NHC copper complexes functionalized with sulfoxide and sulfone moieties

Article abstract of DOI:10.1002/aoc.4983

A series of N-heterocyclic copper carbene complexes bearing sulfoxide and sulfone moieties have been prepared. In case of new copper compounds with sulfone ligand, the solid-state structures were determined using X-Ray crystallography. Obtained complexes

Full text of DOI:10.1002/aoc.4983

Received: 2 January 2019
DOI: 10.1002/aoc.4983
Revised: 12 April 2019
Accepted: 13 April 2019
F U L L P A P E R
NHC copper complexes functionalized with sulfoxide and
sulfone moieties
Anna Szadkowska1
Damian Trzybiński1 | Krzysztof Woźniak1
| Robert Pawłowski1,2 | Ewelina Zaorska1 | Sebastian Staszko1 |
1 Biological and Chemical Research
A series of N‐heterocyclic copper carbene complexes bearing sulfoxide and sul-
Centre, Department of Chemistry,
University of Warsaw, Żwirki i Wigury
101, 02‐089 Warszawa, Poland
2 Faculty of Chemistry, University of
Technology, Noakowskiego 3, 00‐664
Warszawa, Poland
fone moieties have been prepared. In case of new copper compounds with sul-
fone ligand, the solid‐state structures were determined using X‐Ray
crystallography. Obtained complexes were investigated as catalysts in such
transformations as: 1,3‐dipolar cycloaddition of alkynes and azides (CuAAC),
A3 coupling reaction and β‐hydroboration and compared with standard copper
catalytic systems.
Correspondence
Anna Szadkowska, Biological and
Chemical Research Centre, Department of
Chemistry, University of Warsaw, Żwirki i
Wigury 101, 02‐089 Warszawa, Poland.
Email: szadkowska.anna@gmail.com
KEYWORDS
A3 coupling reaction, copper catalysis, CuAAC, NHC ligands, β‐Hydroboration
Funding information
Fundacja na rzecz Nauki Polskiej, Grant/
Award Number: Homing Plus programme
/2013/8‐13; Operational Program Innova-
tive Economy 2009‐2013; European
Regional Development Fund; European
Union; Polish Science
1 | INTRODUCTION
of the NHC copper complexes containing mixed ligands
with a sulfur moiety.[5] Examples of mixed copper com-
A rapid development of the transition metal catalysis led
to discovery of new ligands and their applications for the
preparation of organic and biologically relevant mole-
cules.[1] Simultaneously, a special attention has been
devoted to copper catalysts due to their high efficiency
and good functional group tolerance in the formation of
new carbon‐hydrogen, carbon–carbon and carbon‐
heteroatoms bonds.[2] Among different examples of
sophisticated and complex ligands used in the copper
chemistry, N‐heterocyclic carbenes became a good choice
for the performance of various catalytic transformations
in a simple and efficient way.[3] In particular, the NHC
copper complexes that contained both: the aryl and alkyl
groups with different heteroatoms became an interesting
alternative for the traditional well‐known catalytic sys-
tems.[4] To date, a few groups have reported structures
pounds were presented by Zhai's group and Owen's
group. These complexes were formed as copper sulfide
clusters bearing {(NHC)Cu}2(μ‐S) unit[6] or they have
contained a ditopic bis‐thione ligand[7]. Unfortunately,
no catalytic activities of these complexes were detected.
Quite recently, our group have reported the synthesis
of unsymmetrical NHC copper complexes containing
thioether moiety 1a‐c and their applications in various
catalytic organic transformations (structures 1a‐c on
Scheme 1).[8] The best properties were observed for the
catalyst 1b with unsymmetrical IPr NHC ligand.
Based on these findings, we have wondered, whether
oxidation of thioether moiety to sulfoxide and sulfone
units in NHC precursors will influence on stability and
potential catalytic activity of obtained copper initiators.
Herein, we present our findings on the preparation and
Appl Organometal Chem. 2019;e4983.
wileyonlinelibrary.com/journal/aoc
© 2019 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.4983

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SZADKOWSKA ET AL.
SCHEME 1 Synthesis of NHC copper
complexes with sulfoxide and sulfone
moieties.
activity examination of copper complexes bearing unsym-
metrical NHC ligands with sulfoxide and sulfone motifs.
expected NHC salts 5a,b and 6a,b. Finally, following the
standard procedure,[13] we were able to isolate four new
NHC copper complexes 7a,b and 8a,b with sulfoxide
and sulfone motifs with good yields (50–66%). Presented
copper compounds were characterized using spectro-
scopic methods. For two of the NHC copper complexes
(8a and 8b), crystallographic analyses were also carried
out (for details see: Figure 1 and Table 1). Interestingly,
single‐crystal X‐ray diffraction analysis revealed that the
complex 8b has a dimer structure. Unfortunately, proba-
bly due to a lower stability of the sulfoxide complexes
7a and 7b, all attempts to obtain good quality single‐
crystals of these compounds failed.
2 | RESULTS AND DISCUSSION
2.1 | Syntheses and characterization
The syntheses of new NHC copper complexes: 7a,b and
8a,b were accomplished by easy and well‐established
methods as summarized in Scheme 1.[9]
The preparation of starting materials, and used reac-
tion conditions, were adopted from literature reports.[10]
Initially, the appropriate anilines (2a and 2b) were trans-
formed to 1‐arylimidazoles 3a and 3b with 40% yield and
65% yield, respectively. In analogy to our previous
reported procedures, the compounds 3a and 3b were
alkylated with (phenylthio)methyl chloride to collect
NHC salts 4a and 4b with good yields (76% and 71%).[8]
The crucial step in the presented synthetic pathway was
the oxidation reaction. The compounds: 4a and 4b were
independently converted into derivatives 5a,b and 6a,b
by the treatment with 1.1 eq. and 4 eq. of Oxone® in the
mixture of solvents MeOH/H2O.[11] These four NHC pre-
cursors (5a,b and 6a,b) were obtained as white powders
with acceptable yields (55–70%). Other oxidants includ-
ing: H2O2 and sodium hypochlorite, were also screened
in these transformations, however, no better results were
achieved.[12] We have also studied the application of com-
mercially available alkylation agents such as:
chloromethyl phenyl sulfoxide and chloromethyl phenyl
sulfone instead of oxidation of the compounds 4a and
4b. However, these experiments did not lead to the
2.2 | X‐ray data collection and refinement
of data
The identity of 8a and 8b was proven by the single‐crystal
X‐ray diffraction analysis (Figure 1). It turned out that
investigated compounds crystallize in the monoclinic Cc
(8a) or P21/c (8b) space groups. The values of selected
bond lengths and valence angles are presented in Table 1.
The asymmetric part of the unit cell of 8a contains
except of the molecule of a given compound consists also
the molecule of dichloromethane (Figure 1(a)). The
copper(I) centre in this complex is two coordinated with
the geometry slightly deviating from the linearity (the
value of the C − Cu − Cl angle is 174.51(8)°). The Cu − C
and Cu − Cl bond lengths are 1.883(1) and 2.1035(8)°,
respectively, and these values are in agreement with
those reported by Mankad et al. for the chloro‐(1,3‐
bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene)‐copper(I)

SZADKOWSKA ET AL.
3 of 16
FIGURE 1 Molecular diagrams of 8a
(a) and 8b (b) with atom labelling. The
hydrogen atoms were omitted for clarity.
Displacement ellipsoids are drawn at the
50% probability level. Symmetry code:
(i) − x + 1, −y, −z + 1
dichloromethane solvate.[14] The mean planes defined by
the carbon atoms of the phenyl rings of 2,6‐di-
isopropylphenyl and phenylsulfonylmethyl groups are
twisted by the angles of 96.64(8) and 49,24(8)° relative
to the mean plane defined by the non‐hydrogen atoms
of the NHC moiety.
The 8b complex crystallizes as a centrosymmetric
(μCl)2‐bridged dimer with a half of molecule in the asym-
metric part of the unit cell (Figure 1 (b)). The central
(CuCl)2 core of analyzed compound is slightly symmetric
within the level of error, with the Cu − Cl bond lengths of
2.2073(10) and 2.5067(11) Å (Table 1). The (CuCl)2 frag-
ment forms a plane twisted by the angle of 33.69(11)° to
the mean plane defined by the non‐hydrogen atoms of
the NHC moiety. The Cu − C bond distance is 1.887(3)
Å which is similar to the value observed in the case of
8a (Table 1). The mean planes defined by the carbon
atoms of the phenyl rings of mesityl and
phenylsulfonylmethyl substituents are inclined by the
angles of 70.57(14) and 46.58(14)°, respective to the mean

