Copper complexes bearing an NHC-calixarene unit: Synthesis and application in click chemistry

Article abstract of DOI:10.1039/c6nj02089e

The synthesis of N-heterocyclic carbene (NHC) copper complexes supported by calix[4]arene is reported. Mono-substituted calix[4]arene was prepared through conventional procedures, followed by the attachment of an imidazolyl group to create the precursor o

Full text of DOI:10.1039/c6nj02089e

View Article Online
View Journal
NJC
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: B. OURRI, O.
Tillement, T. Tu, E. Jeanneau, U. Darbost and I. Bonnamour, New J. Chem., 2016, DOI:
1
0.1039/C6NJ02089E.
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
Accepted Manuscripts are published online shortly after
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the Ethical guidelines still
apply. In no event shall the Royal Society of Chemistry be held
responsible for any errors or omissions in this Accepted Manuscript
or any consequences arising from the use of any information it
contains.
www.rsc.org/njc

Page 1 of 9
PNl ee aws eJ do ou rnn oa tl ao df j uC sht emm ai rs gt ir ny s
View Article Online
DOI: 10.1039/C6NJ02089E
Journal Name
ARTICLE
Copper complexes bearing NHC-calixarene unit: synthesis and
application in click chemistry.
a
b
c
a
b
Benjamin Ourri, Olivier Tillement, Tao Tu, Erwann Jeanneau, Ulrich Darbost*, Isabelle
Bonnamour*,a
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
The synthesis of N-heterocyclic carbene (NHC) copper complexes supported by calix[4]arene was reported. A mono-
substituted calix[4]arene was prepared through conventional procedures, followed by the attachment of imidazolyl group
to compose the precursor of NHC ligands. Alkylation with two alkyl bromides followed by metalation gave fully characterized
original complexes. The X-ray structure showed an « out » conformation for the copper. Catalytic activity was studied in click
chemistry, which revealed good performance. In particular, three new triazoles were synthesized in high yields, solvent-free
conditions and fast reaction time. The new synthesized chiral complex was tested in kinetic resolution of racemic azide.
www.rsc.org/
replaced by copper(I) halide to generate [(NHC)CuX]
2
5
26,27
Introduction
complexes , while Cisnetti et al. used ammoniac as solvent
.
Later, copper powder was used directly as the copper source in
015 . At the same time, easy access to homoleptic and
heteroleptic NHC complexes was developed
route to unsymmetrical imidazoliums salts, Mauduit et al.
Organometallic chemistry is one of the most promising field for
the increase of clean and sustainable catalytic processes. The
development of a catalytic system greatly depends on ligands,
which protect the metal centre and change its electronic, steric
hindrance and solubility properties. Phosphines were popular
ligands, but since the early 2000s, the N-heterocyclic carbene
28
2
29,30
. Using another
added chiral arm on an NHC moiety thanks to amino acid and
31
alcohols, which binded to the copper . Supramolecular
platform offers easy access to evolved and multi-function
ligands. Among them, calix[4]arenes are attractive candidates
(NHC) family has attracted increasing attention. NHC have
become significantly interesting because of their steric and
electronic properties, which outperform oxidative addition and
reductive elimination, minimizing ligand dissociation steps.
Bulkiness, strong σ-donor and ambivalent π-bonding characters
make the specific nature of the metal-carbene bond . NHC are
able to facilitate an incredible range of chemical reactions. For
example, these air stable species are known to catalyse alkenes
and alkynes functionalization, C-heteroatom bond formation, C-
32-36
for the design of sophisticated ligands
. Upper and narrow
rim functionalization allows complex skeleton to be built,
displaying advantages such as bulkiness, chimioselectivity, as
well as wide complexation. The cavity can interact with a
metallic centre, inducing a supramolecular effect. To combine
the strengths of an NHC ligand and the calix[4]arene could lead
1
-6
37,38
to selective and efficient catalysts
, for which a chiral feature
can cooperate with the supramolecular impact of the cavity. In
fact, complexation of organic guest such as alkyne by the cavity
could be of particular importance to develop efficient catalysis,
so calix[4]arene are potential applicants to catalyse reaction
involving alkyne, for example [3+2] cycloaddition. This famous
click” reaction of azide with alkyne is a convenient route to
triazole. Pharmaceutical and biological industries are interested
in this family of heterocycle, because of many potential
7
-14
H activation as well as cycloaddition . Furthermore, water-
1
5-
soluble NHC complexes can perform a wide range of reactions
18
.
NHC ligands are also used as promising components for
19
medicinal and material applications . Numerous routes to NHC
precursors offer easy design of unsymmetrical NHC, and much
effort is dedicated to introduce chirality in order to develop
asymmetric reactions
imidazolylidene and imidazolydene has focused attention on
various groups. In 2010, Cu O was proposed as the copper
“
2
0-23
. Among them, the synthesis of
3
9-42
applications
. Copper NHC has recently showed a good
2
performance as the catalyst for [3+2] cycloadditions4 . As
3-46
2
4
source in mild conditions . Then, in 2013, copper(I) oxide is
calix[4]arene-NHC palladium complexes recently showed high
38
catalytic activity and impressive TON in Suzuki coupling ,
calix[4]arene-NHC copper complexes with similar structure
could be good catalysts for [3+2] cycloaddition.
a.Univ Lyon, Université Claude Bernard Lyon 1, ICBMS UMR CNRS 5246, Equipe
Chimie Supramoléculaire Appliquée CSAp, 43 Boulevard du 11 Novembre 1918, F-
6
9622, Villeurbanne, France
b.
Univ Lyon, Université Claude Bernard Lyon 1, ILM UMR CNRS 5306, Equipe FENNEC,
Université de Lyon, Bâtiment Kastler, 10 rue Ada Byron 69622 Villeurbanne CEDEX,
France.
Department of chemistry, Fudan University, 220 Handan Road, 200433 Shanghai,
China
Herein, the preparation of two NHC copper complexes bearing
calix[4]arene moiety is reported. The catalytic activity was
evaluated in click chemistry. New triazoles were synthesized
c.
†Electronic Supplementary Information (ESI) available: [NMR and HRMS (ESI)
spectra, SambVca calculation details, X-ray picture]. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
Please do not adjust margins

PNl ee aws eJ do ou rnn oa tl ao df j uC sht emm ai rs gt ir ny s
Page 2 of 9
ARTICLE
Journal Name
and chiral complex was tested in kinetic resolution of racemic
azide.
Table 1. Metalation of 2a (reaction time = 24 h.)
View Article Online
DOI: 10.1039/C6NJ02089E
Temperature
Entry
Conditions
Solvent
Observations
(°C)
1
2
3
4
Cu(s)
MeCN
DCM
55
40
mixture
mixture
Results and discussion
Complexes synthesis
Cu
2
O
O
As illustrated in scheme 1, two calix[4]arene-NHC copper complexes
were synthesized in two steps from the corresponding calix[4]arene
derivative 1. This intermediate was prepared according to the
Cu
2
Toluene
DCM
110
40
mixture
CuBr, K
2
CO
3
no reaction
38
literature procedure , in a 47% overall yield in 6 steps. Then, the
imidazolyl group was alkylated with two alkyl bromides. (S)-1-bromo-
[(NHC)CuBr]
100%
conversion
5
CuCl, K
2
CO
3
DCM
40
2
-methylbutane was chosen as the chiral source and bromobutane
as the non-chiral analogue. As a result, the salt 2a was synthesized in
1% yield, and the new salt 2b was synthesized in 49% yield. The Then we turned our attention to another way. CuBr was used to
9
NMR analysis showed characteristic acidic protons of imidazolium access the bromide copper complex. But as CuBr was not soluble
salts, respectively at δ = 10.45 and 10.47 ppm, precursors of NHC enough in dichloromethane, no conversion was observed so CuCl
ligands, as described in literature for the same class of was used. In the condition of entry 5, complexes 3a and 3b were
38,47,48
obtained in 64% and 76% yield respectively. This mild-condition
compounds
. These protons are sufficiently acid to generate in
situ the corresponding carbenes. Copper complexes were obtained avoided the use of a strong base as well as the use of inert
through weak base deprotonation and direct coordination to copper atmosphere, which made the complex easier to create51,52. An anion
source. Various conditions were tested, but only the method metathesis occurred to exchange the chloride atom by the bromide
49
atom, although chloride complexes are more stable than bromide
formation of a mixture, with no possible purification, as seen in table complexes, because KCl salt was less soluble than KBr salt in
dichloromethane that is why the equilibrium is displaced in favour of
2 3
described by Matt et al with K CO in dichloromethane avoided the
+
1
2
. A mixture of [(NHC)CuX] and undesired dimerised [(NHC) Cu]
species was a frequent reported issue for copper NHC synthesis, our bromide complexes. In addition, complexes were obtained by
usually dimerised product are obtained in high temperature and easy precipitation in pentane, as calix[4]arene moiety brought a low
2
7,28
solubility in the pentane, and no additional recrystallization was
between the two forms can be rationalized by the bulkiness of the required. Furthermore, imidazolium salts could be recycled and
reengaged in the reaction, as the reaction proceed cleanly and gave
long-time reaction as thermodynamic product
. The balance
50
NHC and the difference of energy between singlet and triplet state .
