites CuI [247]
( Continued )
Table 3. (Continued)
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‘Click’ Chemistry in Polymer and Material Science: An Update
Entry Polymer/substrate Surface Catalyst/conditions Ref.
32 SWNT- nanocomposites CuI [246]
33 self-separating
homogeneous
CuI catalysts
CuCl/heptane/EtOH [45]
34 CuI/NEt3/THF [198]
35 cotton surface CuBr/ N -(n-propyl)-2-
pyridylmethanimine/
toluene/70 -C
[110]
36 Wang resins Cu(PPh3)3Br/DIPEA/DMSO/60 -C [111]
37 enantioselectivecatalysts
on resins
CuI/DIPEA/
DMF:H2O (1: 1)/35 -C
[250]
38 Merrifield resins CuI/DIPEA/DMF/H2O/40 -C [251]
39 pybox resins CuI/DIEA/THF/35-
C [252]
Table 3. (Continued)
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polymersomes, BCP micelles, and liposomes) offer either a
direct approach to modify the already existing surface of
the assembly,[124,125,240,244] or to modify the molecule by
click reaction before the assembly.[241,242,245] The latter
strategy is definitely less elegant, but sometimes more
efficient.
Grafting-to[101,110,236] and grafting-from[81,116] tech-
niques have been employed to effect the attachment of
polymers onto surfaces. Moreover, the reaction has been
extended to carbon nanotubes[246–248] and fullerenes,[249]
solid resins,[111,172,197,250–253] colloidal polymer parti-
cles,[226] and nanoparticles.[78–81,246,254–256] Thus a large
variety of nanoparticles (Au,[80,246,254,255] CdSe,[78]
Fe2O3,[79,81,256] SiO2
[101]) as well as viruses[257] and
Au-nanorods[258] have been surface-functionalized by this
method. Compared to conventional surface-modification
methods, the azide/alkyne methodology enables an
elegant, fast, and efficient approach to functionalized
nanoparticles in a simple mode. An important point has
been observed upon comparing the CuI-catalyzed reaction
with the uncatalyzed, purely thermal click reaction on
CdSe nanoparticles[78] without the use of the CuI catalyst,
the photoluminescence of the final, surface-modified CdSe
nanoparticles remains nearly unchanged, whereas
under CuI catalysis a significant drop in the quantum
yield is observed. Therefore, the purely thermal azide/
alkyne reaction may sometimes be advantageous over the
metal-catalyzed click process.
Conclusion and Outlook
Click chemistry, in particular azide/alkyne click chemistry,
has advanced and found its way into the chemists’ mind.
W. H. Binder, R. Sachsenhofer
Entry Polymer/substrate Surface Catalyst/conditions Ref.
40 functionalized
cross-linked solid
supports
CuBr/PMDETA/DMF/80-C [197]
41 5-substituted tetrazoles toluene/–40 to 120 -C [17]
42 pH sensitive releasing
systems
CuSO4 5H2O/sodium ascorbate/
t -BuOH:H2O (1: 1)
[52]
43 polysaccharides CuSO4 5H2O/sodium
ascorbate/DMSO/r.t.
[185]
44 polymersomes CuSO4.5H2O/sodium
ascorbate/
bathophenanthroline/4 -C
[241]
Table 3. (Continued)
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As with many novel and unconventional approaches (to
cite ‘combinatorial chemistry’ as one prominent example)
the reaction has had its ‘induction period’, and subse-
quently its royal uprise and present general acceptance in
chemistry. Given the short period between discovery to the
present, the reaction has been radically revolutionizing theway organic, material, surface, and in particular polymer
chemists will approach future projects and experiments.
Using azide/alkyne click chemistry, not only more, but
also more complex molecules and materials can now be
approached in cases where in earlier times longer
experiments and planning had been required. With
azide/alkyne click chemistry in hand, polymer chemistry
now approaches the level of small-molecule organic
chemistry in terms of functional broadness, structural
integrity, and molecular addressability. This alone suffices
as the outlook.
In the close future, however, another question will more
urgently press us polymer chemists: ‘‘Useful or not
Useful?’’—It might be this change-in-mind, rather than
the ‘‘New or not New’’ question that remains and will be
posed for a longer period in our hastily changing scientific
world.
Acknowledgements: The authors are thankful for the grant FWF 18740 B03 for financial support.
Received: February 11, 2008; Revised: March 31, 2008; Accepted:March 31, 2008; DOI: 10.1002/marc.200800089
Keywords: 1,3-dipolar cycloaddition; azide/alkyne ‘click’ reac-
tion; polymerization (general); surfaces
[1] W. H. Binder, R. Sachsenhofer, Macromol. Rapid Commun.2007, 28, 15.
[2] M. Meldal, C. W. Tornoe, ‘‘Peptides, The wave of the Future’’in: Proceedings of the Second International and the Seven-teenthAmerican Peptide Symposium, M. lebl, R. A. Houghten,Eds., American Peptide Society, San Diego 2001, p. 263.
[3] C. W. Tornoe, C. Christensen, M. Meldal, J. Org. Chem. 2002,67 , 3057.
[4] V. V. Rostovtsev, L. G. Green, V. V. Fokin, K. B. Sharpless, Angew. Chem. Int. Ed. 2002, 41, 2596.[5] M. Smet, K. Metten, W. Dehaen, Collect. Czech. Chem. Com-
mun. 2004, 69, 1097.[6] D. D. Dı́az, S. Punna, P. Holzer, A. K. McPherson, K. B. Sharp-
less, V.V. Fokin,M. G. Finn, J. Polym. Sci., Part A: Polym. Chem.2004, 42, 4392.