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SZADKOWSKA ET AL.
TABLE 1 Selected bond lengths and valence angles of 8a and 8b
TABLE 2 Optimization of CuAAC reaction conditionsa
Complex Bond or Angle
Catalyst 8a
Catalyst 8b
Cu6 − Cl7 [Å]
Cu6 − C1 [Å]
2.1035(8)
1.883(3)
1.364(3)
1.441(3)
1.805(3)
1.351(3)
1.446(3)
1.350(4)
103.8(2)
132.5(2)
103.72(14)
174.51(8)
‐‐‐‐‐‐
2.1035(8)
1.883(3)
1.364(3)
1.441(3)
1.805(3)
1.351(3)
1.446(3)
1.350(4)
103.8(2)
132.5(2)
103.72(14)
174.51(8)
87.44(4)
C1 − N2 [Å]
Entry
[Cu] cat. (mol%)
Solvent
Yield (%)
N2 − C8 [Å]
1
‐‐‐‐‐‐
MeOH
MeOH
DCM
n. d.
10
C8 − S9 [Å]
2
7a (5)
7a (5)
7a (5)
7a (5)
7a (5)
7a (5)
7a (5)
7b (5)
8a (5)
8b (5)
8a (2)
8a (1)
8a (0.5)
CuCl (3)
C1 − N5 [Å]
3
n. d.
8
N5 − C18 [Å]
4
DMSO
THF
C3 − C4 [Å]
5
7
N2 − C1 − N5 [°]
Cu6 − C1 − N2 [°]
C10 − S9 − C8 [°]
C1 − Cu6 − Cl7 [°]
Cu6 − Cl7 − Cu6i [°]
6
n‐hexane
EtOAc
Toluene
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
H2O
n. d.
n. d.
n. d.
13
7
8
9
10
11
12
13
14
15
70
Symmetry code: (i) − x + 1, −y, −z + 1.
65
plane defined by the non‐hydrogen atoms of the NHC
ring (Table 1).
75
75
63
12b
2.3 | Catalytic activity
aReaction conditions: benzyl bromide S1 (1.0 equiv.), phenylacetylene S2
(1.2 equiv.), NaN3 (1.2 equiv.), solvent (1 ml), 24 hr.
bReaction conditions: benzyl azide (1.05 equiv.), phenylacetylene S2 (1.0
For the assessment of the catalytic activity of new com-
plexes, we have conducted a systematic examination on
three model reactions. We have initiated our study with
the CuAAC transformation which has been found to have
a variety of application in organic chemistry, medicinal
and drug chemistry and materials science.[15] One‐pot
reactions between benzyl bromide, phenylacetylene,
NaN3 and all obtained NHC copper complexes were
explored as the first examples. Tests were provided at
room temperature in various solvents and the results
are presented in Table 2. At first, we have intended to
confirm that the presence of copper complex is essential
to receive the product of CuAAC reaction. For this rea-
son, we carried out this transformation in the absence
of any copper source and as shown in Table 2 (entry 1),
no product was detected. Next, we have focused on
choosing the best conditions for CuAAC transformation
with the use of new complexes. After screening different
reaction media including: methanol, DCM, DMSO,
THF, n‐hexane, ethyl acetate and toluene, we have found
that when 5 mol% of complex 7a was used, the product
P1 was formed exclusively at most 10% yield (entries 2–
8, Table 2).
equiv.), H2O (3 ml), rt, 1 hr, determined by GC.
yields: 13% (7b) and 65% (8b), respectively (Table 2,
entries 9 and 11). We have also performed test reactions
with 2 mol% and 1 mol% of the catalyst 8a, and to our
delight, we have managed to obtain higher yield of P1
(entries 12–13, Table 2). Further decrease in catalyst load-
ing to 0.5 mol% gave a worse result and the yield of P1
reached only 63% (entry 14, Table 2). Based on presented
investigations, we have singled out the use of methanol as
the best solvent and 1 mol% of complex 8a as the final
conditions for CuAAC transformation. For a comparative
study, we have also presented the result of this model
reaction using CuCl. The obtained yield of the product
P1, was clearly lower than in case of new NHC‐Cu com-
plexes (Table 2, entry 15).[15e]
With the optimized conditions in hand, we next turned
our attention to assessing the scope of CuAAC reaction. A
selection of various alkynes and benzyl bromides were
designed to scope study, and the results are illustrated
in Scheme 2. Presented reactions that employed aliphatic
and aromatic alkynes proceeded smoothly, and series of
different substituted triazoles P1‐P8 were afforded in very
good yields up to 92% in two hours (Scheme 2). Gener-
ally, no specific tendency depending on the electronic
Continuing the evaluation step by changing copper
initiators, we have managed to collect the product P1 in
methanol with 70% yield (entry 10, Table 2) by applying
the sulfone catalyst 8a. Other complexes exhibited lower

SZADKOWSKA ET AL.
5 of 16
TABLE 3 Optimization of A3 coupling reaction conditionsa
Entry
[Cu] cat. (mol%)
Solvent
Yield (%)
n. d.
55
1
‐‐‐‐‐‐
MeOH
DCM
2
8a (1)
3
8a (1)
n‐hexane
Toluene
DMSO
THF
40
51
64
68
90
11
23
86
92
89
79
15
91
4
8a (1)
5
8a (1)
6
8a (1)
7
8a (1)
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
8
7a (1)
9
7b (1)
10
11
12
13
14
15
8b (1)
8a (0.5)
8a (0.2)
IPrCuCl (1)
CuCl (1)
1b (0.5)
aReaction conditions: phenylacetylene S2 (1.1 eq.), dimethylamine S3
(1.1 equiv.), cyclohexenecarbaldehyde S4 (1.0 equiv.), solvent (1 ml),
20 min, isolated yield.
SCHEME 2 Scope studies of the CuAAC reaction
nature of starting materials was noticeable. The 1,4‐
disubstituted triazoles were afforded as the products of
CuAAC reaction. The combination of the alkyne and
the benzyl bromide with strong electron‐donating groups
(−Me and –t‐Bu) and (–OMe and –Me) gave the highest
yields during the scope study (Scheme 2, P7 and P8 89%
and 92% respectively). The products bearing electron‐
withdrawing substituents were obtained with slightly
lower yields (P3, 84% and P5, 86%, Scheme 2). Moreover,
the presence of both electronically different groups also
resulted in the formation of the desired triazole P6 in
good yield (90%) (Scheme 2). Finally, for 1,4‐disubstituted
triazoles with aliphatic and heterocyclic motifs, the three‐
component reaction underwent smoothly and provided
the corresponding products: P2 (85%) and P4 (89%)
(Scheme 2).
During further research on catalytic activity of
obtained copper catalysts, we have also investigated the
A3 coupling reaction. This multicomponent transforma-
tion is promoted often by copper catalytic systems and
gives simple access to functionalized amine products.[16]
At the beginning of our examination on A3
coupling reaction, using only model compounds:
results of CuAAC reaction, we chose the complex 8a for
the solvent screening. This study showed that MeOH
was the optimal medium for this A3 coupling transforma-
tion as well, and the expected product P9 was obtained
with 90% yield using 1 mol% of the complex 8a (entry 7,
Table 3). The employment of other solvents like DCM,
n‐hexane, toluene, DMSO and THF did not increase
yields (Table 3, entries 2–6, 40–68%). To ensure, that the
complex 8a was the best catalyst among tested copper
compounds, we have also conducted the model A3 cou-
pling reaction with sulfoxide and sulfone initiators: 7a,
7b and 8a (Table 3, entries 8–10). Trials were provided
in methanol and resulted in decreased yields (11–86%).
To further improve the yielding of the investigated trans-
formation, we have examined the effect of catalyst load-
ing (Table 3, entries 11–12). During this step, we have
managed to collect the desired product P9 in 92% yield
using 0.5 mol% of 8a. Lower loading of the complex 8a
(0.2 mol%) didn't significantly affect the reaction. In Table
3, we have also collated outcomes for well‐established
NHC copper catalyst IPrCuCl, inorganic copper salt
CuCl and the sulfur complex 1b under similar
conditions.[8,17]
cyclohexanecarboxaldehyde,
dimethylamine
and
phenylacetylene without any copper source, we have
noted that the desired product P9 was not formed at all
(Table 3, entry 1). Subsequently, on the basis of previous
After brief survey of solvent and catalyst's loadings, we
have designated the optimal conditions for A3 coupling