In the first attempts, as can be seen in entry 1, 2 and 3, copper no side products. In fact, calix[4]arene derivatives are particularly
powder and copper(I) oxide were used as the copper source. stable. Elemental analysis and X-ray structures confirmed that
Unfortunately, conversion of starting material was uncompleted, bromide is linked to the copper for 3a. All those new structures were
2
and gave several products. We supposed that the products were characterized through NMR spectroscopy. ArCH Ar signals of
1
3
mono and bis NHC complexes, and probably a structure bearing an compounds 2-3 appeared between 33-30 ppm in the C NMR, and
1
hydroxo moiety, as attested by a singlet proton around δ = 9 ppm in
H NMR revealed AB patterns for the corresponding diastereotopic
NMR, which was different from the acidic imidazolium proton at δ = protons. Both observations demonstrated that the skeleton of these
0.4 ppm. Formation of hydroxo complex with NHC was reported in calix[4]arenes are in cone conformation. 2b and 3b showed two
characteristic sets of diastereotopics CH protons around 4.00 and
1
2
6
literature .
2
1
.25 ppm corresponding to the chiral side arm. No chirality transfer
could be observed in NMR from the chiral side arm to neither
imidazolyl protons nor calix[4]arene aromatic protons. Both
complexes showed excellent stability in the air and in solution. The
calix[4]arene unit protected the metallic centre from any oxidation
and modification, which complemented the strong metal-NHC bond.
Indeed the NHC bond occupies one binding site of the copper, and
the macrocyclic cavity sterically protects the copper atom. Indeed its
binding sites are more interested in host binding interaction than
coordination and reaction with water or air.
X-ray analysis
A single crystal from 3a was obtained. The X-ray analysis revealed the
structure of a monomeric specie, in cone conformation for the
backbone and in an out conformation for the metal centre, as can be
seen in figure 1. No interactions between copper centres were
observed in the packing. The Cu-C and Cu-Br bond lengths are 1.87(7)
Å and 2.19(1) Å respectively.
Scheme 1. Synthesis of copper complexes 3a and 3b.
2
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 9
PNl ee aws eJ do ou rnn oa tl ao df j uC sht emm ai rs gt ir ny s
Journal Name
ARTICLE
Table 2. 3a and 3b catalysed synthesis of triazole between pVhieewnyAlratciceletyOlennlinee
DOI: 10.1039/C6NJ02089E
and benzylazide
Entry
Catalyst
3a
mol%
1
Conversiona
52%
Yielda
26%
30%
83%
88%
1
2
3
4
3b
1
52%
3a
10
10
> 99%
> 99%
3b
1
[
a] determined by H NMR with 2-methylfuran as internal standard
The results obtained for the cycloaddition between phenylacetylene
and benzyl azide, two bulky substrates, are shown in table 2. The
system required the use of an amine to promote the reaction, as
none of the tests without base showed conversion, which is common
Figure 1. X-ray structure of 3a.
The metal-C bond is slightly closer than for the palladium (1.95 Å),
38
for the same structure . Cu-C bond is included on the range of
5
4
in a non-aqueous solvent . Regioselectivity is in total favour of 1,4
regioisomer, as expected. Complexes presented an appreciable
catalytic activity in dichloromethane, up to 90% yield at 10 mol%,
52
classical NHC-copper length (1.87-1.96 Å) as well as the Cu-Br bond .
The dihedral angle CArCalix NHC is 42.8(2)°. This unusual
C
ArCalix NHC
N C
value could be rationalized with the establishment of a weak C-H/π
interaction of 4.12(1) Å between the H-imidazole and the proximal
aromatic ring of the calix[4]arene centroid (see figure 38 in the
supporting information). This interaction prevented the metallic
centre from being as far as possible from the calix[4]arene, which
could be particularly interesting for catalysis. Moreover, the complex
adopts a slightly distorted linear geometry with C-Cu-Br angle at
55,56
which is comparable to other catalysts in the same solvent
.
Bromide derivatives are known to be particularly efficient in the
5
7
CuAAC catalysis . The formation of by-products such as bis-triazoles
58
or alkynyl triazoles was limited compared to direct catalysis by CuX
complexes, with X=Cl, Br, I. The reactions proceeded without
precaution, without inert atmosphere and distilled dichloromethane.
58
Inspired by the work of Finn et al. , a kinetic resolution of racemic
azide was therefore investigated to demonstrate the potential
asymmetric catalytic activity of 3b. The resolution was conducted
between (1-azidoethyl)benzene and phenylacetylene, as shown in
scheme 2. Unfortunately, no preferences between the two
enantiomers of the azide were observed. Chiral HPLC clearly showed
the formation of the racemic corresponding triazole. This result could
be rationalized by a long distance between the chiral centre and the
metal, and also by the lack of rigidity of the system, which prevented
any chiral induction on the catalytic cycle. Similar strategy was
1
77.5(2°). The parameter of steric hindrance %Vbur of the NHC ligand
53
was calculated thanks to the SambVca web application . The 3a
ligand was found to be less bulky than classical NHC, with a %Vbur of
2
explained by the dissymmetric environment around the carbene. In
fact, the butyl arm offsets the sterically demanding calix[4]arene
moiety. In fact, (IPr) NHC had a calculated %Vbur of 31.6%, with an
aromatic symmetrical substitution on the NHC. Only unsaturated
NHC with hydrogen substitution showed a lower value of 18.8%,
while methyl substitution presents a similar value of 24.9% . This
accessible metal centre could induce particularly interesting
properties in catalysis. This structure is the first example of
monomeric crystallized calix[4]-NHC-copper complex. Many
attempts to obtain an X-structure from 3b were unsuccessful. In fact,
a lot of crystals were grown from several systems of solvents, but
none were suitable for X-ray analysis, as they were highly
disorganised. Based on the close precedent result, elemental analysis
and NMR, a monomeric structure with a bromide was assumed by
analogy to 3b. We guessed that the difficulty to obtain good quality
crystals for X-ray diffraction was due to the chiral environment of the
molecule, preventing a long range organization between crystalline
cells.
3.8%. These slightly distorted geometry and parameter could be
53
60
ineffective in 1996 . The design of chiral NHC with efficient chiral
induction is a challenge, as many strategies and attempts are
61
unsuccessful . 3a was then chosen to study the scope of the
reaction, because it was less expensive to synthesize and showed a
similar activity to 3b. 10 azides were prepared for this scope, among
them a new azide corresponding to triazole 4f was synthesized and
fully characterized. As shown in scheme 3, a number of triazoles
could be prepared in particularly high yields and short reaction times,
in neat conditions and at 1 mol% of catalyst 3a. The low-melting point
triazoles required longer times than the sterically hindered others.