[7] A. J. Scheel, H. Komber, B. I. Voit, Macromol. Rapid Commun.2004, 25, 1175.
[8] B. Helms, J. L. Mynar, C. J. Hawker, J. M. J. Frechet, J. Am.Chem. Soc. 2004, 126, 15020.
[9] W. H. Binder, C. Kluger, Macromolecules 2004, 37 , 9321.[10] N. V. Tsarevsky, K. V. Bernaerts, B. Dufour, F. E. DuPrez,
K. Matyjaszewski, Macromolecules 2004, 37 , 9308.[11] K. Matyjaszewski, A. E. Müller, Progr. Polym. Sci. 2007, 32, see
whole issue on ‘‘50 Years of Living Polymerization’’.[12] H. C. Kolb, M. G. Finn, K. B. Sharpless, Angew. Chem. Int. Ed.
2001, 40, 2004.[13] Z. P. Demko, K. B. Sharpless, J. Org. Chem. 2001, 66, 7945.
[14] Z. P. Demko, K. B. Sharpless, Org. Lett. 2001, 3, 4091.[15] R. Huisgen, Pure Appl. Chem. 1989, 61, 613.[16] R. Huisgen, G. Szeimies, L. Möbius, Chem. Ber. 1967, 100,
2494.[17] V. Aureggi, G. Sedelmeier, Angew. Chem. Int. Ed. 2007, 46,
8440.[18] Z. P. Demko, K. B. Sharpless, Angew. Chem. Int. Ed. 2002, 41,
2110.[19] W. G. Lewis, L. G. Green, F. Grynszpan, Z. Radic, P. R. Carlier,
P. Taylor, M. G. Finn, K. B. Sharpless, Angew. Chem. Int. Ed.2002, 41, 1053.
[20] G. W. Goodall, W. Hayes, Chem. Soc. Rev. 2006, 35, 280.[21] K. Ruck-Braun, T. H. E. Freysoldt, F. Wierschem, Chem. Soc.
Rev. 2005, 34, 507.[22] V. D. Bock, H. Hiemstra, J. H. v. Maarseveen, Eur. J. Org. Chem.
2006, 2006, 51.[23] H. Nandivada, X. Jiang, J. Lahann, Adv. Mater. 2007, 19,
2197.[24] L. Jean-François, Angew. Chem. Int. Ed. 2007, 46, 1018.[25] L. Barner, T. P. Davis, M. H. Stenzel, C. Barner-Kowollik,
Macromol. Rapid Commun. 2007, 28, 539.[26] D. Fournier, R. Hoogenboom, U. S. Schubert, Chem. Soc. Rev.
2007, 36, 1369.[27] R. A. Evans, Aust. J. Chem. 2007, 60, 384.[28] W. H. Binder, C. Kluger, Curr. Org. Chem. 2006, 10, 1791.[29] B. Voit, New J. Chem. 2007, 31, 1139.[30] S. Dedola, S. A. Nepogodiev, R. A. Field, Org. Biomol. Chem.
2007, 5, 1006.[31] D. Alessandro, Chem. Asian J. 2007, 2, 700.[32] S. G. Spain, M. I. Gibson, N. R. Cameron, J. Polym. Sci., Part A:
Polym. Chem. 2007, 45, 2059.[33] M. V. Gil, M. J. Arévalo, Ó. López, Synthesis 2007, 1589.[34] Y. L. Angell, K. Burgess, Chem. Soc. Rev. 2007, 36, 1674.[35] H. C. Kolb, K. B. Sharpless, Drug Discovery Today 2003, 8,
1128.[36] V. P. Mocharla, B. Colasson, L. V. Lee, S. Röper, K. B. Sharpless,
C.-H. Wong, H. C. Kolb, Angew. Chem. Int. Ed. 2005, 44, 116.[37] P. Scheiner, J. H. Schomaker, S. Deming, W. J. Libbey, G. P.
Nowack, J. Am. Chem. Soc. 1965, 87 , 306.[38] S. Hiki, K. Kataoka, Bioconjugate Chem. 2007, 18, 2191.[39] R. Zirbs, F. Kienberger, P. Hinterdorfer, W. H. Binder, Lang-
muir 2005, 21, 8414.[40] G. Molteni, C. I. Bianchi, G. Marinoni, N. Santo, A. Ponti, New
J. Chem. 2006, 30, 1137.[41] L. D. Pachón, J. H. van Maarseveen, G. Rothenberg, Adv.
Synth. Catal. 2005, 347 , 811.[42] H.A. Orgueira,D. Fokas,Y. Isome, P. C.M. Chan,C. M.Baldino,
Tetrahedron Lett. 2005, 46, 2911.[43] M. B. Thathagar, J. Beckers, G. Rothenberg, J. Am. Chem. Soc.
2002, 124, 11858.[44] B. H. Lipshutz, B. R. Taft, Angew. Chem. Int. Ed. 2006, 45,
8235.[45] D. E. Bergbreiter, P. N. Hamilton, N. M. Koshti, J. Am. Chem.
Soc. 2007, 129, 10666.[46] J. M. Baskin, J. A. Prescher, S. T. Laughlin, N. J. Agard, P. V.
Chang, I. A. Miller, A. Lo, J. A. Codelli, C. R. Bertozzi, Proc. Natl. Acad. Sci. 2007, 104, 16793.
‘Click’ Chemistry in Polymer and Material Science: An Update
Macromol. Rapid Commun. 2008, 29 , 952–981 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.mrc-journal.de 977
-
8/15/2019 Chemistry in Polymer and Material
27/30
[47] X. Ning, J. Guo, M. A. Wolfert, G.-J. Boons, Angew. Chem. Int. Ed. 2008, 47 , 2253.