6 of 16
SZADKOWSKA ET AL.
TABLE 4 Optimization of β‐hydroboration reaction conditions
reaction. These reaction conditions for the assay were:
0.5 mol% loading of complex 8a and methanol as reaction
media. As shown in Scheme 3, different amines, alde-
hydes and alkynes were compatible under introduced
conditions and afforded the expected products in very
good yields (76–93%). The catalytic system 8a tolerated
both electron‐donating (P10, P14) and electron‐
withdrawing phenylalkynes (P11) and the utility of ali-
phatic, aromatic and cyclic amines (P9‐P13, P16, P15
and P14) as well to obtain target compounds. More inter-
estingly, the application of the complex 8a allowed to pro-
vide desired propargylamines in 20 minutes.
Another popular copper‐mediated reaction, that we
have studied during our research, was β‐hydroboration
transformation.[18] Organoboron compounds, due to their
availability and compatibility with variety of functional
groups, are important tools in organometallic chemis-
try.[19] For the trial tests of β‐hydroboration reaction, we
have adopted conditions from Cazin's work and our pre-
vious report (Table 4).[8,20] As our benchmark substrate
was chosen 1‐phenyl‐1‐butyne (S5). Using 0.05 mol% of
catalyst loading and CPME as the solvent, we were able
Entry
[Cu] cat. (mol%)
Solvent
Yield (%)
1
2
3
4
5
6
7
8
7a (0.05)
CPME
CPME
CPME
CPME
i‐PrOH
CPME
CPME
toluene
27a
21a
98a
97a
34b
98c
97a
78d
7b (0.05)
8a (0.05)
8b (0.05)
IPrCuCl (0.04)
IMesCuCl (0.04)
1b (0.05)
CuCl (2)
aReaction conditions: [Cu] cat. (0.05 mol%), B2(pin)2 (1.1 eq), NaOH
(1 mol%), MeOH (0.1 ml), CPME (1 ml), 18 hr, isolated yields, only β isomer
was detected.
bReaction conditions: [Cu] cat. (0.04 mol%), B2(pin)2 (1.1 equiv.), NaOt‐Bu
(1 mol%), MeOH (0.18 ml), i‐PrOH (2.4 ml), 16 hr, isolated yields.
cReaction conditions: [Cu] cat. (0.04 mol%), B2(pin)2 (1.1 equiv.), NaOH
(5 mol%), MeOH (0.05 ml), CPME (0.6 ml), 16 hr, isolated yield.
dReaction conditions: HBpin (1.5 equiv.), [Cu] cat. (2.0 mol%), ligand MeAr‐
Xan (2.0 mol%), t‐BuONa (12 mol%), toluene (1.0 ml), 20 hr, isolated yield.
to afford the product of hydroboration P17 with a wide
range of yields after 18 hours (Table 4, entries 1–4, 21–
98%). As in the case of previous studies, the best reactivity
was observed for sulfone complexes, and especially the
initiator 8a with 2,6‐diisopropylphenyl group provided
the highest yield in hydroboration (Table 4, entry 3,
98%). Still, the complexes with sulfoxide moiety gave the
lowest yields (Table 4, entries 1–2, 21–27%), even when
β‐hydroboration was prolonged to 48 hours. To complete
the activity picture, we have gathered the results obtained
for compounds 7a‐8b with activities of various com-
plexes: IPrCuCl, IMesCuCl (Table 4, entries 5–6), as
well as for other sulfur derivative 1b and CuCl (Table 4,
entry 7–8).[8,20] In general, all catalysts proceeded very
well the addition of boron group to alkyne S5 and exhib-
ited high regioselectivity, however with one exception
(Table 4, entry 5). This outcome was probably caused by
utilization of a different reaction media (i‐PrOH instead
of CPME).
Following the trial β‐hydroboration reaction, further
examination was conducted with the best catalyst namely
8a (Scheme 4). We have attempted to expand the catalytic
scope towards β‐hydroboration reaction of triple and dou-
ble bonds. As illustrated in Scheme 4, six different
alkynes and alkenes were used and treated with bis
(pinacolato)diboron in air by using the green solvent
CPME. Both electron‐rich and electron‐deficient sub-
strates gave the desired pinacol boronic esters (P17‐P22)
SCHEME 3 Scope studies of the A3 coupling reaction.

SZADKOWSKA ET AL.
7 of 16
naphthalenes and heterocycles scaffolds were reactive in
the presence of the copper catalyst 8a and the addition
of boron group to unsaturated compounds underwent in
simple and efficient way. Regarding the tested substrates,
excellent regioselectivity was observed, because all prod-
ucts (P17‐P19) were collected as single isomers.
To summarize catalytic activity of novel complexes, on
Scheme 5 were presented possible catalytic cycles of
examined transformations. The cycle A shows a plausible
mechanism for CuAAC reaction according to Jin et al.
[21]
latest findings.
The A3 coupling mechanism involves
C–H activation of the alkyne by the NHC copper catalyst
(cycle B).[16] For the hydroboration reaction, a boryl cop-
per species (LCu–Bpin) may be generated as the catalytic
species (cycle C).[22]
3 | CONCLUSIONS
In conclusion, new NHC copper complexes with sulfox-
ide and sulfone moieties have been accomplished and
examined in transformations based on C‐H bond
functionalization including 1,3‐dipolar cycloaddition, A3
coupling reaction and β‐hydroboration. Obtained copper
compounds revealed various activities depending on the
oxidation state of the sulfur atom in the NHC ligand. In
framework of our studies, copper initiators with sulfone
motifs exhibited better stability and catalytic efficiency.
SCHEME 4 Scope studies of the β‐hydroboration reaction
in excellent yields (94–98%) using 0.05 mol% of 8a and
1 mol% of NaOH in 18 hours. We have confirmed that
wide range of useful functionalities including: aliphatic,
SCHEME 5 Possible catalytic cycles for the NHC copper‐catalyzed reactions

8 of 16
SZADKOWSKA ET AL.
Conducted activity experiments revealed that, the com-
plex 8a with 2,6‐diisopropylphenyl group and sulfone
moiety exhibited suitable electronic and steric properties
and led to high catalytic performance. Attempts to under-
stand the difference between activity of three groups of
copper complexes bearing sulfur on various oxidation
states are in progress in our laboratory.
4.2 | Synthetic procedures of ligands and
complexes
4.2.1 | 1‐(2,6‐diisopropylphenyl)‐1H‐imid-
azole (3a)
2,6‐Diisopropylaniline 2a (8.9 g, 9.4 mL, 50 mmol) and
30% glyoxal (8 ml) were stirred in methanol (45 ml) at
room temperature, for 24 hr. Next, ammonium chloride
(5.4 g), 37% solution of formaldehyde (8 ml) and metha-
nol (200 ml) were added the reaction mixture and
refluxed for 1 hr. Subsequently, a solution of 85% H3PO4
(7 ml) was added to the reaction mixture and refluxed
for another 1 hr. The reaction was monitored by TLC
(n‐hexane/ethyl acetate, v/v = 1:1). After completion of
reaction the solvent was evaporated. The reaction mix-
ture was poured into 300 g of crushed ice and 40% solu-
tion of KOH was gradually added until the pH = 9. The
resulting mixture was extracted with Et2O (5 x 75 ml).
The collected organic layers were dried over anhydrous
MgSO4. After concentration by evaporation under the
reduced pressure, the crude product was purified by col-
umn chromatography (n‐hexane/ethyl acetate, v/
v = 1:1). The product 3a was obtained as a dark brown
4 | EXPERIMENTAL
4.1 | General
All commercially available compounds and solvents were
purchased from Sigma‐Aldrich and used as received with-
out further purification. Solvents had HPLC purity. Flash
columns were performed using silica gel 60 (230–400
mesh). NMR spectra were recorded in CDCl3 and CD2Cl2
solvents on Varian 400 MHz. Chemical shifts (δ) are
given in ppm relative to TMS, coupling constants are (J)
in Hz. In IR spectra wavenumbers are in cm−1. MS spec-
tra were recorded on LCMS‐IT TOF Shimadzu spectrom-
eter. IR spectra were recorded on Thermo Scientific™
Nicolet™ iS™50 FT‐IR Spectrometer. Melting points were
recorded by MPM‐HVZ Paul Marienfeld GmbH & Co. KG
Melting Point Meters.
Crystallographic studies were carried out to confirm
the structures of novel copper complexes. Good‐quality
single‐crystals of 8a and 8b were selected for the X‐ray
diffraction experiments at T = 100(2) K. They were
mounted with paratone‐N oil to the MiTeGen micro‐
mounts. Diffraction data were collected on the Agilent
Technologies SuperNova Dual Source diffractometer
using CrysAlis RED software.[23] The analytical numeric
absorption correction using a multifaceted crystal model
based on expressions derived by R.C. Clark & J.S. Reid[24]
implemented in SCALE3 ABSPACK scaling algorithm
was applied.[24] The structural determination procedure
was carried out using the SHELX package.[25] The struc-
tures were solved with direct methods and then succes-
sive least‐squares refinements were carried out based on
full‐matrix least‐squares on F 2 using the SHELXL‐97 pro-
gram.[25] All H‐atoms were positioned geometrically, with
C–H equal to 0.93, 0.96, 0.97 and 0.98 Å for the aromatic,
methyl, methylene and methine H‐atoms, respectively,
and constrained to ride on their parent atoms with
Uiso(H) = xUeq(C), where x = 1.2 for the aromatic, meth-
ylene and methine H‐atoms and x = 1.5 for the methyl H‐
atoms. All presented interactions were found using the
PLATON program.[26] The figures for this publication
were prepared using ORTEP‐3 and Mercury
programs.[27],[28]
1
solid in 40% yield (4.55 g). H NMR (400 MHz, CDCl3):
δ 7.49–7.36 (m, 2H), 7.28–7.14 (m, 3H), 3.44 (s, 1H),
2.45–2.32 (m, 2H), 1.11 (d, J = 6.9 Hz, 12H) ppm;
13C{1H} NMR (101 MHz, CDCl3): δ 146.5, 129.8, 129.4,
123.7, 122.8, 28.1, 24.4, 24.3 ppm. Spectroscopic data for
the compound 3a were consistent with the previously
reported ones.[9]
4.2.2 | 1‐(2,4,6‐trimethylylphenyl)‐1H‐
imidazole (3b)
2,4,6‐trimethylaniline 2b (6.8 g, 7.0 ml, 50 mmol) and 30%
glyoxal (8.1 ml) were placed into a round bottom flask
and were stirred in methanol (30 ml) at room tempera-
ture for 24 hr. Next, ammonium chloride (5.4 g), 37%
solution of formaldehyde (8 ml) and methanol (200 ml)
were transferred to the flask and refluxed for 1 hr. After
this time, 85% solution of H3PO4 (7 ml) was added to
the reaction mixture and was refluxed for another 1 hr.
The reaction was monitored by TLC (n‐hexane/ethyl ace-
tate, v/v = 1:1). After completion of reaction the solvent
was evaporated. The reaction mixture was poured into
300 g of crushed ice and 40% solution of KOH was grad-
ually added until the pH = 9. The resulting mixture was
extracted with Et2O (5 x 75 ml). The collected organic
layers were dried over anhydrous MgSO4. After concen-
tration by evaporation under reduced pressure the crude
product was purified by column chromatography (n‐