The reaction proceeded cleanly, without side products and was easy
to monitored, as the triazoles precipitated. Among them, 3 new
triazoles 4d-f were synthesized and fully characterized. No
correlation between the electronic properties and the results could
be established. These results are similar with the one previously
Catalysis of copper catalysed [3+2] cycloaddition between an
alkyne and an azide CuAAC
57
obtained by Nolan et al. with (SIMes)CuBr at 0.8 mol% (98% of yield
in 20 mn for the reaction between phenylacetylene and benzyl azide,
compared to 99%, scheme 3, 4b), which highlights the performance
of the NHC ligand.
The catalytic activity of 3a and 3b was evaluated in the preparation
of [1,2,3]-triazoles by click chemistry.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

PNl ee aws eJ do ou rnn oa tl ao df j uC sht emm ai rs gt ir ny s
Page 4 of 9
ARTICLE
Journal Name
This function could be strongly attached with the calix[4]arene
View Article Online
DOI: 10.1039/C6NJ02089E
cavity, avoiding catalysis. This phenomena proved the potential
power of the calix[4]arene as pre-complexation unit for catalysis.
Scheme 2. Kinetic resolution trial on (1-azidoethyl)benzene
Conclusion
The formation of triazoles in neat conditions are faster with 3a than We have prepared and characterized the first examples of a
in solution. The reaction of phenylacetylene and benzylazide (Table new family of [(NHC)CuX] bearing a calix[4]arene. The two
2
, entry 3) gave 83% of yield compared to the 99% of yield in neat complexes were notably air stable, making them good
condition (scheme 3, 4b). There are no by-products in the solvent- candidates for copper catalysis. X-ray analysis showed an
free catalysis, as the catalytic steps proceed faster and because the interesting structure for 3a
with an unusual “out”
,
solubility of water and air in is limited. Combined with the protection conformation for the metal thanks to a weak C-H/π. Herein, the
of the macrocyclic cavity, it prevents any formation of by-products. complexes have proved good catalytic activity in copper-
Moreover, an elution on a short pad of silica transformed the catalyzed [3+2] cycloaddition, at low concentration, room
complexes into their imidazolium salt. The corresponding temperature and in solvent-free conditions. 10 triazoles were
imidazolium salts 2a could be easily recovered by this filtration and synthesized in high yield and in short time reaction. Among
recycled. Elution of the salt was fast thanks to the hydrophobic them, 3 new triazoles were prepared. The potential of the
calix[4]arene. 2a could then be reengaged in the metalation step to catalyst was attested by the range of tolerated function of both
be reused. 3a obtained by this recycling process is rigorously identical alkyne and azide. Moreover, thanks to the stability and the
and presents the same catalytic properties as the 3a synthetized. 2a properties of solubility of the calix[4]arene, the catalysts could
recovered from a silica pad is also rigorously identical as the 2a be recycled as well as the corresponding imidazolium salts in the
synthesized. By this solvent-free catalysis, triazoles including metalation step. Unfortunately, our first example of chiral
functions such as bromide, cyano, linear alkane, aromatics, alkene complex was unable to separate racemic azide by kinetic
and alcohols were prepared. This scope demonstrated the high resolution. This result can be rationalized through the
functionality tolerance of 3a, as only the dioxane function was not significant distance between the chiral centre and the copper as
tolerated in the reaction.
well as the free rotation of the C-N bond for the chiral side arm.
New chiral compounds from this family are currently under
preparation, using the introduction of alkyl group through
alkylation of imidazole derivative. We are also investigating the
use of calix[6/8]arene, in order to create a supramolecular
nanoreactor for click chemistry.
Experimental
Materials and methods
All commercial reagents were used as received. Solvents were dried
by conventional methods. All reactions were carried out under
nitrogen. Column chromatography was performed using silica gel
(
0.040-0.063 nm). Reactions were monitored by TLC on silica gel
1
13
plate and visualized by UV light. H NMR and C NMR spectra were
recorded on a Bruker DRX at 400 or 300 MHz. J value are given in Hz.
Mass spectra were acquired on an LCQ Advantage ion trap
instrument, detecting positive ions in the ESI mode. Optical rotations
were measured at 20°C by a Perkin Elmer polarimeter 343. [α]
D
-1
-1
values are given in g .mL.dm . Melting points were determined by a
Buchï Melting point B-540. IR spectra were recorded on a Shimadzu
IRaffinity-1S spectrometer. HPLC analysis was performed on a UFLC
XR- Shimadzu equipped with the Chiralcel column OD-1 (elution n-
hexane / iPrOH, Vinjection = 1 μL, flow = 1 mL/mn).
Crystallography
A Suitable crystals from 3a (N° CCDC 1476585) were selected and
mounted on a Gemini kappa-geometry diffractometer (Agilent
Technologies UK Ltd) equipped with an Atlas CCD detector using Mo
radiation (λ = 0.71073 Å). Intensities were collected at 150 K by
1
Scheme 3. 3a catalysed synthesis of triazoles. Yield determined by H NMR
with 2-methylfuran as internal standard
62
means of the CrysalisPro software . Reflection indexing, unit-cell
4
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 5 of 9
PNl ee aws eJ do ou rnn oa tl ao df j uC sht emm ai rs gt ir ny s
Journal Name
ARTICLE
parameters refinement, Lorentz-polarization correction, peak 1066.6, 1087.8, 1161.1, 1195.9, 1244.1, 1292.3, 1383.0, 1452.4,
View Article Online
DOI: 10.1039/C6NJ02089E
integration and background determination were carried out with the 1548.5, 2873.9, 2933.7, 2960.7
CrysalisPro software. An analytical absorption correction was applied
63
using the modeled faces of the crystal . The resulting sets of hkl was [5-(3-Butylimidazol-2-yliden-1-yl)-25,26,27,28-tetrapropyloxy-
used for structure solution and refinement. The structures were calix[4]arene] copper bromide 3a (cone)
solved by direct methods with SIR9764 and the least-square A suspension of the corresponding imidazolium bromide salt 2a
65
refinement on F2 was achieved with the CRYSTALS software . All (0.530 g, 0.67 mmol), finely crushed K
2 3
CO (1.256 g, 9.55 mmol) and
non-hydrogen atoms were refined anisotropically. The hydrogen CuCl (0.098 g, 0.98 mmol) in CH Cl (26 mL) was stirred at 40°C under
2
2
atoms were initially positioned geometrically and initially refined nitrogen atmosphere overnight. The completion is monitored by
with soft restraints on the bond lengths and angles to regularize their NMR. The mixture was filtered through a filter paper and the filter
geometry (C---H in the range 0.93-0.98 Å) and Uiso(H) (in the range was washed with CH
2
Cl
2
(3 x 10 mL). The filtrate was concentrated
1
.2-1.5 times Ueq of the parent atom), after which the positions were under vacuum to a minimum. Pentane (20 mL) was added and the
refined with riding constraints.
resulting white precipitate was decanted. After removal of the
supernatant, the solid was washed with pentane (3 x 5 mL), then
dried under vacuum to afford pure white solid (0.367 g, 64%); Mp.
Synthesis of complexes 3a-b.
1
C
13.4-116.5 °C; elemental analysis found: C, 63.8; H, 6.95; N, 3.25%
58BrCuN requires C, 65.76; H, 6.81; N, 3.26%. Crystals suitable
47
H
2 4
O
5
-(3-butyl)-1-imidazolylium)-25,26,27,28-
for X-ray analysis were grown by slow cooling of a solution of the
tetrapropyloxycalix[4]arene bromide 2a (cone)
1
complex in hot acetonitrile. H NMR (400 MHz ,CDCl
3
) δ 0.95 (m, 9 H,
), 1.30 - 1.39 (m, 2 H,
C), 1.93 (m, 8 H, OCCH C), 3.20
Ar), 3.70 - 3.83
C), 4.12 (t, J = 7.2 Hz, 2 H,
The stirred mixture of 1 (0.593 g, 0.90 mmol,1.0 eq) and
bromobutane (2 mL) was heated at reflux for 24 h. After cooling
down to room temperature, the mixture was evaporated to dryness.