[48] J.-C. Meng, V. V. Fokin, M. G. Finn, Tetrahedron Lett.2005, 46,4543.
[49] W. G. Lewis, F. G. Magallon, V. V. Fokin, M. G. Finn, J. Am.Chem. Soc. 2004, 126, 9152.
[50] P. L. Golas, N. V. Tsarevsky, B. S. Sumerlin, K. Matyjaszewski, Macromolecules 2006, 39, 6451.[51] Y. Angell, K. Burgess, Angew. Chem. Int. Ed. 2007, 46, 3649.[52] P. Bertrand, J. P. Gesson, J. Org. Chem. 2007, 72, 3596.[53] L. Zhang, X. Chen, P. Xue, H. H. Y. Sun, I. D. Williams, K. B.
Sharpless, V. V. Fokin, G. Jia, J. Am. Chem. Soc. 2005, 127 ,15998.
[54] S. Oppilliart, G. Mousseau, L. Zhang, G. Jia, P. Thuery, B.Rousseau, J.-C. Cintrat, Tetrahedron 2007, 63, 8094.
[55] D. V. Partyka, J. B. Updegraff, M. Zeller, A. D. Hunter, T. G.Gray, Organometallics 2007, 26, 183.
[56] C. Chowdhury, S. B. Mandal, B. Achari, Tetrahedron Lett.2005, 46, 8531.
[57] B. Khanetskyy, D. Dallinger, C. O. Kappe, J. Comb. Chem.2004, 6, 884.
[58] P. Appukkuttan, W. Dehaen, V. V. Fokin, E. VanderEycken,Org. Lett. 2004, 6, 4223.
[59] D. T. S. Rijkers, G. W. v. Esse, R. Merkx, A. J. Brouwer, H. J. F.Jacobs, R. J. Pieters, R. M. J. Liskamp, Chem. Commun. 2005,4581.
[60] Y. Wang, Z. Iqbal, S. Mitra, Carbon 2005, 43, 1015.[61] C. Bouillon, A. Meyer, S. Vidal, A. Jochum, Y. Chevolot, J. P.
Cloarec, J. P. Praly, J. J. Vasseur, F. Morvan, J. Org. Chem. 2006,71, 4700.
[62] J. Li, H. Grennberg, Chem. Eur. J. 2006, 12, 3869.[63] V. O. Rodionov, V. V. Fokin, M. G. Finn, Angew. Chem. Int. Ed.
2005, 44, 2210.[64] S. Punna, J. Kuzelka, Q. Wang, M. G. Finn, Angew. Chem. Int.
Ed. 2005, 44, 2215.[65] G. Molteni, A. Ponti, Chem. Eur. J. 2003, 9, 2770.
[66] F. Himo, T. Lovell, R. Hilgraf, V. V. Rostovtsev, L. Noodleman,K. B. Sharpless, V. V. Fokin, J. Am. Chem. Soc. 2005, 127 , 210.
[67] B. F. Straub, Chem. Commun. 2007, 3868.[68] J.-C. Meng, G. Siuzdak, M. G. Finn, Chem. Commun. 2004,
2108.[69] J. Wang, G. Sui, V. P. Mocharla, R. J. Lin, M. E. Phelps,
H. C. Kolb, H.-R. Tseng, Angew. Chem. Int. Ed. 2006, 45,5276.
[70] H. Nandivada, H.-Y. Chen, L. Bondarenko, J. Lahann, Angew.Chem. Int. Ed. 2006, 45, 3360.
[71] D. I. Rozkiewicz, D. Janczewski, W. Verboom, B. J. Ravoo,D. N.Reinhoudt, Angew. Chem. Int. Ed. 2006, 45, 5292.
[72] D. A. Long, K. Unal, R. C. Pratt, M. Malkoch, J. Frommer, Adv. Mater. 2007, 19, 4471.
[73] W. H. Binder, D. Machl, C. Kluger, Polym. Prepr. (Am. Chem.
Soc. Div. Polym. Chem.) 2004, 45, 692.[74] W. H. Binder, C. Kluger, C. J. Straif, G. Friedbacher, Macro-
molecules 2005, 38, 9405.[75] W. H. Binder, C. Kluger, M. Josipovic, C. J. Straif, G.
Friedbacher, Macromolecules 2006, 39, 8092.[76] C. Kluger, W. H. Binder, J. Polym. Sci., Part A: Polym. Chem.
2007, 45, 485.[77] W. H. Binder, L. Petraru, T. Roth, P. W.Groh, V. Pálfi, S. Keki, B.
Ivan, Adv. Funct. Mater. 2007, 17 , 1317.[78] W. H. Binder, R. Sachsenhofer, C. J. Straif, R. Zirbs, J. Mater.
Chem. 2007, 17 , 2125.[79] W. H. Binder, H. C. Weinstabl, Monatsh. Chem. 2007,
138, 315.
[80] W. H. Binder, L. Petraru, R. Sachenshofer, R. Zirbs, Monatsh.Chem. 2006, 137 , 835.
[81] W. H. Binder, D. Gloger, H. Weinstabl, G. Allmaier, E. Pitte-nauer, Macromolecules 2007, 40, 3097.
[82] D. A. Ossipov, J. Hilborn, Macromolecules 2006, 39, 1709.[83] N. V. Tsarevsky, B. Dufour, K. Matyjaszewski, PMSE Prepr.
2004, 45, 1065.[84] J.-F. Lutz, H. G. Börner, K. Weichenhan, Macromol. RapidCommun. 2005, 26, 514.
[85] J. A. Opsteen, J. C. M. v. Hest, Chem. Commun. 2005, 57.[86] B. S. Sumerlin, N. V. Tsarevsky, G. Louche, R. Y. Lee, K.