SZADKOWSKA ET AL.
9 of 16
hexane/ethyl acetate, v/v = 1:1) to give yellow solid (65%,
6.0 g). H NMR (400 MHz, CDCl3): δ 7.42 (t, J = 1.0 Hz,
for C22H26N2OS [M–H–Cl]+: 367.1839, found 367.1841;
IR (diamond tip): ν 2964, 1544, 1444, 1193, 1084, 1044,
806, 758, 742, 719, 690, 667, 614, 555, 513, 458 cm−1. M.
p. = 152 °C.
1
1H), 7.22 (t, J = 1.1 Hz, 1H), 7.00–6.92 (m, 2H), 6.88 (t,
J = 1.2 Hz, 1H), 2.33 (s, 3H), 1.98 (s, 6H) ppm; 13C{1H}
NMR (101 MHz, CDCl3): δ 138.8, 137.5, 135.4, 133.4,
129.5, 128.9, 120.0, 28.1, 21.0, 17.3 ppm. Spectroscopic
data for the compound 3b were consistent with the previ-
ously reported ones.[29]
4.2.5 | Ligand precursor (6a)
In a 10 ml flask, Oxone™ (1.6 g, 5.2 mmol, 4 eq.) was dis-
solved in water (4 ml). The flask was cooled down to
10 °C and the solution of compound 4a (0.5 g, 1.3 mmol)
in methanol (4 ml) was slowly dropped to the mixture.
The reaction mixture was brought to room temperature.
After completion of reaction solvents were evaporated,
and the resulting compound 6a was purified by column
chromatography (dichloromethane/methanol, from v/
v = 95:5 to v/v = 9:1). The product was obtained as a
4.2.3 | Ligand precursor (4a)
A 25 ml flask was charged with compound 3a (2 g,
0.0087 mol) and chloromethyl phenyl sulfide (1.45 g;
1.2 ml; 0.009 mol) then dry DMF (6 ml) was added. The
reaction was carried out at 100 °C under an inert atmo-
sphere. The reaction was monitored by TLC (dichloro-
methane/methanol v/v = 9:1). After completion of
reaction the solvent was evaporated, the resulting com-
pound 4a was purified by column chromatography
1
white solid in 66% yield (0.35 g). H NMR (400 MHz,
CDCl3): δ 10.40 (s, 1H), 7.89 (s, 1H), 7.63 (d, J = 7.6 Hz,
2H), 7.45 (t, J = 7.8 Hz, 1H), 7.34–7.27 (m, 3H), 7.21(d,
J = 8 Hz, 2H), 7.04 (s, 1H), 6.41 (s, 2H), 1.97 (sep, 2H),
1.05 (m, 12H) ppm; 13C{1H} NMR (101 MHz, CDCl3): δ
145.2, 138.9, 132.2, 131.8, 129.9, 129.8, 129.7, 128.7,
124.6, 124.1, 122.1, 52.8, 28.6, 24.4. 24.3 ppm; HRMS‐ESI
(m/z) calcd for C22H26N2SO2 [M–H–Cl]+: 383.1788, found
383.1798; IR (diamond tip): ν 2967, 1546, 1448, 1328,
1273, 1196, 1148, 1085, 1068, 1046, 1020, 806, 757, 735,
673, 631, 612, 577, 550, 525, 516, 480, 461, 445, 415 cm
−1. M. p. = 161 °C.
(dichloromethane/methanol, v/v
=
9:1).
Then
crystallisation was carried out with dichloromethane/n‐
pentane. The product was obtained as a dark brown solid
in 76% yield (2.65 g). 1H NMR (400 MHz, CDCl3): δ 10.48
(s, 1H), 7.88 (br, 1H), 7.70–7.65 (m, 2H), 7.50–7.40 (m,
1H), 7.38–7.27 (m, 3H), 7.25–7.18 (m, 2H), 6.39 (s, 2H),
1.96 (dd, J = 13.5, 6.8 Hz, 2H), 1.05 (dd, J = 25.7,
6.8 Hz, 12H) ppm; 13C{1H} NMR (101 MHz, CDCl3): δ
145.2, 139.0, 132.0, 131.8, 129.9, 129.7, 129.6, 128.7,
124.6, 124.0, 122.0, 52.8, 28.5, 24.3, 24.1 ppm; Spectro-
scopic data for the compound 4a were consistent with
the previously reported ones.[8]
4.2.6 | Copper complex (7a)
In dry and argon flushed Schlenk flask were placed
copper(I) chloride (0.047 g; 0.47 mmol), ligand precursor
5a (0.18 g; 0.45 mmol), potassium tert‐butoxide (0.053 g;
0.47 mmol). All reagents were dissolved in dry THF
(8 ml). The mixture was stirred for 24 hr at room temper-
ature under argon atmosphere. The reaction was moni-
tored by TLC (n‐hexane/ethyl acetate, v/v = 7:3). After
completion of the reaction the solvent was evaporated.
The crude product was purified by column chromatogra-
4.2.4 | Ligand precursor (5a)
In a 10 ml flask, Oxone™ (0.28 g, 0.9 mmol, 1.1 equiv.)
was dissolved in water (3 ml). The flask was cooled down
to 10 °C and the solution of compound 4a (0.32 g,
0.8 mmol) in methanol (3 ml) was slowly dropped to
the mixture. The reaction mixture was brought to room
temperature. After completion of reaction solvents were
evaporated, and the resulting compound 5a was purified
by column chromatography (dichloromethane/methanol,
from v/v = 95:5 to v/v = 9:1). The product was obtained
as a white solid in 60% yield (0.2 g). 1H NMR
(400 MHz, CDCl3): δ 9.91 (s, 1H), 7.99 (s, 1H), 7.85 (dd,
J = 1.8, 8 Hz, 2H), 7.58–7.49 (m, 4H), 7.29–7.23 (m,
2H), 7.00 (m, 1H), 6.93 (d, J = 12 Hz, 1H), 2.22–2.19 (m,
1H), 1.89 (sep, 2H), 1.26 (d, J = 4 Hz, 2H), 1.13–1.03
(m, 9H) ppm; 13C{1H} NMR (101 MHz, CDCl3): δ 145.4,
145.0, 138.1, 137.6, 132.0, 131.9, 129.7, 129.6, 124.9,
124.7, 124.6, 124.0, 123.2, 66.8, 34.1, 28.6, 28.4, 24.5,
24.3, 24.2, 24.1, 22.3, 14.0 ppm; HRMS‐ESI (m/z) calcd
phy (n‐hexane/ethyl acetate, from v/v
= 95:5 to
v/v = 7:3). Subsequently, the crystallization from
dichloromethane/n‐pentane was carried out to give the
1
complex 7a as a white solid in 52% yield (0.09 g). H
NMR (400 MHz, CDCl3): δ 7.89 (s, 1H), 7.63 (d,
J = 7.6 Hz, 2H), 7.45 (t, J = 7.8 Hz, 1H), 7.34–7.27 (m,
3H), 7.21 (d, J = 8 Hz, 2H), 7.04 (s, 1H), 6.41 (s, 2H),
1.97 (sep, 2H), 1.05 (m, 12H) ppm; 13C{1H} NMR
(101 MHz, CDCl3): δ 151.2, 14.3, 147.4, 145.6, 145.2,
140.3, 138.2, 133.8, 132.0, 131.6, 130.6, 129.9, 129.6,
129.3, 124.5, 123.9, 123.8, 121.9, 113.5, 11.5, 70.4, 65.8,
28.3, 27.9, 24.7, 24.4, 24.2, 24.0, 23.7, 23.6 ppm; HRMS‐

