Supramolecular ensemble of PBI derivative and copper nanoparticles: A light harvesting antenna for photocatalytic C(sp2)-H functionalization

Article abstract of DOI:10.1039/c6gc01728b

Supramolecular aggregates of triazole-appended perylene bisimide (PBI) derivative 3 served as reactors for the generation of copper nanoparticles (CuNPs). During the reduction process, these aggregates were oxidized to triazole N-oxide species 4. Interestingly, the in situ generated CuNPs, in combination with oxidized species 4 (supramolecular ensemble 4:CuNPs), exhibited excellent photocatalytic efficiency in C(sp²)-H alkynylation and amination reactions of arenes under mild and eco-friendly conditions (inexpensive catalyst, room temperature, mixed aqueous media, aerial conditions and visible light irradiation).

Full text of DOI:10.1039/c6gc01728b

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DOI: 10.1039/C6GC01728B
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Received 00th January
20xx,
Supramolecular ensemble of PBI derivative and copper
nanoparticles: A light harvesting antenna for photocatalytic
C(sp2)-H functionalization
Sandeep Kaur, Manoj Kumar and Vandana Bhalla*
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
Supramolecular aggregates of triazole appended perylene bisimide (PBI) derivative 3 served as reactors for generation of
copper nanoparticles (CuNPs). During the reduction process, these aggregates themselves got oxidized to triazole N-oxide
species 4. Interestingly, the in situ generated CuNPs in combination with oxidized species 4 (supramolecular ensemble
4:CuNPs) exhibited excellent photocatalytic efficiency in C(sp2)-H alkynylation and amination reaction of arenes under mild
and eco-friendly conditions (inexpensive catalyst, room temperature, mixed aqueous media, aerial conditions and visible
light irradiation).
ensembles of fluorescent materials and metal nanoparticles5
as catalytic systems for carrying out various organic
transformations.5 Recently, we reported the utilization of
Introduction:
Transition metal catalysed direct C-H alkynylation/amination
of arenes has been recognized as a powerful and convenient
strategy for the preparation of important structural motifs of
various natural products, pharmaceuticals and functional
nanomaterials.1 The direct transformation of carbon-hydrogen
bond to a C-C/C-N bond via C(sp2)-H functionalization is a
straightforward and atom economical approach, however,
homo-coupling2 of terminal alkynes under the reaction
conditions is a big hurdle towards large scale industrial
application of this strategy. To overcome this problem, the
directing group assisted C-H functionalization3,4 of activated
arenes have been developed which resolved the issue of
formation of side products but the utilization of high loading of
costly and toxic metal based catalytic systems in the reactions
actually increased the economic and environmental
disadvantages of this strategy. Very recently, Cu(II)-promoted
and directing group assisted ortho alkynylation3a and
amination4a of arenes have been reported. Although this
approach contributed toward atom economy and cost
reduction of the catalytic system, however, the
recyclability/reusability of the catalyst was not explored. Thus,
the development of a simple, efficient and economic catalytic
system for ortho alkynylation and amination reactions via
C(sp2)-H functionalization in aqueous media under mild and
eco-friendly conditions is a challenge yet to achieve.
supramolecular photocatalytic systems for carrying out C-C
bond formation reactions under mild and eco-friendly
conditions.5a-c Photocatalytic systems harvest the clean and
abundant solar energy to carry out organic reactions and
contribute a lot towards the development of sustainable
chemical industry. In our pursuit for making C-H
functionalization more ‘green’, we were interested in the
development of photocatalytic system for C(sp2)-H activation
reactions. Recently, we developed the aggregates of the
perylene bisimide (PBI) derivative which acted as reactors and
stabilizers for the preparation of superparamagnetic Fe3O4 NPs
and these nanoparticles exhibited excellent catalytic efficiency
in C-H activation reactions under thermal conditions.5e
However, lack of spectral overlap between emission spectrum
of PBI derivative and absorbance spectrum of Fe3O4 NPs ruled
out the possibility of energy transfer in this catalytic system for
carrying out C-H functionalization under photocatalytic
conditions. In continuation of this work, we were then
interested to develop
a photocatalytic supramolecular
ensemble having favourable energy transfer between dye stuff
and metal nanoparticles and for this purpose we designed and
synthesized perylene bisimide derivative
3 appended with
triazole moieties. PBI moiety is scaffold of our choice as it is
known for its role as light harvesting antenna.6 Copper is metal
of our choice due to its known catalytic efficiency in C(sp2)-H