The product was isolated by flash chromatography on silica gel
OCCCH
NCCCH
3 3 3
, NCCCCH ), 1.04 - 1.13 (m, 6 H, OCCCH
2
C), 1.78 - 1.86 (m, 2 H, NCCH
2
2
2
and 4.48 (AB spin systems, JAB = 13.3 Hz, 2*4 H, ArCH
2
(
m, 4 H, OCH
2
C), 3.93 – 4.03 (m, 4 H, OCH
2
(
DCM/MeOH 100/1 to 10/1). The product was dried under vacuum
1
N-CH C), 6.13 (m, 1 H, Ar), 6.26 (d, J = 7.2 Hz, 2 H, Ar), 6.48 (m, 2 H,
to afford brown solid (651 mg, 91%); H NMR (300 MHz, CDCl
3
) δ 0.89
), 1.09 (q, J = 7.5 Hz, 6 H, O-C-C-CH ), 1.36
, N-C-CH ),
Ar), 3.68
), 4.53 - 4.61 (m, 2
), 6.06 (t, J = 7.5 Hz, 1 H, Ar), 6.22 - 6.28 (m, 2 H, Ar), 6.42 (m,
H, Ar), 6.74 (s, 1 H, N-CH), 6.87 (t, J = 7.5 Hz, 2 H, Ar), 6.98 – 7.04
m, 2 H, Ar), 7.04 - 7.10 (m, 2 H, Ar), 7.31 (s, 1 H, N-CH), 10.45 (s, 1 H,
2
Ar), 6.53 (d, J = 3.8 Hz, 1H, NCHC), 6.82 (t, J = 7.3 Hz, 2 H, Ar), 6.86 (d,
–
-
3
-
1.00 (m, 9 H, N-C-C-C-CH
1.48 (m, 2 H, N-C-C-CH
3
3
13
J = 3.9 Hz, 1H, NCHC), 6.93 – 7.07 (m, 4 H, Ar) ppm; C NMR (400
MHz ,CDCl ) δ 9.9, 10.6, 10.6, 13.6, 14.0, 19.7, 22.3, 23.0, 23.4, 23.4,
2
), 1.85 – 2.01 (m, 10 H, O-C-CH
2
2
2
.21 and 4.47 (AB spin systems, JAB = 13.3 Hz, 2*4 H, ArCH
3.82 (m, 4 H, O-CH ), 3.91 – 4.08 (m, 4 H, O-CH
2
3
3
1
0.9, 31.0, 33.4, 34.1, 51.5, 76.6, 76.9, 77.1, 77.2, 119.9, 120.6, 121.5,
22.1, 127.3, 128.9, 133.5, 134.1, 135.7, 135.8, 136.3, 155.8, 157.4
2
2
H, N-CH
2
(
2
-1
ppm; IR νmax/cm 675.1, 748.4, 877.6, 962.5, 1004.9, 1035.8, 1062.8,
085.9, 1099.4, 1244.1, 1292.3, 1383.0, 1433.1, 1452.4, 1477.5,
1585.5, 2873.9, 2929.9, 2958.9
1
38
N-CH-N) ppm, data matched with literature reference .
[
5-(3-(2(S)-methyl-butyl)imidazol-2-yliden-1-yl)-25,26,27,28-
5
-(3-(2(S)-methyl-butyl)-1-imidazolylium)-25,26,27,28-
tetrapro-pyloxycalix[4]arene] 3b copper bromide (cone)
A suspension of the corresponding imidazolium bromide salt 2b
tetrapropylo-xycalix[4]arene bromide 2b (cone)
The stirred mixture of 1 (0.316 g, 0.48 mmol, 1.0 equiv) and (S)-(+)-
(
0.210 g, 0.26 mmol), finely crushed K
2 3
CO (0.152 g, 3.71 mmol) and
1-Bromo-2-methylbutane (1 mL) was heated at 80°C for 48 h. The
CuCl (0.037 g, 0.38 mmol) in CH Cl (8 mL) was stirred at 40°C under
nitrogen atmosphere overnight. The completion is monitored by
NMR. The mixture was filtered through a filter paper and the filter
2
2
mixture was cooled down to room temperature and then
evaporated. The product was isolated by flash chromatography on
silica gel (DCM/MeOH 100/1 to 10/1). The product was dried under
2
0
2 2
was washed with CH Cl (3 x 10 mL). The filtrate was concentrated
vacuum to afford pink solid (0.517 g, 49%). Mp. 153.6-156.8 °C. [α
D
]
-1
-1
+
under vacuum to a minimum. Pentane (20 mL) was added and the
resulting white precipitate was decanted. After removal of the
supernatant, the solid was washed with pentane (3 x 5 mL), then
dried under vacuum to afford pure white solid (0.172 g, 76%); Mp.
=
7
0.78 g .mL.dm (CHCl
29,4601, calculated 729.4626 for [C48
) δ 0.88 - 0.96 (m, 12 H, OCCCH
.03 - 1.11 (m, 6 H), 1.26 (m, 1 H, NCC(C)CH
NCC(C)CH C), 1.85 – 2.04 (m, 9 H, OCCH C, NCCH(C)(C)), 3.21 and
.47 (AB spin systems, 2JAB = 13.4 Hz, 2*4 H, ArCH
Ar), 3.69 - 3.80 (m,
H, OCH C), 3.90 – 4.02 (m, 4 H, OCH C), 4.41 (m, 2 H, NCH C), 6.07
3
, C = 0.51 g/mL). HRMS (ESI) [M-Br] found
+
1
H
61
N
2
O
4
] ; H NMR (400
, NCC(C)CCH , NCC(CH )C),
C), 1.45 (m, 1H,
MHz ,CDCl
1
3
3
3
3
2
20
-1
-1
1
24.8-128.1°C, [α
D
]
3
= 0.68 g .mL.dm (CHCl , C = 1.03 g/mL).