10 of 16
SZADKOWSKA ET AL.
ESI (m/z) calcd for C22H26N2OSCu [M–Cl]+: 429.1062,
found 429.1064; IR (diamond tip): ν 2920, 2182, 2028,
1986, 1691, 1489, 1443, 1255, 1212, 1085, 1046, 749,
Spectroscopic data for the compound 4b were consistent
with the previously reported ones.[8]
691 cm−1
.
4.2.9 | Ligand precursor (5b)
4.2.7 | Copper complex (8a)
In a 10 ml flask, Oxone™ (0.5 g, 1.6 mmol, 1.1 eq.) was
dissolved in water (2 ml). The flask was cooled down to
10 °C and the solution of compound 4b (0.49 g, 1.5 mmol)
in methanol (2 ml) was slowly dropped to the mixture.
The reaction mixture was brought to room temperature.
After completion of reaction solvents were evaporated,
and the resulting compound 5b was purified by column
chromatography (dichloromethane/methanol, from v/
v = 95:5 to v/v = 9:1). The product was obtained as a
In dry and argon flushed Schlenk flask were placed
copper(I) chloride (0.056 g; 0.64 mmol), ligand precursor
6a (0.23 g; 0.54 mmol), potassium tert‐butoxide (0.063 g;
0.56 mmol). All reagents were dissolved in dry THF
(16 ml). The mixture was stirred for 24 hr at room tem-
perature under argon atmosphere. The reaction was mon-
itored by TLC (n‐hexane/ethyl acetate, v/v = 7:3). After
completion of the reaction the solvent was evaporated.
The crude product was purified by column chromatogra-
phy (n‐hexane/ethyl acetate, from v/v = 95:5 to
v/v = 7:3). Subsequently, the crystallization from
dichloromethane/n‐pentane was carried out to give the
1
white solid in 55% yield (0.29 g). H NMR (400 MHz,
CDCl3) δ 10.01 (t, J = 1.4 Hz, 1H), 8.13–8.09 (m, 1H),
8.00–7.90 (m, 2H), 7.61 (d, J = 7.5 Hz, 1H), 7.51 (t,
J = 7.8 Hz, 2H), 7.24–7.20 (m, 1H), 6.86 (s, 2H), 6.76 (s,
2H), 2.22 (s, 3H), 1.87 (s, 6H) ppm; 13C{1H} NMR
(101 MHz, CDCl3): δ 141.3, 139.4, 135.2, 134.4, 134.0,
129.7, 129.3, 124.5, 123.2, 65.8, 21.0, 17.4 ppm; HRMS‐
ESI (m/z) calcd for C19H21N2SO [M–H–Cl]+: 325.1369,
found 325.137; IR (diamond tip): ν 3346, 2971, 2918,
1667, 1548, 1441, 1380, 1274, 1200, 1086, 1044, 879, 748,
692, 577 cm−1. M. p. = 162 °C.
1
complex 8a as a white solid in 66% yield (0.35 g). H
NMR (400 MHz, CDCl3): δ 7.86 (d, J = 7.6 Hz, 2H), 7.72
(t, J = 8 Hz, 1H), 7.64–7.53 (m, 3H), 7.40 (t, J = 8 Hz,
1H), 7.18 (d, J = 8 Hz, 2H), 5.59 (s, 2H), 5.28 (d,
J = 0.5 Hz, 1H), 2.05 (sep, J = 7 Hz, 2H), 1.15–0.97 (m,
12H); 13C NMR (100 MHz, CDCl3) δ 145.2, 135.3, 134.3,
133.5 130.7, 130.1, 129.0, 124.3, 69.2, 53.5, 34.1, 28.1,
24.5, 24.4 22.5, 14.0 ppm; HRMS‐ESI (m/z) calcd for
C22H26N2SO2Cu [M–Cl]+: 445.1011, found 445.1014; IR
(diamond tip): ν 2965, 1550, 1447, 1382, 1330, 1255,
1188, 1145, 1082, 1043, 1016, 914, 856, 755, 727, 671,
4.2.10 | Ligand precursor (6b)
630, 611, 574, 549, 524 cm−1
.
In a 20 ml flask, Oxone™ (1.1 g, 1.34 mmol, 4 eq.) was
dissolved in water (4 ml). The flask was cooled down to
10 °C and the solution of compound 4b (0.3 g, 0.87 mmol)
in methanol (4 ml) was slowly dropped to the mixture.
The reaction mixture was brought to room temperature.
After completion of reaction solvents were evaporated,
and the resulting compound 6b was purified by column
chromatography (dichloromethane/methanol, from v/
v = 95:5 to v/v = 9:1). The product was obtained as a
4.2.8 | Ligand precursor (4b)
A Schlenk flask was charged with compound 3b (2 g,
0.0087 mol) and chloromethyl phenyl sulfide (1.45 g;
1.2 ml; 0.009 mol). Next, dry DMF (6 ml) was added to
the reaction mixture. The reaction was carried out at
100 °C under an argon atmosphere and was monitored
by TLC (dichloromethane/methanol v/v = 9:1). After
completion of reaction the solvent was evaporated and
the resulting compound 4b was purified by column chro-
matography (dichloromethane/methanol, v/v = 9:1).
1
white solid in 70% yield (0.23 g). H NMR (400 MHz,
CDCl3) δ 9.88 (s, 1H), 7.82 (d, J = 7.1 Hz, 3H), 7.52 (dt,
J = 20.7, 7.0 Hz, 3H), 7.05–6.89 (m, 3H), 6.78 (d,
J = 13.3 Hz, 1H), 6.11 (d, J = 13.2 Hz, 1H), 2.32 (s, 3H),
2.03 (s, 3H), 1.75 (s, 3H) ppm; 13C{1H} NMR (101 MHz,
CDCl3): δ 141.6, 138.2, 137.7, 132.0, 130.0, 130.2, 129.8,
124.9, 123.9, 122.2, 67.0, 21.1, 17.6, 17.4 ppm; HRMS‐ESI
(m/z) calcd for C19H21N2SO2 [M–H–Cl]+: 341.1318, found
341.1319; IR (diamond tip): ν 3374, 2922, 1608, 1548,
1484, 1447, 1328, 1313, 1208, 1145, 1083, 1066, 1023,
998, 932, 855, 755, 685, 671, 631, 600, 570, 549, 525,
438 cm−1. M. p. = 171 °C.
Then,
crystallisation
was
carried
out
with
dichloromethane/n‐pentane. The product was obtained
as a yellow solid in 71% yield (2.67 g). 1H NMR
(400 MHz, CDCl3): δ 10.33 (s, 1H), 7.81–7.79 (m, 1H),
7.60–7.55 lub 7.57 (dd, J = 8.2, 1.4 Hz, 2H), 7.34–7.20
(m, 4H), 7.05 (s, 2H), 6.88 (d, J = 0.5 Hz, 2H), 6.29 (s,
2H), 2.26 (s, 2H), 1.79 (s, 6H) ppm; 13C{1H} NMR
(101 MHz, CDCl3): δ 141.3, 138.7, 134.1, 132.5, 130.4,
129.8, 129.7, 128.2, 123.1, 122.05, 53.0, 21.0, 17.3 ppm;

SZADKOWSKA ET AL.
11 of 16
4.3 | General procedure for the three
component CuAAC reaction reaction
4.2.11 | Copper complexes (7b)
Under an atmosphere of argon imidazolium salt 5b
(0.08 g; 0.23 mmol) and potassium tert‐butoxide
(0.03 g; 0.24 mmol) were dissolved dry THF (7 ml).
Next, copper(I) chloride (0.02 g; 0.24 mmol) was added
to the reaction. The mixture was stirred for 24 hr at
room temperature under an atmosphere of argon. The
reaction was monitored by TLC (DCM/MeOH, v/
v = 9:1). After completion of reaction the solvent was
evaporated. The crude product was purified by column
chromatography (DCM/MeOH, from v/v = 100:0 to
v/v = 98:2). Then crystallization was carried out using
mixture of solvents: dichloromethane/n‐pentane to give
the complex 7b as a light brown solid in 50% yield
Organic halide (0.013 mmol, 1.0 eq), NaN3 (1.2 mmol),
alkyne (0.16 mmol, 1.2 eq.), the appropriate copper com-
plex (1 mol%) and solvent (1 ml) were introduced to the
vial fitted with a screw cap. The reaction was carried
out at room temperature for 1.5 hr and controlled by
TLC (n‐hexane/ethyl acetate, v/v = 7:3). After completion
of the reaction, the solvent was evaporated. The crude
product was purified by column chromatography (n‐hex-
ane/ethyl acetate, v/v = 8:2). The isolated product was
dried under vacuum.
1
4.3.1 | (1‐benzyl‐4‐phenyl‐5‐
(phenylethynyl)‐1H‐1,2,3‐triazole, P1),
white solid, yield 75%
(0.049 g). H NMR (400 MHz, CDCl3) δ 7.94–7.77 (m,
2H), 7.76–7.66 (m, 2H), 7.64–7.44 (m, 3H), 6.96–6.83
(m, 2H), 5.57 (bs, 2H), 2.40–2.15 (m, 3H), 1.89–1.53
(m, 6H) ppm; 13C{1H} NMR (101 MHz, CDCl3): δ
139.9, 135.3, 134.2, 134.1, 130.2, 129.5, 123.4, 121.6,
69.3, 21.0, 17.8, 17.7 ppm; HRMS‐ESI (m/z) calcd for
C19H20N2SOCu [M–Cl]+: 387.0592, found 387.0590; IR
(diamond tip): ν 2963, 2928, 2868, 1694, 1470, 1444,
1427, 1385, 1363, 1255, 1085, 1047, 954, 817, 759, 746,
1H NMR (400 MHz, CDCl3): δ 7.85–7.74 (m, 2H), 7.65 (s,
1H), 7.46–7.27 (m, 8H), 5.57 (s, 2H) ppm; 13C{1H} NMR
(100 MHz, CDCl3): δ 148.2, 134.6, 130.5, 129.1, 129.0,
128.8, 128.1, 125.7, 119.4, 54.2 ppm.
Spectroscopic data for the compound P1 were consis-
tent with the previously reported ones.[30]
691 cm−1
.
4.3.2 | (4‐cyclohexyl‐1‐(2‐iodobenzyl)‐1H‐
1,2,3‐triazole, P2), white crystals, yield 85%
4.2.12 | Copper complexes (8b)
1H NMR (400 MHz, CDCl3): δ 7.88 (d, J = 8.8 Hz, 1H),
7.32 (td, J = 1.2, 7.6 Hz, 1H), 7.03 (t, J = 7.6 Hz, 2H),
5.58 (s, 2H), 2.76 (s, 1H), 2.05 (s 2H), 1.79–1.70 (m, 5H),
1.41–1.22 (m, 4H) ppm; 13C{1H} NMR (101 MHz, CDCl3):
δ 139.8, 137.7, 130.2, 129.4, 129.0, 128.4, 98.5, 58.3, 35.3,
33.0, 32.1, 26.1 ppm. IR (diamond tip) ν 3105, 2943,
1620, 1579, 1565, 1498, 1456, 1444, 1421, 1326, 1302,
1264, 1244, 1225, 1172, 1139, 1105, 1068, 1052, 978, 859,
817, 797, 774, 751, 673, 626, 605, 591, 463, 411 cm−1. M.
p. = 211.5 °C.
Under an atmosphere of argon imidazolium salt 6b
(0.1 g; 0.26 mmol) and potassium tert‐butoxide
(0.032 g; 0.28 mmol) were dissolved dry THF (7 ml).
Next, copper(I) chloride (0.028 g; 0.28 mmol) was
added to the reaction. The mixture was stirred for
24 hr at room temperature under an atmosphere of
argon. The reaction was monitored by TLC (n‐hexane/
EtOAc, v/v = 1:1). After completion of reaction the sol-
vent was evaporated. The crude product was purified by
column chromatography (n‐hexane/EtOAc, from
v/v = 7:3 to v/v = 3:7). Then crystallization was carried
out using mixture of solvents: dichloromethane/n‐pen-
tane to give the complex 8b as a light brown solid in
63% yield (0.072 g). 1H NMR (400 MHz, CDCl3) δ
8.00–7.46 (m, 7H), 7.05–6.80 (m, 2H), 5.55 (bs, 2H),
2.45–2.30 (m, 3H), 1.95–1.70 (m, 6H) ppm; 13C{1H}
NMR (101 MHz, CDCl3): δ 138.5, 133.4, 134.1, 133.1,
133.0, 132.4, 130.4, 130.3, 129.1, 69.3, 20.8, 17.7,
16.0 ppm; HRMS‐ESI (m/z) calcd for C19H20N2SO2Cu
[M–Cl]+: 403.0541, found 403.0544; IR (diamond tip): ν
2918, 1699, 1488, 1446, 1325, 1309, 1144, 1083, 1024,
999, 967, 934, 904, 747, 733, 686, 551, 525, 471, 457,
4.3.3 | (4‐(4‐fluorophenyl)‐1‐(2‐
iodobenzyl)‐1H‐1,2,3‐triazole, P3), white
crystals, yield 84%
1H NMR (400 MHz, CDCl3): δ 7.89 (dd, J = 7.9, 1.2 Hz,
1H), 7.84–7.78 (m, 2H), 7.76 (s, 1H), 7.43–7.37 (m, 2H),
7.36–7.28 (m, 2H), 7.12 (dd, J = 7.8, 1.6 Hz, 1H), 7.08–
7.02 (m, 1H), 5.66 (s, 2H) ppm; 13C{1H} NMR
(101 MHz, CDCl3): δ 148.1, 139.9, 137.4, 130.4, 129.6,
129.1, 128.8, 128.2, 125.7, 119.8, 98.6, 58.5 ppm.
Spectroscopic data for the compound P3 were consis-
tent with the previously reported ones.[31]
436 cm−1
.