Matyjaszewski, Macromolecules 2005, 38, 7540.[87] H. Gao, K. Matyjaszewski, Macromolecules 2006, 39, 4960.[88] J. A. Johnson, D. R. Lewis, D. D. Diaz, M. G. Finn, J. T.
Koberstein, N. J. Turro, J. Am. Chem. Soc. 2006, 128, 6564.[89] B. A. Laurent, S. M. Grayson, J. Am. Chem. Soc. 2006, 128,
4238.[90] J. F. Lutz, H. G. Borner,K. Weichenhan, Macromolecules2006,
39, 6376.[91] G. Deng, D. Ma, Z. Xu, Eur. Polym. J. 2007, 43, 1179.[92] B. L. Droumaguet,G. Mantovani, D. M. Haddleton, K. Velonia,
J. Mater. Chem. 2007, 17 , 1916.[93] H. Gao, K. Matyjaszewski, J. Am. Chem. Soc. 2007, 129, 6633.[94] H. Gao, K. Min, K. Matyjaszewski, Macromol. Chem. Phys.
2007, 208, 1370.[95] P. L. Golas, N. V. Tsarevsky, B. S. Sumerlin, L. M. Walker, K.
Matyjaszewski, Aust. J. Chem. 2007, 60, 400.[96] E. Gungor, G. Cote, T. Erdogan, H. D. A. L. Demirel, G. Hizal, U.
Tunca, J. Polym. Sci., Part A: Polym. Chem. 2007, 45, 1055.[97] X. Jiang, M. C. Lok, W. E. Hennink, Bioconjugate Chem. 2007,
18, 2077.[98] J. A. Johnson, M. G. Finn, J. T. Koberstein, N. J. Turro, Macro-
molecules 2007, 40, 3589.[99] Q. Liu, P. Zhao, Y. Chen, J. Polym. Sci., Part A: Polym. Chem.
2007, 45, 3330.[100] J. A. Opsteen, J. C. M. v. Hest, J. Polym. Sci., Part A: Polym.
Chem. 2007, 45, 2913.[101] R. Ranjan, W. J. Brittain, Macromolecules 2007, 40, 6217.[102] N. V. Tsarevsky, S. A. Bencherif, K. Matyjaszewski, Macro-
molecules 2007, 40, 4439.[103] W. Van Camp, V. Germonpre, L. Mespouille, P. Dubois, E. J.
Goethals, F. E. Du Prez, React. Funct. Polym. 2007, 67 , 1168.[104] J. Xu, J. Ye, S. Liu, Macromolecules 2007, 40, 9103.[105] J. Zhu, X. Zhu, E. T. Kang, K. G. Neoh, Polymer 2007, 48, 6992.[106] N. V. Tsarevsky, B. S. Sumerlin, K. Matyjaszewski, Macro-
molecules 2005, 38, 3558.[107] H. Gao, G. Louche, B. S. Sumerlin, N. Jahed, P. Golas, K.
Matyjaszewski, Macromolecules 2005, 38, 8979.[108] A. J. Dirks, S. S. v. Berkel, N. S. Hatzakis, J. A. Opsteen, F. L. v.
Delft, J. J. L. M. Cornelissen, A. E. Rowan, J. C. M. v. Hest, F. P.J. T. Rutjes, R. J. M. Nolte, Chem. Commun. 2005, 4172.
[109] V. Ladmiral, G. Mantovani, G. J. Clarkson, S. Cauet, J. L. Irwin,D. M. Haddleton, J. Am. Chem. Soc. 2006, 128, 4823.
[110] G. Chen, L. Tao, G. Mantovani, V. Ladmiral, D. P. Burt, J. V.Macpherson, D. M. Haddleton, Soft Matter 2007, 3, 732.
[111] G. Chen, L. Tao, G. Mantovani, J. Geng, D. Nystrom, D. M.Haddleton, Macromolecules 2007, 40, 7513.
[112] C. N. Urbani, C. A. Bell, D. Lonsdale, M. R. Whittaker, M. J.Monteiro, Macromolecules 2008, 41, 76.
[113] A.Sinaga, P.Ravi, T.A. Hatton, K. C.Tam, J. Polym. Sci., Part A: Polym. Chem. 2007, 45, 2646.
[114] A. P. Vogt, B. S. Sumerlin, Macromolecules 2006, 39, 5286.[115] G. Mantovani, V. Ladmiral, L. Tao, D. M. Haddleton, Chem.
Commun. 2005, 2089.
W. H. Binder, R. Sachsenhofer
978
Macromol. Rapid Commun. 2008 , 29 , 952–981
2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/marc.200800089
-
8/15/2019 Chemistry in Polymer and Material
28/30
[116] B.S. Lee,J. K.Lee, W.J. Kim,Y. H.Jung, S.J. Sim,J. Lee,I. S.Choi, Biomacromolecules 2007, 8, 744.
[117] X. P. Qiu, F. Tanaka, F. M. Winnik, Macromolecules 2007, 40,7069.
[118] R. K. O’Reilly, M. J. Joralemon, C. J. Hawker, K. L. Wooley,Chem. Eur. J. 2006, 12, 6776.
[119] D. Gromadzki, J. Lokaj, P. Cernoch, O. Diat, F. Nallet, P.Stepanek, Eur. Polym. J. 2008, 44, 189.[120] B. Sieczkowska, M. Millaruelo, M. Messerschmidt, B. Voit,
Macromolecules 2007, 40, 2361.[121] B. Gacal, H. Durmaz, M. A. Tasdelen, G. Hizal, U. Tunca, Y.