2
2
elemental analysis found: 65.38; H, 7.03; N, 3.27% C H BrCuN O
48 60
2
4
4
4
2
1
requires C, 66.08; H, 6.93; N, 3.21%. H NMR (400 MHz ,CDCl
0.96 (m, 12 H, OCCCH , NC(CH )C, NC(C)CCH ), 1.04 - 1.12 (m, 6 H,
OCCCH ), 1.16 - 1.25 (m, 1 H, NC(C)CH C), 1.35 - 1.44 (m, 1 H,
NC(C)CH , NCCH(C)(C)), 3.20 and 4.48
3
) δ 0.90
2
2
2
-
3
3
3
(
t, J = 7.8 Hz, 1 H, Ar), 6.26 (d, J = 7.6 Hz, 2 H, Ar), 6.44 - 6.49 (m, 2 H,
Ar), 6.79 (t, J = 1.8 Hz, 1 H, NCHC), 6.85 (t, J = 7.1 Hz, 2 H, Ar), 6.97 (d,
J = 7.5 Hz, 2 H, Ar), 7.05 (d, J = 7.4 Hz 2 H, Ar), 7.37 (t, J = 1.7 Hz, 1 H,
NCHC), 10.47 (s, 1 H, NCHN) ppm; C NMR (400 MHz ,CDCl
1
5
1
1
7
3
2
2
C), 1.88 – 2.00 (m, 9 H, OCCH
2
2
13
(AB spin systems, J = 13.3 Hz, 2*4 H, ArCH Ar), 3.72 - 3.82 (m, 4 H,
OCH
Ar), 6.51 (m, 2 H, Ar), 6.27 (d, J = 7.6 Hz, 2 H, Ar), 6.55 (d, J = 1.7 Hz,
1
6.95 (dd, J = 1.5, 7.6 Hz, 2 H, Ar), 7.00 - 7.05 (m, 2 H, Ar) ppm; C
3
NMR (400 MHz ,CDCl ) δ 10.0, 10.6, 10.6, 11.2, 16.9, 23.0, 23.4, 23.4,
) δ 9.9,
AB
2
3
2
C), 3.88 – 4.05 (m, 6 H, OCH
2
C, NCH
2
C), 6.13 (t, J = 7.8 Hz, 1 H,
0.5, 10.6, 11.1, 16.3, 22.3, 23.0, 23.3, 23.4, 26.3, 30.9, 30.9, 35.7,
5.6, 76.6, 77.2, 120.3, 121.1, 121.1, 121.2, 122.2, 122.4, 127.2,
27.3, 128.3, 128.9, 128.9, 129.1, 134.2, 134.2, 135.3, 136.0, 136.3,
36.3, 137.0, 137.1, 156.0, 157.2, 157.3 ppm; IR νmax/cm 624.9,
29.1, 758.0, 800.5, 833.2, 875.7, 889.2, 964.4, 1003.0, 1035.8,
H, NCHC), 6.83 (t, J = 7.1 Hz, 2 H, Ar), 6.84 - 6.85 (m, 1 H, NCHC),
1
3
-
1
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
Please do not adjust margins

PNl ee aws eJ do ou rnn oa tl ao df j uC sht emm ai rs gt ir ny s
Page 6 of 9
ARTICLE
Journal Name
2
1
1
8
1
2
6.7, 30.9, 31.0, 36.6, 57.6, 76.6, 76.9, 77.1, 77.2, 120.4, 120.5, 121.5, ppm; IR νmax/cm-1 1259.5, 1280.7, 1348.2, 1442.7, 1542.4, 1639.5,
View Article Online
DOI: 10.1039/C6NJ02089E
22.1, 122.1, 127.3, 128.9, 133.4, 134.2, 135.7, 135.7, 136.3, 155.9, 2097.5, 2856.6, 2929.9
-1
55.9, 157.3 ppm; IR νmax/cm 667.4, 702.1, 736.8, 756.1, 763.8,
71.8, 962.5, 1004.9, 1035.8, 1064.7, 1084.0, 1097.5, 1157.3, 1192.0, 1-azidooctane
1
211.3, 1226.7, 1244.1, 1292.3, 1383.0, 1545.3, 1585.5, 2873.9, Obtained as a colorless oil (1.441 g, 93%); H NMR (300 MHz, CDCl
916.4, 2929.9, 2960.7 δ 0.89 (t, J = 7.0 Hz, 3 H, CH ), 1.25 - 1.42 (m, 10 H, CH ), 1.60 (quin, J
7.3 Hz, 2 H, CH -C-N ), 3.25 (t, J = 7.0 Hz, 2 H, CH -N
) ppm; 13C NMR
(300 MHz, CDCl ) δ 14.0, 22.6, 26.7, 28.8, 29.1, 31.7, 51.4 ppm. Data
3
)
3
2
=
2
3
2
3
General procedure for azide synthesis
A mixture of sodium azide (0.715 g, 11 mmol, 1.1 eq) and alkyl matched with literature reference .
bromide (10 mmol, 1 eq) in DMSO (22 mL) was stirred overnight. The
3
66
reaction was quenched with H
x 30 mL). The organic phase was washed with H
brine (30 mL), and then was dried (Mg SO ) and filtered. The solvent δ 3.30 - 3.37 (m, 2 H, CH
2
O (50 mL), and extracted with Et
2
O (3 2-(azidomethyl)-1,3-dioxolane
1
2
O (2 x 30 mL) and Obtained as an orange oil (1.077 g, 83%); H NMR (300 MHz, CDCl )
3
2
4
2
-N
3
), 3.85 – 4.03 (m, 4 H, O-CH
2
-CH
2
-O), 5.04
) δ 32.3, 65.4,
66
13
was removed by vacuum to afford pure alkyl azides .
- 5.11 (m, 1 H, O-CH-O) ppm; C NMR (300 MHz, CDCl
3
6
9
1
01.8 ppm. Data matched with literature reference .
Synthesis of azide
General procedure for catalysis in dichloromethane (4a)
(
azidomethyl)benzene
To a solution of alkyne (0.1 mmol, 1 eq) in dichloromethane (1.5 mL)
was added 3a (8.7 mg, 0.01 mmol, 0.1 eq) or 3b (8.6 mg, 0.01 mmol,
1
Obtained as a colorless oil (1.330 g, 99%); H NMR (300 MHz, CDCl
3
)
1
3
δ 4.37 (s, 2 H, CH
CDCl ) δ 54.7, 128.2, 128.2, 128.8 ppm. Data matched with literature (0.1 mmol, 1 eq). iPr
reference .
2
), 7.28 - 7.47 (m, 5 H, Ar), ppm; C NMR (300 MHz, 0.1 eq). The mixture was stirred for 5 minutes, and azide was added.
3
2
NEt was then added (3.48 μL, 0.02 mmol, 0.2
66
eq) and the mixture was stirred at room temperature. Conversion
1
was monitored by H NMR.
(
1-azidoethyl)benzene
Obtained as a colorless oil (1.450 g, 99%); H NMR (300 MHz, CDCl
δ 1.43 (d, J = 6.8 Hz, 3 H, CH
1
3
)
General procedure for solvent-free catalysis (4b-j)
3
), 4.51 (q, J = 6.9 Hz, 1 H, CH), 7.14 - 7.32 Alkyne (1 mmol, 1 eq) and 3a (8.7 mg, 0.01 mmol, 0.01 eq) were
m, 5 H, Ar) ppm; 13C NMR (300 MHz, CDCl
) δ 21.5, 61.0, 126.3, charged in a vial. Azide (1 mmol, 1 eq) was added and the resulting
(
3
6
6
1
28.0, 128.7, 140.8 ppm. Data matched with literature reference .
solution was stored at room temperature. Conversion was
1
monitored by H NMR. The product was isolated by flash
(
E)-(3-azidoprop-1-en-1-yl)benzene
Obtained as a yellow oil (1.389 g, 87%); H NMR (300 MHz, CDCl
.98 (d, J = 7.0 Hz, 2 H, CH -N ), 6.28 (td, J = 6.6, 15.0 Hz, 1 H, CH=C- Synthesis of triazoles 4a-j
Ar), 6.70 (d, J = 15.8 Hz, 1 H, C=CH-Ar), 7.28 - 7.48 (m, 5 H, Ar) ppm;
chromatography on silica gel (pentane / ethyl acetate 100/1 to 1/1).
1
3
) δ
3
2
3
1
3
C NMR (300 MHz, CDCl
3
) δ 52.9, 122.3, 126.6, 128.6, 134.4, 135.9 (+/-) 4-phenyl-1-(1-phenylethyl)-1H-1,2,3-triazole 4a
6
6
1
ppm. Data matched with literature reference .
White solid; H NMR (300 MHz, CDCl
3 3
) δ 2.04 (d, J = 7.2 Hz, 3 H, CH ),
5
.88 (q, J = 7.2 Hz, 1 H, CH), 7.28 - 7.41 (m, 8 H, Ar), 7.66 (s, 1 H, C=CH-
4
-azidobutanenitrile
Obtained as a colorless oil (0.667 g, 61%); H NMR (300 MHz, CDCl
δ 1.86 (quin, J = 7.0 Hz, 2 H, C-CH -C), 2.42 (t, J = 7.5 Hz, 2 H, CH -N
-CN) ppm; 13C NMR (300 MHz, CDCl
) δ
4.2, 24.6, 49.3, 118.5 ppm. Data matched with literature 1-benzyl-4-phenyl-1H-1,2,3-triazole 4b
N), 7.78 - 7.85 (m, 2 H, Ar) ppm. Retention time of both enantiomers
1
3
)
(elution n-hexane / iPrOH 80/20) 5.27 mn and 10.28 mn. Data
70
2
2
3
), matched with literature reference .
3.43 (t, J = 6.4 Hz, 2 H, CH
2
3
1
67
1
reference .