12 of 16
SZADKOWSKA ET AL.
1185, 1116, 1072, 1048, 1021, 976, 824, 807, 770, 762,
751, 730, 711, 3065, 3027, 2962, 2928, 2884, 2850, 2813,
1849, 1732, 1625, 1591, 1563, 1468, 1412, 1342, 1284,
1270, 1200, 1159, 1123, 1051, 1022, 996, 955, 931, 883,
795, 772, 756, 718, 695, 637 559, 532, 489, 473, 426 cm
−1; m.p. 223 °C.
4.3.4 | (4‐phenyl‐1‐(2‐(thiophen‐2‐yl)
Ethan‐2‐on‐1‐yl)‐1H‐1,2,3‐triazole, P4,
orange crystals, yield 89%
1H NMR (400 MHz, CDCl3): δ 7.96 (s, 1H), 7.89–7.83 (m,
3H), 7.79 (dd, J = 5.0, 1.1 Hz, 1H), 7.45–7.40 (m, 2H), 7.34
(d, J = 7.5 Hz, 1H), 7.22 (dd, J = 5.0, 3.9 Hz, 1H), 5.78 (s,
2H) ppm; 13C{1H} NMR (101 MHz, CDCl3): δ 183.2,
146.7, 135.9, 133.2, 131.0, 128.8 (d, J = 7.2 Hz), 128.3,
125.8, 121.2, 119.8, 104.1, 55.4 ppm.
4.3.8 | (4‐(4‐methoxyphenyl)‐1‐(4‐
methylbenzyl)‐1H‐1,2,3‐triazole, P8, white
solid, yield 92%
Spectroscopic data for the compound P4 were consis-
tent with the previously reported ones.[32]
1H NMR (400 MHz, CDCl3): δ 7.70 (d, J = 8.9 Hz, 2H),
7.53 (s, 1H), 7.19–7.18 (m, 4H), 6.91 (d, J = 8.9 Hz, 2H),
5.50 (s, 2H), 3.81 (s, 3H), 2.34 (s, 3H) ppm; 13C{1H}
NMR (100 MHz, CDCl3): δ 159.5, 148.0, 138.7, 131.7,
129.8, 128.1, 127.0, 123.3, 118.5, 114.1, 55.3, 54.0,
21.2 ppm; HRMS‐ESI: (m/z) [M + H]+ calcd for
C17H17ON3: 279.1372, found 279.1369; IR (diamond tip):
ν 2919, 1615, 1579, 1559, 1517, 1497, 1469, 1455, 1444,
1417, 1343, 1313, 1301, 1264, 1244, 1222, 1202, 1187,
1136, 1105, 1072, 1051, 1024, 976, 828, 814, 796, 757,
742, 694, 661, 606, 540, 469, 455 cm−1; m.p. 149 °C.
4.3.5 | (4‐phenyl‐1‐(4‐(trifluoromethyl)
benzyl)‐1H‐1,2,3‐triazole, P5, white solid,
yield 86%
1H NMR (400 MHz, CDCl3) δ 7.91–7.90 (m, 1H), 7.78–
7.76 (m, 2H), 7.72 (s, 1H), 7.34–7.32 (m, 1H), 7.18–7.02
(m, 4H), 5.66 (s, 2H) ppm; 13C{1H} NMR (100 MHz,
CDCl3): δ 163.9, 161.4, 147.3, 139.9, 137.3, 130.5, 129.7,
129.1, 127.5, 127.4, 126.7, 126.6, 119.5, 115.9, 115.7, 98.7,
58.5 ppm; 19F NMR (376 MHz, CDCl3): δ −113.5 (d,
J = 8.6 Hz) ppm. Spectroscopic data for the compound
P5 were consistent with the previously reported ones.[33]
4.4 | General procedure for the A3
coupling reaction
In a vial fitted with a screw cap, aldehyde (1.3 mmol,
1.0 eq), alkyne (1.4 mmol, 1.1 eq) and amine (1.3 mmol,
1.1 eq) were dissolved in methanol (1 ml). Next, the
appropriate copper catalyst (0.5 mol%) was introduced
to the reaction mixture. The reaction was performed at
room temperature and was monitored by TLC (n‐hex-
ane/ethyl acetate, v/v = 7:3). After completion of the
reaction (20 mins), the reaction mixture was extracted
with diethyl ether (3 x 1 ml). The combined organic
phases were dried over anhydrous MgSO4 and concen-
trated on a rotary evaporator. The crude product was
purified by column chromatography (n‐hexane/ethyl ace-
tate, v/v = 8:2). The isolated product was dried under
vacuum.
4.3.6 | (1‐(4‐chlorobenzyl)‐4‐(4‐
methoxyphenyl)‐1H‐1,2,3‐triazole, P6),
white crystals, yield 90%
1H NMR (400 MHz, CDCl3) δ 7.71 (d, J = 8.8 Hz, 2H),
7.58 (s, 1H), 7.34 (d, J = 8.4 Hz, 2H), 7.22 (d,
J = 8.4 Hz, 2H), 6.92 (d, J = 8.8 Hz, 2H), 5.50 (s, 2H),
3.81 (s, 3H) ppm; 13C{1H} NMR (101 MHz, CDCl3): δ
159.6, 148.2, 134.7, 133.3, 129.3, 127.0, 126.9, 123.1,
118.6, 114.2, 55.2, 53.4 ppm.
Spectroscopic data for the compound P6 were consis-
tent with the previously reported ones.[32]
4.3.7 | (4‐(4‐(tert‐butyl)phenyl)‐1‐(4‐
methylbenzyl)‐1H‐1,2,3‐triazole, P7, white
solid, yield 89%
4.4.1 | (1‐cyclohexyl‐N,N‐dimethyl‐3‐
fenylprop‐2‐yn‐1‐amine, P9), light‐yellow
oil, yield 92%
1H NMR (400 MHz, CDCl3): δ 7.71 (d, J = 8.5 Hz, 2H),
7.59 (s, 1H), 7.40 (d, J = 8.5 Hz, 2H), 7.18 (s, 4H), 5.51
(s, 2H), 2.34 (s, 3H), 1.31 (s, 9H); 13C{1H} NMR
(100 MHz, CDCl3): δ 151.2, 148.1, 138.6, 131.7, 129.7,
128.0, 127.7, 125.7, 125.4, 119.1, 54.0, 34.6, 31.3,
21.1 ppm; HRMS‐ESI: (m/z) [M + H] + calcd for
C20H23N3: 306.1965, found 306.1973; IR (diamond tip): ν
2958, 2866, 1515, 1495, 1426, 1362, 1268, 1219, 1204,
1H NMR (400 MHz, CDCl3): δ 7.47–7.40 (m, 2H), 7.33–
7.26 (m, 3H), 3.15 (d, J = 10 Hz, 1H), 2.28 (s, 6H), 2.15–
2.07 (m, 1H), 2.04–1.96 (m, 1H), 1.80–1.71 (m, 2H),
1.70–1.63 (m, 1H), 1.54 (ddd, J = 14.5, 11.0, 6.1 Hz, 2H),
1.29–1.16 (m, 2H), 0.99 (ddd, J = 24.0, 11.9, 3.2 Hz, 2H)
ppm; 13C{1H} NMR (101 MHz, CDCl3): δ 131.7, 128.2,