Yagci, A. L. Demirel, Macromolecules 2006, 39, 5330.[122] M. Malkoch, R. J. Thibault, E. Drockenmuller, M. Messersch-
midt, B. Voit, T. P. Russell, C. J. Hawker, J. Am. Chem. Soc.2005, 127 , 14942.
[123] S. Fleischmann, H. Komber, D. Appelhans, B. I. Voit, Macro-mol. Chem. Phys. 2007, 208, 1050.
[124] R. K. O’Reilly, M. J. Joralemon, K. L. Wooley, C. J. Hawker,Chem. Mater. 2005, 17 , 5976.
[125] R. K. O’Reilly, M. J. Joralemon, C. J. Hawker, K. L. Wooley, J. Polym. Sci., Part A: Polym. Chem. 2006, 44, 5203.
[126] O. A. Tintas, G. Hizal, U. Tunca, J. Polym. Sci., Part A: Polym.Chem. 2006, 44, 5699.
[127] S. R. Gondi, A. P. Vogt, B. S. Sumerlin, Macromolecules 2007,40, 474.
[128] Y. Li, J. Yang, B. C. Benicewicz, J. Polym. Sci., Part A: Polym.Chem. 2007, 45, 4300.
[129] S. R. S. Ting, A. M. Granville, D. Quemener, T. P. Davis,M. H. Stenzel, C. Barner-Kowollik, Aust. J. Chem. 2007, 60,405.
[130] A. P. Vogt, S. R. Gondi, B. S. Sumerlin, Aust. J. Chem. 2007, 60,396.
[131] D. Quémener, M. L. Hellaye, C. Bissett, T. P. Davis, C. Bar-ner-Kowollik, M. H. Stenzel, J. Polym. Sci., Part A: Polym.Chem. 2008, 46, 155.
[132] R. Vestberg, M. Malkoch, M. Kade, P. Wu, V. V. Fokin, K. B.
Sharpless, E. Drockenmuller, C. J. Hawker, J. Polym. Sci., Part A: Polym. Chem. 2007, 45, 2835.
[133] R. K. O’Reilly, M. J. Joralemon, C. J. Hawker,K. L. Wooley, New J. Chem. 2007, 31, 718.
[134] R. J. Thibault, K. Takizawa, P. Lowenheilm, B. Helms, J. L.Mynar, J. M. J. Frechet, C. J. Hawker, J. Am. Chem. Soc. 2006,128, 12084.
[135] D. Quemener, T. P. Davis, C. Barner-Kowollik, M. H. Stenzel,Chem. Commun. 2006, 5051.
[136] Y. Xia, R. Verduzco, R. H. Grubbs, J. A. Kornfield, J. Am. Chem.Soc. 2008, 130, 1735.
[137] J. J. Murphy, K. Nomura, R. M. Paton, Macromolecules 2006,39, 3147.
[138] S. K. Yang, M. Weck, Macromolecules 2008, 41, 346.[139] D. J. Coady, C. W. Bielawski, Macromolecules 2006, 39, 8895.
[140] R. Riva, S. Schmeits, F. Stoffelbach, C. Jerome, R. Jerome, P.Lecomte, Chem. Commun. 2005, 5334.
[141] P. Lecomte, R. Riva, S. Schmeits, J. Rieger, K. Van Butsele, C.Jérôme, R. Jérôme, Macromol. Symp. 2006, 240, 157.
[142] H.Li, R. Riva, R. Jerome, P. Lecomte, Macromolecules2007, 40,824.
[143] B. Parrish, R. B. Breitenkamp, T. Emrick, J. Am. Chem. Soc.2005, 127 , 7404.
[144] B. Parrish, T. Emrick, Bioconjugate Chem. 2007, 18, 263.[145] R. Luxenhofer, R. Jordan, Macromolecules 2006, 39, 3509.[146] Q. Shi, X. Chen, T. Lu, X. Jing, Biomaterials 2008, 29, 1118.[147] R. Hoogenboom, B. C. Moore, U. S. Schubert, Chem. Commun.
2006, 4010.
[148] X. Jiang, E. B. Vogel, M. R. Smith, G. L. Baker, Macromolecules2008, 41, 1937.
[149] A. D. Thomsen, E. Malmström, S. Hvilsted, J. Polym. Sci., Part A: Polym. Chem. 2006, 44, 6360.
[150] E. Schwartz, H. J. Kitto, Rd. Gelder, R. J. M. Nolte, A. E. Rowan,J. J. L. M. Cornelissen, J. Mater. Chem. 2007, 17 , 1876.
[151] Z. Li, Q. Zeng, S. Dong, Z. Zhu, Q. Li, C. Ye, C. Di, Y. Liu, J. Qin, Macromolecules 2006, 39, 8544.[152] N. L. Baut, D. D. Diaz, S. Punna, M. G. Finn, H. R. Brown,
Polymer 2007, 48, 239.[153] Y. Liu, D. D. Dı́az, A. A. Accurso, K. B. Sharpless, V. V. Fokin,
M. G. Finn, J. Polym. Sci., Part A: Polym. Chem. 2007, 45,5182.
[154] A. Qin, C. K. W. Jim, W. Lu, J. W. Y. Lam, M. Haussler, Y. Dong,H. H. Y. Sung, I. D. Williams, G. K. L. Wong, B. Z. Tang,
Macromolecules 2007, 40, 2308.[155] Y. Zhu, Y. Huang, W.-D. Meng, H. Li, F.-L. Qing, Polymer 2006,
47 , 6272.[156] V. Aucagne, D. A. Leigh, Org. Lett. 2005, 8, 4505.[157] B. C. Englert, S. Bakbak, U. H. F. Bunz, Macromolecules 2005,
38, 5868.