White solid; H NMR (300 MHz, CDCl
3 2
) δ 5.60 (s, 2 H, N-CH -Ar), 7.31
-
7.44 (m, 8 H, Ar), 7.69 (s, 1 H, C=CH-N), 7.83 (dd, J = 1.3, 8.3 Hz, 2 H,
71
1
-(2-azidoethyl)-4-nitrobenzene
Ar) ppm. Data matched with literature reference .
1
Obtained as a colorless oil (1.702 g, 88%); H NMR (300 MHz, CDCl
3
)
δ 3.00 (t, J = 6.9 Hz, 2 H, CH
(
2
-Ar), 3.59 (t, J = 6.9 Hz, 2 H, CH
2
-N
3
), 7.40 1-cinnamyl-4-phenyl-1H-1,2,3-triazole 4c
d, J = 9.0 Hz, 2 H, Ar), 8.17 (d, J = 8.8 Hz, 2 H, Ar) ppm; 13C NMR (300 White solid; H NMR (300 MHz, CDCl
1
3
) δ 5.19 (dd, J = 1.3, 6.6 Hz, 2 H,
MHz, CDCl
with literature reference .
3
) δ 35.0, 51.6, 123.7, 126.7, 129.6 ppm. Data matched CH
2
-N), 6.26 - 6.31 (m, 1 H, CH=C), 6.40 (td, J = 6.6, 16.1 Hz, 1 H,
6
8
CH=C), 7.29 - 7.46 (m, 8 H , Ar), 7.82 (s, 1 H, C=CH- N), 7.83 - 7.88 (m,
72
2
H) ppm. Data matched with literature reference .
8
-azidooct-1-ene
+
Obtained as a yellow oil (1.357 g, 89%), HRMS (EI) [M+H] found 4-(4-phenyl-1H-1,2,3-triazol-1-yl)butanenitrile 4d
+
1
+
1
52.1179, calculated 152.1183 for [C
CDCl ) δ 1.30 - 1.46 (m, 6 H, CH ), 1.59 (quin, J = 7.0 Hz, 2 H, CH
.05 (q, J = 6.6 Hz, 2 H, CH -C=C), 3.25 (t, J = 7.0 Hz, 2 H, CH -N ), 4.89 (quin, J = 6.4 Hz, 2 H, C-CH
5.04 (m, 2 H, C=CH -N), 7.40 - 7.45 (m, 2 H, Ar), 7.32 - 7.37 (m, 1 H,
), 5.69 - 5.87 (m, 1 H, C-CH=C) ppm; 13C NMR (t, J = 6.6 Hz, 2 H, CH
8 14 3
H N ] ; H NMR (400 MHz, White solid; HRMS (ESI) [M+H] found 213.1127, calculated 213.1135
+
1
3
2
2
), for [C12
H
13
N
4
] ; Mp: 88.9-91.1°C; H NMR (400 MHz, CDCl
3
) δ 2.33
2
–
2
2
3
2
-C), 2.43 (t, J = 6.4 Hz, 2 H, CH -CN), 4.53
2
2
2
13
(
3
400 MHz, CDCl3) δ 26.4, 28.5, 28.6, 28.7, 33.5, 51.3, 114.2, 138.7 C=CH-N), 7.78 - 7.85 (m, 3 H, Ar) ppm; C NMR (400 MHz, CDCl ) δ
6
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 7 of 9
PNl ee aws eJ do ou rnn oa tl ao df j uC sht emm ai rs gt ir ny s
Journal Name
4.5, 25.8, 48.2, 118.2, 120.1, 125.6, 128.3, 128.8, 130.1, 147.9 ppm, CH
ARTICLE
1
2
-N), 7.20 - 7.29 (m, 3 H, Ar, C=CH-N), 7.33 - 7.41 (m, 3 H, Ar) ppm;
View Article Online
IR νmax/cm 1022.3, 1051.2, 1072.4, 1082.1, 1141.9, 1182.4, 1201.6, 13C NMR (400 MHz, CDCl
-1
DOI: 10.1039/C6NJ02089E
) δ 25.3, 25.5, 32.1, 54.0, 62.2, 120.6, 127.9,
3
-1
1
2
209.2, 1325.1, 1354.0, 1371.4, 1419.7, 1446.6, 1465.9, 1485.2, 128.6, 129.0, 129.4, 134.8 ppm ; IR νmax/cm 1030.0, 1053.5,
249.0,2956.9, 3099.6, 3124.7.
1131.14, 1178.5, 1215.1, 1330.9, 1431.2, 1142.7, 1492.9, 1552.7,
726.3, 2860.4, 2934.5, 3055.2, 3107.3, 3392.8, 3344.0. Data
1
75
1
-(4-nitrophenethyl)-4-phenyl-1H-1,2,3-triazole 4e
matched with literature reference .
+
Orange white solid; HRMS (ESI) [M+H] found 295.1188, calculated
2
+
1
95.1190 for [C16
H
15 4
N O
2
] ; Mp: 177.3-179.6; H NMR (400 MHz, 4-hexyl-1-phenyl-1H-1,2,3-triazole 4 j
1
DMSO) δ 3.38 (t, J = 7.3 Hz, 2 H, Ar-CH
2
-C-N), 4.74 (t, J = 7.1 Hz, 2 H, White solid; H NMR (300 MHz, CDCl
3
) δ 0.80 (t, J = 7.0 Hz, 3 H, CH
), 1.86 (quin, J = 7.1 Hz, 2 H, CH -C-N), 4.31
-N), 7.23 - 7.38 (m, 3 H, Ar), 7.66 (s, 1 H, C=CH-
.55 (s, 1 H, C=CH-N) ppm; C NMR (400 MHz, DMSO) δ 35.2, 49.9, N), 7.72 - 7.79 (m, 2 H, Ar), ppm. Data matched with literature
3
)
CH
-
2
-N), 7.32 (tt, J = 1.5, 7.3 Hz, 1 H, Ar), 7.48 - 7.53 (m, 2 H, Ar), 7.40 1.15 - 1.32 (m, 10 H, CH
7.46 (m, 2 H, Ar), 7.78 - 7.82 (m, 2 H, Ar), 8.11 - 8.16 (m, 2 H, Ar), (t, J = 7.2 Hz, 2 H, CH
2
2
2
13
8
1
76
21.4, 123.5, 125.1, 127.8, 128.9, 130.1, 130.7, 146.0, 146.2, 146.4 reference .
-1
ppm ; IR νmax/cm 1016.5, 1030.0, 1047.3, 1074.3, 1109.1, 1183.4,
1
1
192.0, 1220.9, 1315.4, 1348.8, 1427.3, 1440.8, 1454.3, 1462.0,
483.3, 1494.8, 1507.3, 1599.0
Acknowledgements
We gratefully acknowledge the funding support received from
Region Rhône-Alpes within the COOPERA program.