SZADKOWSKA ET AL.
13 of 16
127.7, 123.6, 86.5, 64.2, 41.6, 40.1, 31.1, 30.3, 26.7,
26.1 ppm.
753, 737, 689, 655, 639, 624, 601, 577, 567, 547, 523, 507,
475, 422 cm−1
.
Spectroscopic data for the compound P9 were consis-
tent with the previously reported ones.[8]
4.4.5 | (3‐(4‐(tert‐butyl)phenyl)‐1‐
cyclohexyl‐N,N‐dimethylprop‐2‐yn‐1‐amine,
P13), yellow oil, yield 93%
4.4.2 | (1‐cyclohexyl‐3‐(4‐methoxyphenyl)‐
N,N‐dimethylprop‐2‐yn‐1‐amine, P10),
light‐yellow oil, yield 90%
1H NMR (400 MHz, CDCl3): δ 7.41–7.35 (m, 2H), 7.33–
7.29 (m, 2H), 3.13 (d, J = 9.9 Hz, 3H), 2.27 (s, 6H),
2.15–2.05 (m, 2H), 2.03–1.95 (m, 2H), 1.28 (s, 9H), 1.23–
1.12 (m, 2H), 1.05–0.92 (m, 2H) ppm; 13C{1H} NMR
(101 MHz, CDCl3): δ 150.9, 133.5, 131.4, 125.2, 115.5,
86.5, 85.7, 64.2, 41.6, 40.1, 34.7, 31.1, 30.3, 26.7, 26.7,
26.1 ppm.
1H NMR (400 MHz, CDCl3): δ 7.40–7.32 (m, 2H), 6.85–
6.77 (m, 2H), 3.79 (s, 3H), 3.12 (d, J = 9.9 Hz, 1H), 2.27
(s, 6H), 2.15–2.05 (m, 1H), 2.03–1.95 (m, 1H), 1.79–1.71
(m, 2H), 1.70–1.63 (m, 1H), 1.55–1.45 (m, 1H), 1.30–1.14
(m, 3H), 1.07–0.88 (m, 2H) ppm; 13C{1H} NMR
(101 MHz, CDCl3): δ 159.1, 133.0, 115.7, 113.8, 86.2,
84.8, 64.2, 55.3, 41.6, 40.1, 31.1, 30.3, 26.7, 26.1 ppm.
Spectroscopic data for the compound P10 were consis-
tent with the previously reported ones.[8]
Spectroscopic data for the compound P13 were consis-
tent with the previously reported ones.[8]
4.4.6 | (4‐(3‐(4‐chlorophenyl)‐3‐
(pyrrolidin‐1‐yl)prop‐1‐yn‐1‐yl)‐N,N‐
dimethylaniline, P14), yellow oil, yield 76%
4.4.3 | (1‐cyclohexyl‐N,N‐dimethyl‐3‐(4‐
(trifluoromethoxy)phenyl)prop‐2‐yn‐1‐
amine, P11), light‐yellow oil, yield 88%
1H NMR (400 MHz, CD2Cl2) δ 7.58 (dd, J = 0.4, 8.8 Hz,
2H), 7.34 (dd, J = 1.6, 8.8 Hz, 4H), 6.65 (dd, J = 1.6,
6.8 Hz, 2H), 4.88 (s, 1H), 2,98 (s, 6H), 2.68–2.61 (m,
4H), 1.79–1.76 (m, 4H) ppm; 13C{1H} NMR (101 MHz,
CD2Cl2) δ 150.2, 139.1, 132.8, 132.6, 129.6, 128.1, 111.6,
109.5, 88.0, 83.2, 58.2, 49.8, 39.9, 23.5 ppm; HRMS‐ESI
(m/z) calcd for C21H24ClN2 [M + H]+: 339.1628, found:
339.1635; IR (diamond tip) ν 3034, 2968, 2800, 1608,
1519, 1488, 1459, 1441, 1408, 1355, 1289, 1270, 1223,
1187, 1060, 1035, 1014, 974, 943, 877, 850, 834, 812, 737,
1H NMR (400 MHz, CDCl3) δ 7.45 (d, J = 8.8 Hz, 2H),
7.14 (d, J = 8.8 Hz, 2H), 3.15 (d, J = 10 Hz, 1H), 2.28 (s,
6H), 2.05 (dd, J = 13, 29.8 Hz, 2H), 1.78–1.67 (m, 3H),
1.58–1.49 (m, 1H), 1.31–1.16 (m, 3H), 1.07–0.93 (m, 2H)
ppm; 13C{1H} NMR (101 MHz, CDCl3): δ 148.5, 133.1,
122.4, 121.6, 120.8, 119.1, 87.6, 85.2, 64.1, 41.6, 40.0,
31.1, 30.2, 26.6, 26.1, 25.9 ppm; 19F NMR (376 MHz,
CDCl3)
δ 57.9 ppm; HRMS‐ESI (m/z) calcd for
C18H23NOF3 [M + H]+: 326.1760, found 326.1768; IR
(diamond tip) ν 2926, 2852, 1505, 1450, 1250, 1219,
1204, 1163, 1122, 1100, 1086, 1044, 1019, 850, 826, 808,
708, 692, 643, 627, 532, 489, 444 cm−1
.
605 cm−1
.
4.4.7 | (N‐benzyl‐3‐(4‐(tert‐butyl)phenyl)‐
1‐cyclohexyl‐N‐methylprop‐2‐yn‐1‐amine,
P15), yellow oil, yield 79%
4.4.4 | (N,N‐dimethyl‐1‐(naphthalen‐2‐yl)‐
3‐phenylprop‐2‐yn‐1‐amine, P12),
light‐yellow oil, yield 86%
1H NMR (400 MHz, CD2Cl2) δ 7.43–7.30 (m, 8H), 7.27–
7.22 (m, 1H), 3.72 (d, J = 13.4 Hz, 1H), 3.55 (d,
J = 13.4 Hz, 1H), 3.23 (d, J = 10.4 Hz, 1H), 2.24 (s, 3H),
2.12 (d, J = 12.4 Hz, 1H), 1.78–1.56 (m, 5H), 1.33 (s,
9H), 1.29–1.15 (m, 3H), 1.04–0.86 (m, 2H) ppm; 13C{1H}
NMR (101 MHz, CD2Cl2) δ 131.5, 128.2, 127.7, 123.6,
96.3, 92.6, 86.7, 86.3, 81.9, 64.0, 41.3, 40.1, 31.2, 30.2,
26.7, 26.2, 26.0 ppm; HRMS‐ESI (m/z) calcd for
C27H36N [M + H]+: 374.2848, found: 374.12851; IR (dia-
mond tip) ν 2926, 1546, 1498, 1450, 1398, 1343,
1H NMR (400 MHz, CDCl3) δ 8.1 (s, 1H), 7.89–7.85 (m,
3H), 7.75–7.73 (m, 1H), 7.60–7.58 (m, 2H), 7.50–7.48 (m,
2H), 7.38–7.36 (m, 3H), 5.01 (s, 1H), 2.39 (s, 6H) ppm;
13C{1H} NMR (101 MHz, CDCl3): δ 136.2, 133.5, 131.9,
128.4, 128.2, 128.1, 128.0, 127.6, 127.3, 126.0, 123.2, 88.7,
84.7, 62.4, 41.7 ppm; HRMS‐ESI (m/z) calcd for
C21H20N [M + H]+: 286.1590, found 286.1586; IR (dia-
mond tip) ν 2821, 2777, 1597, 1506, 1488, 1468, 1453,
1441, 1357, 1325, 1287, 1265, 1254, 1240, 1170, 1150,
1119, 1043, 1019, 1000, 949, 912, 898, 862, 834, 811, 780,
746,697,596, 528, 508, 490, 418.cm−1
.