[158] S. Bakbak, P. J. Leech, B. E. Carson, S. Saxena, W. P. King,U. H. F. Bunz, Macromolecules 2006, 39, 6793.
[159] A. R. Katritzky, N. K. Meher, S. Hanci, R. Gyanda, S. R. Tala, S.Mathai, R. S. Duran, S. Bernard, F. Sabri, S. K. Singh, J.Doskocz, D. A. Ciaramitaro, J. Polym. Sci., Part A: Polym.Chem. 2008, 46, 238.
[160] Za. Li, Q.Zeng,G. Yu, Z.Li,C. Ye, Y.Liu, J.Qin, Macromol. RapidCommun. 2008, 29, 136.
[161] D. J. V. C. v. Steenis, O. R. P. David, G. P. F. v. Strijdonck, J. H. v.Maarseveen, J. N. H. Reek, Chem. Commun. 2005, 4333.
[162] Y.Li, W.Zhang,J. Chang, J. Chen,G. Li, Y. Ju, Macromol. Chem. Phys. 2008, 209, 322.
[163] M. Malkoch, R. Vestberg, N. Gupta, L. Mespouille, P. Dubois,A. F. Mason, J. L. Hedrick, Q. Liao, C. W. Frank, K. Kingsbury,C. J. Hawker, Chem. Commun. 2006, 2774.
[164] D. D. Diaz, K. Rajagopal, E. Strable, J. Schneider, M. G. Finn, J. Am. Chem. Soc. 2006, 128, 6056.
[165] P. Screenivas, D. D. Diaz, L. Chunmei, K. B. Sharpless, V. V.Fokin, M. G. Finn, PMSE Prepr. 2004, 45, 778.
[166] D. D. Diaz, J. J. Marrero Tellado, D. G. Velazquez, A. G. Ravelo,Tetrahedron Lett. 2008, 49, 1340.
[167] W. S. Horne, M. K. Yadav, C. D. Stout, M. R. Ghadiri, J. Am.Chem. Soc. 2004, 126, 15366.
[168] W. S. Horne, C. D. Stout, M. R. Ghadiri, J. Am. Chem. Soc. 2003,125, 9372.
[169] M. Salvati, F. M. Cordero, F. Pisaneschi, F. Bucelli, A. Brandi,Tetrahedron 2005, 61, 8836.
[170] C. D. Tatko, M. L. Waters, J. Am. Chem. Soc. 2002, 124,9372.
[171] W. Agut, D. Taton, S. Lecommandoux, Macromolecules 2007,
40, 5653.[172] J. M. Holub, H. Jang, K. Kirshenbaum, Org. Biomol. Chem.
2006, 4, 1497.[173] X. L. Sun, C. L. Stabler, C. S. Cazalis, E. L. Chaikof, Bioconjugate
Chem. 2006, 17 , 52.[174] Y. Zhang, S. Luo, Y. Tang, L. Yu, K. Y. Hou, J. P. Cheng, X. Zeng,
P. G. Wang, Anal. Chem. 2006, 78, 2001.[175] E. Fernandez-Megia, J. Correa, I. Rodriguez-Meizoso, R.
Riguera, Macromolecules 2006, 39, 2113.[176] S. Hotha, S. Kashyap, J. Org. Chem. 2006, 71, 364.[177] E. Fernandez-Megia, J. Correa, R. Riguera, Biomacromolecules
2006, 7 , 3104.[178] J.-F. Lutz, H. G. Borner, Progr. Polym. Sci. 2008, 33, 1.
‘Click’ Chemistry in Polymer and Material Science: An Update
Macromol. Rapid Commun. 2008, 29 , 952–981 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.mrc-journal.de 979
-
8/15/2019 Chemistry in Polymer and Material
29/30
[179] J. M. Langenhahn, J. S. Thorson, Curr. Org. Synth. 2005, 2, 59.[180] S. Dorner, B. Westermann, Chem. Commun. 2005, 2852.[181] F. Fazio, M. C. Bryan, O. Blixt, J. C. Paulson, C. H. Wong, J. Am.
Chem. Soc. 2002, 124, 14397.[182] Q. Chen, F. Yang, Y. Du, Carbohydr. Res. 2005, 340, 2476.[183] T. Hasegawa, M. Umeda, M. Numata, C. Li, A.-H. Bae, T.
Fujisawa,S. Haraguchi, K. Sakurai, S. Shinkai, Carbohydr.Res.2006, 341, 35.
[184] V. Crescenzi, L. Cornelio, C. DiMeo, S. Nardecchia, R.Lamanna, Biomacromolecules 2007, 8, 1844.
[185] T. Liebert, C. Hänsch, T. Heinze, Macromol. Rapid Commun.2006, 27 , 208.
[186] J. Gierlich, G. A. Burley,P. M. E. Gramlich, D. M. Hammond, T.Carell, Org. Lett. 2006, 8, 3639.
[187] N. Minakawa, Y. Ono, A. Matsuda, J. Am. Chem. Soc. 2003,125, 11545.
[188] T. S. Seo, Z. Li, H. Ruparel, J. Ju, J. Org. Chem. 2003, 68, 609.[189] C. Ornelas, J. Ruiz Aranzaes, E. Cloutet, S. Alves, D. Astruc,
Angew. Chem. Int. Ed. 2007, 46, 872.[190] J. W. Lee, B. K. Kim, H. J. Kim, S. C. Han, W. S. Shin, S. H. Jin,
Macromolecules 2006, 39, 2418.
[191] S. Svenson, D. A. Tomalia, Adv. Drug Delivery Rev. 2005, 57 ,2106.