1
-(oct-7-en-1-yl)-4-phenyl-1H-1,2,3-triazole 4f
+
White solid; Mp: 66.1-67.6°C; HRMS (ESI) [M+H] found 256.1808,
+
1
calculated 256.1808 for [C16
1.43 (m, 6 H, CH ), 1.91 - 1.98 (m, 2 H, CH
CH -C-N), 4.38 (t, J = 7.2 Hz, 2 H, CH -N), 4.91 – 5.03 (m, 2 H, C=CH
.73 - 5.84 (m, 1 H, C-CH=C), 7.30 - 7.36 (m, 1 H, Ar), 7.39 - 7.45 (m,
22 3 3
H N ] ; H NMR (400 MHz, CDCl ) δ 1.32
-
2
2
-C=C), 2.00 - 2.07 (m, 2 H, Notes and references
2
2
2
),
1
2
D. G. Gusev, Organometallics. 2009, 28, 6458–6461
A. A. Tukov, A. T. Normand, M. S. Nechaev, Dalton Trans.
5
2
1
3
H, Ar), 7.75 (s, 1 H, C=CH-N), 7.82 - 7.86 (m, 2 H, Ar) ppm; C NMR
) δ 26.3, 28.4, 28.5, 30.2, 33.5, 50.3, 114.4, 119.3,
2
009, 7015–7028
T. Dröge, F. Glorius, Angew. Chem. Int. Ed. 2010, 49, 6940–
952
S. Diez-Gonzalez, S. P. Nolan, Coord. Chem. Rev. 2007, 251
74–883
(
400 MHz, CDCl
3
3
4
-
1
1
1
1
25.6, 128.0, 128.7, 130.6, 138.6, 147.6 ppm; IR νmax/cm 1024.2,
053.1, 1078.2, 1188.1, 1215.1, 1356.0, 1438.9, 1454.2, 1483.3,
643.3, 2850.8, 2926.0, 3064.9, 3082.2, 3120.8
6
,
8
5
6
7
D. Nelson, S. P. Nolan, Chem. Soc. Rev. 2013, 42, 6723–6753
H. V. Huynh, G. Frison, J. Org. Chem. 2013, 78, 328–338
1
-benzyl-4-(2-bromoethyl)-1H-1,2,3-triazole 4g
+
White solid; Mp: 71.9-74.3°C; HRMS (ESI) [M+H] found 266.0283,
S. Díez-González, N. M. Scott, S. P. Nolan, Organometallics,
006, 25, 2355-2358
+
1
calculated 266.0287 for [C11
.28 (t, J = 7.0 Hz, 2 H, CH -C-Br), 3.64 (t, J = 6.8 Hz, 2 H, CH
s, 2 H, CH -N), 7.25 - 7.29 (m, 2 H, Ar), 7.34 - 7.42 (m, 4 H, Ar, C=CH-
H
13BrN
3
] ; H NMR (400MHz, CDCl
3
) δ
-Br), 5.53
2
3
(
2
2
8
9
1
1
1
1
1
1
1
C. S. J. Cazin, O. Santoro, F. Lazreg, Y. Minenkov, L. Cavallo,
Dalton Trans. 2015, 44, 18138-18144
C. S. J. Cazin, M. Trose, F. Lazreg, M. Lesieur, J. Org. Chem.
2
13
3
N) ppm; C NMR (400 MHz,CDCl ) δ 29.4, 31.4, 54.0, 121.6, 127.9,
-1
1
1
1
28.6, 129.0, 129.4, 134.6 ppm; IR νmax/cm 1028.0, 1051.1, 1126.4,
2
015, 80, 9910-9914
0 E. Brenner, D. Matt, M. Teci, L, Toupet, Dalton Trans, 2015,
, 13991-13998
1 C. S. J. Cazin, F. Lazreg, F. Nahra, Coord. Chem. Rev, 2015 48-
205.5, 1245.4, 1294.2, 1325.1, 1350.2, 1421.5, 1435.0, 1454.3,
494.8, 1546.9, 2852.7, 2920.2, 3030.2, 3068.7, 3124.7. Data
4
4
73
matched with literature reference .
7
9
(+/-) 1-(1-benzyl-1H-1,2,3-triazol-4-yl)ethanol 4h
2 S. P. Nolan, J. Egbert, C. S. J. Cazin, Catal. Sci. Technol. 2013,
12-926
3 S. P. Nolan, S. Diez-Gonzàlez, N. Marion, Chem. Rev. 2009,
09, 3612-3676
3,
+
Blue white solid ; Mp: 49.7-51.2°C; HRMS (ESI) [M+Na] found
9
NaO] ; 1H NMR
+
2
26.0944, calculated 226.0951 for [C11
400MHz, CDCl ) δ 1.51 - 1.62 (m, 3 H, CH
br. s., 1 H, CH), 5.49 (s, 2 H, CH ), 7.25 - 7.29 (m, 2 H, Ar), 7.35 - 7.39
m, 3 H, Ar), 7.42 (br. s, 1 H, C=CH-N) ppm; 13C NMR (400 MHz, CDCl
23.0, 54.1, 77.2, 120.1, 127.4, 128.0, 128.7, 129.0, 134.4, 129.0,
H
13
N
3
(
(
(
3
3
), 3.29 (br. s., 1 H, OH), 5.06
1
2
4 S. P. Nolan, S. N-Heterocyclic Carbenes: Effective Tools for
Organometallic Synthesis. Wiley-VCH Weinhem, 2014
5 L. Schaper, S. J. Hock, W. A. Herrmann, F. E. Kühn, Angew.
Chem. Int. Ed. 2013, 52, 270-289
3
)
=
-1
1
1
1
28.7, 128.0 ppm; IR νmax/cm 1041.6, 1055.1, 1082.1, 1132.2,
141.9, 1182.4, 1215.1, 1253.7, 1303.9, 1334.7, 1367.5, 1441.9,
446.6, 1465.9, 1496.8, 2968.4, 3066.8, 3124.7, 3358.1. Data
6 H. Horvth, G. Papp, R. Szabolcsi, K. Gnes; F. Jo, ChemSusChem,
2
015, 8, 3036-3038
74
matched with literature reference .
1
1
7 C. Zhang, J Liu, C. Xia, Chin. J. Cat. 2015, 36, 1387-1391
8 C. Czegeni, P. Enik; Papp, A. Katho, F. Jo, J. Mol. Cat. A-Chem.
4-(1-benzyl-1H-1,2,3-triazol-4-yl)butan-1-ol 4i
2
011, 340, 1-8
+
White solid; Mp: 77.3-79.8°C; HRMS (ESI) [M+H] found 232.1445,
1
2
9 L. Meres, M. Albrecht, Chem. Soc.Rev, 2010, 39, 1903-1912
0 T. Soeta, T. Ishizaka, Y. Ukaji, J. Org. Chem. 2016, 81, 2817-
+
1
calculated 232.1444 for [C13
.59 - 1.67 (m, 2 H, CH -C-C-OH), 1.69 - 1.80 (m, 2 H, CH
t, J = 7.5 Hz, 2 H, CH -C=C), 3.62 - 3.71 (m, 2 H, CH -OH), 5.49 (s, 2 H,
H
18
N
3
O] ; H NMR (400 MHz, CDCl
3
) δ
-C-OH), 2.73
1
(
2
2
2
826
2
2
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 7
Please do not adjust margins

PNl ee aws eJ do ou rnn oa tl ao df j uC sht emm ai rs gt ir ny s
Page 8 of 9
ARTICLE
Journal Name
2
1 J. John, C. Wilson-Konderka, C. Metallinos, Adv. Synt. Cat. 48 E. Brenner, D. Matt, M. Henrion, M. Teci L. Toupet Dalton
View Article Online
DOI: 10.1039/C6NJ02089E
2
015, 357, 2071-2081
Trans. 2011, 40, 9889-9898
2
2
2
2 S. Zhang,Y. Zhao, P. Tian, G. Lin, Synlett, 2013, 24, 437-444
3 J. Park, D. T. McQuade, Synthesis, 2012, 44, 1485-1490
4 C. A. Citadelle, E. Le Nouy, F. Bisaro, A. M. Z. Slawin, C. S. J. 50 A. Poater, F. Ragone, S. Giudice, C. Costabile, R. Dorta, S. P.
Cazin, Dalton Trans. 2010, 39, 4489-4491 Nolan, L. Cavallo, Organometallics, 2008, 27, 2679-2681
5 S. P. Nolan, C. S J. Cazin, O. Santoro, A. Collado, A. M. Z. Slawin, 51 S. P. Nolan, S. Diez-Gonzalez, E. Escudero-Adan, S. J. Benet-
49 D. Matt, E. Brenner, M. Teci, C. Gourlaouen, L. Toupet, Chem.
Eur. J. 2015, 21, 10997-11000
2
2
2
2
2
3
3
Chem. Comm. 2013, 49, 10483-10485
6 H. Ibrahim, R. Guillot, F. Cisnetti, A.Gautier, Chem. Comm.
Buchholz, E. Stevens, A. Slawin, Dalton Trans. 2010, 39, 7595-
7606
52 S. R. Zhu, R. Liang, H. Jiang, Tetrahedron, 2012, 68, 7949-7955
2
014, 50, 7154-7156
7 C. Gibard, H. Ibrahim, A. Gautier,F. Cisnetti, Organometallics, 53 A. Poater,B. Cosenza, A. Correa, S. Giudice, F. Ragone, V.