14 of 16
SZADKOWSKA ET AL.
2.46 (m, 2H), 1.52–1.36 (m, 4H), 1.28 (bs, 12H), 0.93 (t,
J = 7.1 Hz, 3H) ppm; 13C{1H} NMR (101 MHz, CDCl3): δ
140.8, 133.9, 129.6, 126.7, 126.6, 83.4, 31.4, 30.0, 24.7,
23.1, 14.1 ppm.
Spectroscopic data for the compound P18 were consis-
tent with the previously reported ones.[35]
4.4.8 | (N‐allyl‐N‐(1‐cyclohexyl‐3‐
mesitylprop‐2‐yn‐1‐yl)prop‐2‐en‐1‐amine,
P16), yellow oil, yield 86%)
1H NMR (400 MHz, CDCl3): δ 6.86 (d, J = 0.5 Hz, 2H), 5.82
(dddd, J = 17.2, 10.1, 8.3, 4.1 Hz, 2H), 5.21 (dtd, J = 17.2,
2.1, 1.0 Hz, 2H), 5.12–5.06 (m, 2H), 3.44 (d,
J = 10.2 Hz, 1H), 3.34 (dt, J = 4.0, 1.9 Hz, 1H), 3.30 (dt,
J = 4.0, 1.9 Hz, 1H), 2.94 (dd, J = 14.3, 8.3 Hz, 2H), 2.40
(s, 6H), 2.26 (s, 3H), 2.16–2.08 (m, 2H), 1.78–1.70 (m, 2H),
1.68–1.57 (m, 2H), 1.29–1.17 (m, 3H), 1.09–0.97 (m, 1H),
0.95–0.83 (m, 1H) ppm; 13C{1H} NMR (101 MHz, CDCl3):
δ 139.9, 137.0, 127.5, 120.5, 116.7, 95.3, 83.0, 59.0, 54.1,
40.4, 31.4, 30.4, 26.7, 26.2, 26.0, 21.4, 21.2 ppm.
4.5.3 | (4‐(2‐(4,4,5,5‐tetramethyl‐1,3,2‐
dioxaborolan‐2‐yl)hex‐1‐en‐1‐yl)benzoyl
chloride, P19), colourless oil, 96%
1H NMR (400 MHz, CDCl3): δ 7.92–7.278 (m, 2H), 7.62–
7.44 (m, 2H), 3.32 (s, 2H), 1.70–1.59 (m, 2H), 1. 35–1.30
(m, 2H), 1.27–1.23 (m, 12H), 1.21–1.08 (m, 6H), 0.85–
0.75 ppm; 13C{1H} NMR (101 MHz, CDCl3): δ 199.1,
135.9, 131.6, 129.7, 127.7, 83.1, 31.8, 29.9, 27.7, 24.7,
22.6, 14.0 ppm. HRMS‐ESI (m/z) calcd for C13H15ClO
[M + H]+: 222.0813, found: 222.0815; IR (diamond tip)
ν 2926, 1546, 1498, 1450, 1398, 1343, 746,697,596, 528,
Spectroscopic data for the compound P16 were consis-
tent with the previously reported ones.[8]
4.5 | General procedure for the
β‐hydroboration of internal alkynes and
alkenes
508, 490, 418 cm−1
.
4.5.4 | ((4,4,5,5‐tetramethyl‐2‐(4‐
methylbenzyl)‐1,3,2‐dioxaborolane, P20),
colorless oil, yield 94%
In dry and argon flushed a 5 ml flask were added the appro-
priate copper complex (0.05 mol%), alkyne or alkene
(1.3 mmol, 1.0 eq), B2(pin)2 (1.5 mmol, 1.1 eq) and NaOH
(1 mol%, 0.0013 mmol). Then was added dry methanol
(0.1 ml) and CPME (1 ml). The reaction mixture was stirred
at room temperature for 18 hr under argon atmosphere.
The reaction was monitored by TLC (n‐hexane/ethyl ace-
tate, v/v = 7:3). After completion of the reaction, the sol-
vent was removed in vacuo, and the product was purified
by column chromatography (n‐hexane/ethyl acetate,
v/v = 9:1). The isolated product was dried under vacuum.
1H NMR (400 MHz, CDCl3): δ 7.07 (dt, J = 8.5, 4.4 Hz,
4H), 2.72–2.65 (m, 2H), 2.29 (d, J = 3.4 Hz, 3H), 1.26
(bs, 12H) ppm; 13C{1H} NMR (101 MHz, CDCl3): δ
141.4, 134.8, 128.9, 128.8, 127.8, 125.4, 83.1, 29.8, 25.0,
24.8, 24.5, 21.0 ppm.
Spectroscopic data for the compound P20 were consis-
tent with the previously reported ones.[20b]
4.5.5 | ((4,4,5,5‐tetramethyl‐2‐(naphthalen‐
1‐ylmethyl)‐1,3,2‐dioxaborolane, P21),
colourless oil, yield 97%
4.5.1 | (2‐(1‐phenylhex‐1‐en‐2‐yl)‐4,4,5,5‐
tetramethyl‐1,3,2‐dioxaborolane, P17),
colourless oil, 18 hr, yield 98%
1H NMR (400 MHz, CDCl3): δ 8.08 (dd, J = 8.3, 1.1 Hz,
1H), 7.85–7.81 (m, 1H), 7.70–7.65 (m, 1H), 7.47 (ddd,
J = 9.2, 7.8, 1.4 Hz, 2H), 7.41–7.34 (m, 2H), 3.23–3.17
(m, 2H), 1.24 (s, 12H) ppm; 13C{1H} NMR (101 MHz,
CDCl3): δ 140.4, 133.8, 131.7, 128.6, 126.3, 125.5, 125.3,
125.0, 123.9, 83.1, 26.9, 25.0, 24.8 ppm.
1H NMR (400 MHz CDCl3): δ 7.33–7.29 (m, 4H), 7.19 (s,
1H), 2.38 (dd, J = 7.5, 0.9 Hz, 2H), 1.30 (s, 12H), 1.09 (d,
J = 7.5 Hz, 1H) ppm; 13C{1H} NMR (101 MHz, CDCl3): δ
141.3, 137.9, 128.9, 128.0, 127.0, 83.4, 24.8, 22.7, 22.3,
14.7, 14.1 ppm.
Spectroscopic data for the compound P17 were consis-
tent with the previously reported ones.[34]
Spectroscopic data for the compound P21 were consis-
tent with the previously reported ones.[35]
4.5.2 | (4,4,5,5‐tetramethyl‐2‐(1‐(thiophen‐
2‐yl)‐hex‐1‐en‐2‐yl)‐1,3,2‐dioxaborolane,
P18), colourless oil, yield 95%
4.5.6 | ((4,4,5,5‐tetramethyl‐2‐(4‐
(trifluoromethyl)benzyl)‐1,3,2‐
dioxaborolane, P22, colourless oil, yield 97%
1H NMR (400 MHz, CDCl3): δ 7.34–7.28 (m, 2H), 7.11 (ddd,
J = 3.6, 1.1, 0.6 Hz, 1H), 7.00 (dd, J = 5.1, 3.6 Hz, 1H), 2.56–
1H NMR (400 MHz, CDCl3): δ 7.52–7.47 (m, 2H), 7.34–
7.27 (m, 2H), 2.82–2.75 (m, 2H), 1.20 (bs, 12H) ppm;

SZADKOWSKA ET AL.
15 of 16
13C{1H} NMR (101 MHz, CDCl3): δ 148.5, 128.3, 125.7,
125.1 (q, J = 3.8 Hz), 83.2, 29.8, 25.0, 24.8, 24.7 ppm;
19F NMR (376 MHz, CDCl3) δ −62.27 ppm.
2009, 362, 1247. b)H. V. Huynh, C. H. Yeo, G. K. Tan, Chem.
Commun. 2006, 3833. c)S. K. Quek, L. M. Lyapkalo, H. V. Huynh,
Tetrahedron 2006, 62, 3137. d)H. Seo, H.‐J. Park, B. Y. Kim, J. K.
Lee, S. U. Son, J. K. Chung, Organometallics 2003, 22, 618. e)X.
Xie, H. V. Huynh, Org. Chem. Front. 2015, 2, 1598. f)J. C.
Bernhammer, H. V. Huynh, Organometallics 2014, 33, 4295.
Spectroscopic data for the compound P22 were consis-
tent with the previously reported ones.[20b]
[5] M. Bierensteil, E. D. C. Cross, Chem. Rev. 2011, 255, 574.
ACKNOWLEDGEMENTS
[6] J. Zhai, A. Filatov, G. Hillhouse, M. Hopkins, Chem. Sci. 2016,
7, 589.
Authors sincerely thank Foundation for Polish Science
(Fundacja na rzecz Nauki Polskiej) for financial support
(Homing Plus programme/2013/8‐13, “Novel approaches
to transition metal complexes based on ligands contain-
ing sulfur moiety and their direct application in C‐H
bond transformations”). The project was co‐financed by
the European Union by the European Regional Develop-
ment Fund, Operational Program Innovative Economy
2009‐2013. Project was carried out using the infrastruc-
ture of Biological and Chemical Research Centre of Uni-
versity of Warsaw.
[7] M. Slivarichova, R. Costa, J. Nunn, R. Ahmad, M. Haddow, H.
Sparkes, T. Gray, G. Owen, J. Org. Chem. 2017, 847, 224.
[8] A. Szadkowska, E. Zaorska, S. Staszko, R. Pawłowski, D.
Trzybiński, K. Woźniak, Eur. J. Org. Chem. 2017, 4078.
[9] a)J. Liu, J. Chen, J. Zhao, Y. Zhao, L. Li, H. Zhang, Synthesis
2003, 17, 2661. b)A. Paczal, A. C. Benyei, A. Kotschy, J. Org.
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ORCID
Anna Szadkowska https://orcid.org/0000-0001-7322-189X
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SUPPORTING INFORMATION
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How to cite this article: Szadkowska A,
Pawłowski R, Zaorska E, Staszko S, Trzybiński D,
Woźniak K. NHC copper complexes functionalized
with sulfoxide and sulfone moieties. Appl
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