[192] P. Wu, A. K. Feldman, A. K. Nugent, C. J. Hawker, A. Scheel, B.Voit, J. Pyun, J. M. J. Fréchet, K. B. Sharpless, V. V. Fokin,
Angew. Chem. Int. Ed. 2004, 43, 3928.[193] P. Wu, A. K. Feldman, A. K. Nugent, C. J. Hawker, A. Scheel, B.
Voit, J. Pyun, J. M. J. Fréchet, K. B. Sharpless, V. V. Fokin, Angew. Chem. 2004, 116, 4018.
[194] J.W. Lee,B. K.Kim, J.H. Kim,W. S.Shin,S. H.Jin, J. Org. Chem.2006, 71, 4988.
[195] J. Lenoble, N. Maringa, S. Campidelli, B. Donnio, D. Guillon, R.Deschenaux, Org. Lett. 2006, 8, 1851.
[196] P. Wu, M. Malkoch, J. N. Hunt, R. Vestberg, E. Kaltgrad, M. G.Finn, V. V. Fokin, K. B. Sharpless, C. J. Hawker, Chem. Com-mun. 2005, 5775.
[197] C. N. Urbani, C. A. Bell, D. E. Lonsdale, M. R. Whittaker, M. J.Monteiro, Macromolecules 2007, 40, 7056.
[198] A. Gissibl, C. Padie, M. Hager, F. Jaroschik, R. Rasappan, E.Cuevas-Yanez, C. O. Turrin, A. M. Caminade, J. P. Majoral, O.Reiser, Org. Lett. 2007, 9, 2895.
[199] R. K. O’Reilly, M. J. Joralemon, C. J. Hawker, K. L. Wooley, PMSE Prepr. 2005, 46, 92.
[200] J. W. Lee, J. H. Kim, B.-K. Kim, Tetrahedron Lett. 2006, 47 ,2683.
[201] J.W. Lee, J.H. Kim,B.-K. Kim,W. S.Shin, S.-H. Jin, Tetrahedron2006, 62, 894.
[202] J. W. Lee, J. H. Kim, H. J. Kim, S. C. Han, W. S. Shin, S. H. Jin, Bioconjugate Chem. 2007, 18, 579.
[203] X. M. Liu, A. Thakur, D. Wang, Biomacromolecules 2007, 8,2653.
[204] O. Altinas, B. Yankul, G. Hizal, U. Tunca, J. Polym. Sci., Part A: Polym. Chem. 2006, 44, 6458.
[205] M. R. Whittaker, C. N. Urbani, M. J. Monteiro, J. Am. Chem.Soc. 2006, 128, 11360.
[206] O. Altintas, G. Hizal, U. Tunca, J. Polym. Sci., Part A: Polym.Chem. 2008, 46, 1218.
[207] J. Lutz, H. G. Baerner, K. Weichenhan, Aust. J. Chem. 2007, 60,410.
[208] H. Durmaz,A. Dag, O. Altintas, T. Erdogan, G. Hizal, U. Tunca, Macromolecules 2007, 40, 191.
[209] M. Ergin, B. Kiskan, B. Gacal, Y. Yagci, Macromolecules 2007,40, 4724.
[210] Q. Zeng, Z. Li, C. Ye, J. Qin, B. Z. Tang, Macromolecules 2007,40, 5634.
[211] F. Morvan, A. Meyer, A. Jochum, C. Sabin, Y. Chevolot, A.Imberty, J. P. Praly, J. J. Vasseur, E. Souteyrand, S. Vidal,
Bioconjugate Chem. 2007, 18, 1637.[212] H. Pu, S. Ye, D. Wan, Electrochim. Acta 2007, 52, 5879.
[213] J.-H. Jung, Y.-G. Lim, K.-H. Lee, B. T. Koo, Tetrahedron Lett.2007, 48, 6442.
[214] Q. Liu, Y. Chen, J. Polym. Sci., Part A: Polym. Chem. 2006, 44,6103.
[215] X.-Y. Wang, A. Kimyonok, M. Weck, Chem. Commun. 2006,3933.
[216] P. Antoni, D. Nystrom, C. J. Hawker, A. Hult, M. Malkoch,Chem. Commun. 2007, 2249.
[217] M. Malkoch, K. Schleicher, E. Drockenmuller, C. J. Hawker,T. P. Russell, P. Wu, V. V. Fokin, Macromolecules 2005, 38,3663.
[218] S. Campidelli, J. Lenoble, J. Barbera, F. Paolucci, M. Marcaccio,D. Paolucci, R. Deschenaux, Macromolecules 2005, 38,7915.
[219] M. J. Joralemon, A. K. Nugent, J. B. Matson, R. K. O’Reilly, C. J.
Hawker, K. L. Wooley, PMSE Prepr. 2004, 91, 195.[220] S. Campidelli, E. Vazquez, D. Milic, M. Prato, J. Barbera, D. M.
Guldi, M. Marcaccio, D. Paolucci, F. Paolucci, R. Deschenaux, J. Mater. Chem. 2004, 14, 1266.
[221] J. W. Lee, J. H. Kim, B.-K. Kim, J. H. Kim, W. S. Shinc, S.-H. Jinc,Tetrahedron 2006, 62, 9193.
[222] C. Li, M. G. Finn, J. Polym. Sci., Part A: Polym. Chem. 2006, 44,5513.
[223] A. Gopin, S. Ebner, B. Attali, D. Shabat, Bioconjugate Chem.2006, 17 , 1432.
[224] W. Z. Chen, P. E. Fanwick, T. Ren, Inorg. Chem. 2007, 46,3429.