013, 32, 4279-7283 Scarano, L. Cavallo, Eur. J. Inorg. Chem. 2009, 13, 1759-1766
8 W. Chen, B. Liu, X. Ma, F. Wu, Dalton Trans, 2015, 44, 1836- 54 C. Shao, X. Wang, Q. Zhang, S. Luo, J. Zhao, Y. Hu, J. Org.
844 Chem., 2011, 76, 6832-6836
9 O. Santoro, F. Lazreg, D. B. Cordes, A. M. Z. Slawin, C. S. J. Cazin 55 S. Kovács, K. Zih-Peréni, Á. Révész, Z. Novák, Synthesis, 2012,
Dalton Trans. 2016, 45, 4970–4973 44, 3722-3730
0 C. S. J. Cazin, F. Lazreg, D. Cordes, A. M. Z. Slawin, 56 C. Shao, X. Wang, J. Xu, J. Zhao, Q. Zhang, Y. Hu, J. Org. Chem.
Organometallics, 2015, 34, 419-425 2010, 75, 7002-7005
1 C. Jahier-Diallo, M. S. T. Morin, P. Queval, M. Rouen, I. Artur, 57 S. Diez-Gonzalez, A. Correa, L. Cavallo, S. P. Nolan, Chem. Eur.
2
1
P. Querard, L. Toupet, C Crévisy, O. Baslé, M. Mauduit, Chem.
Eur. J. 2015, 21, 993-997
2 A. Vigalok, V. Rawat, K. Press, I. Goldberg, Org. Biomol. Chem.
J. 2006, 12, 7558-7564
5
8 L. Li, X. Fan, Y. Zhang, A. Zhu, G. Zhang Tetrahedron, 2013, 69,
9
939-9946
3
3
3
5
6
9 J. Meng, V. V. Fokin, M.G. Finn, Tet. Lett. 2005, 46, 4543-4546
0 W. A. Herrmann, L. J. Goossen, C. Köcher, G. R. J. Artus,
Angew. Chem. Int. Ed. Engl., 1996, 35, 2805–2807
1 K. Y. Wan, A. J. Lough, R. H. Morris, Organometallics, 2016, 35
1604–1612
2
015, 13, 11189-11193
3 M. Vézina, J. Gagnon, K. Villeneuve, M. Drouin, D. Harvey,
Organometallics, 2015, 20, 273-281
4 R. Ungaro, R. Cacciapaglia, A. Casnati, L. Mandolini, D.
6
,
Reinhoudt, R. Salvio, A. Sartori, J. Am. Chem. Soc. 2006, 128
2322-12330
5 M. Yilmaz, E. Akceylan, A. E. Uyanik, O. Sahin, Applied
Catalysis A: General, 2015, 499, 205-212
,
62 CrysAlisPro, Agilent Technologies, Version 1.171.34.49
(release 20-01-2011 CrysAlis171 .NET) (compiled Jan 20
2011,15:58:25)
63 R. C. Clark, J. S. Reid, Acta Cryst. 1995, A51, 887-897
64 A. Altomare, M. C. Burla, M. Camalli, G. L. Cascarano, C.
Giacovazzo, A. Guagliardi, A. Grazia, G. Moliterni, G. Polidori,
R. Spagna, J. App. Cryst. 1999, 32, 115-119
65 P. W. Betteridge, J. R. Carruthers, R. I. Cooper, K. Prout, D. J.
Watkin, J. Appl. Cryst. 2003, 36, 1487
66 S. G. Alvarez, M. T. Alvarez, Synthesis, 1997, 4, 413-414
1
3
3
3
3
3
6 M. Yilmaz, A. Uyanik, M. E. Bayrakci, Tetrahedron, 2014, 70
307-9313
,
9
7 E. Brenner, D. Matt, H. Henrion, M. Teci, L. Toupet, Dalton
Trans., 2011, 40, 9889-9898
8 I. Bonnamour, U. Darbost, T. Tu, E. Jeanneau, H. Ren,
Tetrahedron, 2014, 70, 2829-2837
9 P. Michael, W. H. Binder, Angew. Chem. Int. Ed. 2015, 54
3918-13922
0 M. Meldal, C. W. Tornøe, Chem. Rev. 2008, 108, 2952-3015
1 D. D. Diaz, S. Punna, P. Holzer, A. K. McPherson, K. B. 68 C. Yu, B. Liu, L. Hu, J. Org. Chem. 2001, 66, 919-924
Sharpless, V. V. Fokin, M. G. Finn, J. Polym. Sci. Part A, 2004, 69 A. Ionescu, D. Cornut, S. Soriano, C. Guissart, P. Van
,
67 G. Colombano, C. Travelli, U. Galli, A. Caldarelli, M. G. Chini, P.
L. Canonico, G. Sorba, G. Bifulco, G. C. Tron, A. A. Genazzani,
J. Med. Chem. 2010 , 53, 616-623
1
4
4
4
2
, 4392-4403
2 Y. Liu, D. D. Diaz, A. A. Accurso, K. B. Sharpless, V. V. Fokin, M. 70 C. Shao, X. Wang, J. Xu, J. Zhao, Q. Zhang, Y. Hu, J. Org. Chem.
G. Finn, J. Polym. Sci. Part A, 2007, 45, 5182-5189 2010, 75, 7002-7005
3 Y. D. Bidal, M. Lesieur, M. Melaimi, F. Nahra, D. B. Cordes, K. 71 Y. D. Bidal, M. Lesieur, M. Melaimi, D. B. Cordes, A. M. Z.
Antwerpen, I. Jabin, Tet. Lett. 2013, 54, 6087-6089
4
4
S. Athurokala Arachchige, A. M. Z. Slawin, G. Bertrand, C. S. J.
Slawin, G. Bertrand, C. S. J. Cazin, Chem. Comm. 2015, 51,
Cazin, Adv. Synth. Catal, 2005, 357, 3155-3161
4778-4781
4
4 S. Diez-Gonzalez, E. C. Escudero-Adan, J. Benet-Buchholz, E. D. 72 M. Liu, O. Reiser, Org. Lett. 2011, 13, 1102-1105
Stevens, A. M. Z. Slawin, S. P. Nolan, Dalton Trans. 2010, 39
595-7606
,
73 V. Fiandanese, F. Iannone, G. Marchese, A. Punzi,
7
Tetrahedron, 2011, 67, 5254-5260
4
4
4
5 H. Diaz-Velazquez, Y. R. Garcia, M. Vandichel, A. Madder, F. 74 S. C. Sau, S. R. Roy, T. K. Sen, D. Mullangi, S. K. Mandala, Adv.
Verpoort, Org. Biomol. Chem. 2014, 12, 9350-9356 Synth. Catal. 2013, 355, 2982-2991
6 C. Gaulier, A. Hospital, B. Legeret, A. F. Delmas, V. Aucagne, F. 75 Y. M. A. Yamada, A. Ohno, T. Sato, Y. Uozumi, Chem. Eur. J.
Cisnetti, A. Gautier, Chem. Commun. 2012, 48, 4005-4007 2015, 21, 17269-17273
7 I. Dinarès, C. Garcia de Miguel, M. Font-Bardia, X. Solans E. 76 J. H. Kim, S. Kim, RSC Advances, 2014, 4, 26516-26523
Alcalde, Organometallics, 2007, 26, 5125-5128
8
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 9 of 9
New Journal of Chemistry
View Article Online
DOI: 10.1039/C6NJ02089E
Sentence :
Novel N-heterocyclic carbene (NHC) copper complexes supported by calix[4]arene were
synthesized showing good performance in catalytic activity in click chemistry.
Image