[225] B. G. D. Geest, W. V. Camp, F. E. D. Prez, S. C. D. Smedt,J. Demeesterb, W. E. Hennink, Chem. Commun. 2008, 190.
[226] J. D. D. Evanoff,S. E. Hayes,Y. Ying, G. H. Shim, J. R. Lawrence,
J. B. Carroll, R. D. Roeder, J. M. Houchins, C. F. Huebner, S. H.Foulger, Adv. Mater. 2007, 19, 3507.
[227] L. V. Lee, M. L. Mitchell, S. J. Huang, V. V. Fokin, K. B.Sharpless, C. H. Wong, J. Am. Chem. Soc. 2003, 125, 9588.
[228] J. P. Collman, N. K. Devaraj, C. E. D. Chidsey, Langmuir 2004,20, 1051.
[229] J. P. Collman, N. K. Devaraj, T. P. A. Eberspacher, C. E. D.Chidsey, Langmuir 2006, 22, 2457.
[230] N. K. Devaraj, R. A. Decreau, W. Ebina, J. P. Collman, C. E. D.Chidsey, J. Phys. Chem. B 2006, 110, 15955.
[231] T. Lummerstorfer, H. Hoffmann, J. Phys. Chem. B 2004, 108,3963.
[232] J. K. Lee, Y. S. Chi, I. S. Choi, Langmuir 2004, 20, 3844.[233] R. D. Rohde, H. D. Agnew, W. S. Yeo, R. C. Bailey, J. R. Heath,
J. Am. Chem. Soc. 2006, 128, 9518.
[234] J.-C. Meng, C. Averbuj, W. G. Lewis, G. Siuzdak, M. G. Finn, Angew. Chem. Int. Ed. 2004, 43, 1255.
[235] S. Prakash, T. M. Long, J. C. Selby, J. S. Moore, M. A. Shannon, Anal. Chem. 2007, 79, 1661.
[236] R. V. Ostaci, D. Damiron, S. Capponi, G. Vignaud, L. Leger,Y. Grohens, E. Drockenmuller, Langmuir 2008, 24, 2732.
[237] G. K. Such, J. F. Quinn, A. Quinn, E. Tjipto, F. Caruso, J. Am.Chem. Soc. 2006, 128, 9318.
[238] G. K. Such, E. Tjipto, A. Postma, A. P. R. Johnston, F. Caruso, Nano Lett. 2007, 7 , 1706.
[239] D. E. Bergbreiter, B. S. Chance, Macromolecules 2007, 40,5337.
W. H. Binder, R. Sachsenhofer
980
Macromol. Rapid Commun. 2008 , 29 , 952–981
2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/marc.200800089
-
8/15/2019 Chemistry in Polymer and Material
30/30
[240] J. A. Opsteen, R. P. Brinkhuis, R. L. M. Teeuwen, D. W. P. M.Lowik, J. C. M. v. Hest, Chem. Commun. 2007, 3136.
[241] S. F. M. v. Dongen, M. N. Sanne, S. Jeroen, J. L. M. Cornelissen,R. J. M. Nolte, J. C. M. v. Hest, Macromol. Rapid Commun.2008, 29, 321.
[242] B. Li, A. L. Martin, E. R. Gillies, Chem. Commun. 2007, 5217.
[243] F. SaidHassane, B. Frisch, F. Schuber, Bioconjugate Chem.2006, 17 , 849.
[244] S. Cavalli, A. R. Tipton, M. Overhand, A. Kros, Chem. Com-mun. 2006, 3193.
[245] H.-J. Musiol, S. Dong, M. Kaiser, R. Bausinger, A. Zumbusch,U. Bertsch, L. Moroder, Chem. Bio. Chem. 2005, 6, 625.
[246] R. Voggu, P. Suguna, S. Chandrasekaran, C. N. R. Rao, Chem. Phys. Lett. 2007, 443, 118.
[247] Y. G. H. Xiong, H. M. Li, ePolymers 2007, 416.[248] H.Li, F. Cheng, A.M. Duft, A.Adronov, J. Am. Chem. Soc. 2005,
127 , 14518.[249] W.-B. Zhang, Y. Tu, R. Ranjan, R. M. Van Horn, S. Leng, J.
Wang, M. J. Polce, C. Wesdemiotis, R. P. Quirk, G. R. New-kome, S. Z. D. Cheng, Macromolecules 2008, 41, 515.
[250] A. Bastero, D. Font, M. A. Pericas, J. Org. Chem. 2007, 72,2460.
[251] E. Alza, X. C. Cambeiro, C. Jimeno, M. A. Pericas, Org. Lett.2007, 9, 3717.
[252] M. Tilliet, S. Lundgren, C. Moberg, V. Levacher, Adv. Synth.Catal. 2007, 349, 2079.
[253] S. Lober, P. Rodriguez-Loaiza, P. Gmeiner, Org. Lett. 2003, 5,1753.[254] D. A. Fleming, C. J. Thode, M. E. Williams, Chem. Mater.2006,
18, 2327.[255] J. L. Brennan, N. S. Hatzakis, T. R. Tshikhudo, N. Dirvians-
kyite, V. Razumas, S. Patkar, J. Vind, A. Svendsen, R. J. M.Nolte, A. E. Rowan, M. Brust, Bioconjugate Chem. 2006, 17 ,1373.
[256] M. A. White, J. A. Johnson, J. T. Koberstein, N. J. Turro, J. Am.Chem. Soc. 2006, 128, 11356.
[257] Q. Zeng, T. Li, B. Cash, S. Li, F. Xie, Q. Wang, Chem. Commun.2007, 1453.
[258] A. Gole, C. J. Murphy, Langmuir 2008, 24, 266.
‘Click’ Chemistry in Polymer and Material Science: An Update