and C(sp3)-H functionalization of activated arenes under
thermal conditions.7 Triazole moieties were incorporated due
to their known affinity for Cu2+ ions.8 To our pleasure,
Our research work involves development of supramolecular
a.Department of Chemistry, UGC Sponsored Centre for Advanced Studies-II, Guru
Nanak Dev University, Amritsar 143005, and Punjab, India
E-mail: vanmanan@yahoo.co.in † Footnotes relating to the title and/or authors
should appear here.
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
supramolecular aggregates of PBI derivative
reactors for generation of CuNPs. During the reduction
process, aggregates of derivative themselves got oxidized
and aggregates of oxidized species
3 served as
3
4
acted as stabilizers for
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CuNPs. Till date, various methods such as hydrothermal,9 emission bands at 530 (Ф = 0.43) and 570 nm (Ф = 0.26), when
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solvothermal,10 reduction,11 micelle supported,12 etc.13 have excited at 485 nm. Upon addition of water fraction up to 60%
DOI: 10.1039/C6GC01728B
been reported for the preparation of CuNPs, however, most of (volume fraction) to the THF solution of 3, both the bands
these methods suffer from limitations such as longer reaction were slightly red shifted and a decrease in emission intensity
time, requirement of reducing agents and lack of reusability of of both the emission bands (537 nm, Ф = 0.24 and 574 nm, Ф =
the catalytic system. On the other hand, the wet chemical 0.15) was observed (Fig. S2, ESI†). The concentration-
method being reported in the present article for the dependent 1H NMR studies showed average upfield shift of the
preparation of CuNPs is fast and convenient (Table S1, ESI†). aromatic protons by 0.08 ppm (Fig. S3, ESI†). The scanning
Furthermore, the in situ generated supramolecular ensemble electron microscope (SEM) image of compound
3 in H2O/THF
of aggregates of oxidized species and CuNPs could efficiently (6:4, v/v) showed the presence of spherical aggregates (Fig. S4,
4
harvest the visible light radiations and exhibited excellent ESI†). The UV-vis, fluorescence and concentration-dependent
photocatalytic efficiency in directing group assisted C(sp2)-H 1H NMR studies suggested the formation of J- aggregates.
alkynylation and amination of arenes under visible light
irradiation14 (Table S2-S4, ESI†). To the best of our knowledge,
this is the first report where aggregates of PBI derivative in
combination with CuNPs have been used as a light harvesting
antenna for carrying out C-H functionalization reactions.
335 nm
Cu2+ (Equiv.)
30
485
563
0
595 nm
Results and Discussion:
Synthesis and characterization of PBI derivative 3:
LSPR band
of CuNPs
Derivative
115a with boronic ester 215b in 72% yield (Scheme 1). The
structure of derivative was confirmed from its spectroscopic
and analytical data (Fig. S27-S30, ESI†). The H NMR spectrum
of derivative shows three singlets at 7.75, 7.47 and 5.38 ppm
3 was synthesised via Suzuki-Miyaura coupling of
3
1
3
Fig. 1: UV-Vis spectra of compound 3 (5 µM) showing the response to the
Cu2+ ion (0-30 equiv.) in H2O/THF (6:4, v/v) mixture; Inset showing the UV-
vis spectra of derivative 3 in presence of Cu2+ ions at lower concentration
(0-2.5 equiv.).
(2H, 4H, 8H); three doublets at 8.55, 8.13 and 7.06 ppm (2H,
2H, 2H); seven triplets at 7.81, 7.68, 4.40, 4.33, 1.95, 1.87 and
0.87 (2H, 2H, 8H, 4H, 8H, 4H, 18H) and one multiplet at 1.42-
1.25 (60H), respectively. The 13C NMR spectrum showed peak
at 163.2 ppm corresponding to carbonyl carbon and other
peaks at 150.4, 145.2, 143.7, 138.6, 133.9, 132.6, 130.3, 129.2,
127.8, 127.5, 125.0, 120.2, 116.4, 115.4 ppm corresponding to
aromatic carbons and peaks at 82.0, 60.1, 45.8, 29.7, 27.7,
25.8, 22.6, 19.3, 14.1 ppm corresponding to aliphatic chains.
The MALDI-TOF mass spectrum showed a parent ion peak at
1604.0645 (m/z). These spectroscopic data corroborate the
The presence of triazole groups in derivative
3 prompted us to
investigate its binding behavior toward different metal ions viz.
Cd2+, Ba2+, Hg2+, Fe2+, Fe3+, Ni2+, Zn2+, Cu2+, Pd2+, Ca2+, Co2+, Ag+
and Au3+ as their perchlorate/chloride salts by UV-Vis and
fluorescence spectra in H2O/THF (6:4, v/v) solvent mixture (Fig.
S5A-B, ESI†). The UV-vis spectrum of derivative
3 in H2O/THF
(6:4; v/v) mixture showed the presence of broad absorption
bands at 335, 485 and 563 nm. Upon addition of Cu2+ ions (0-
2.5 equiv.) the intensity of the band at 563 nm slightly
decreased, however, an increase in absorbance in the range of
300-500 nm was observed (inset of Fig. 1). Further addition of
Cu2+ ions (3-30 equiv.) to the solution resulted in the
appearance of a new band at 595 nm within 30 min
corresponding to localised surface plasmon resonance (LSPR)
band of CuNPs11e, 16 (Fig. 1). The above studies suggest that the
structure ‘
3
’ for this compound.
2
Dry THF, 80°C
Pd(PPh3)2Cl2, K2CO3
supramolecular aggregates of derivative
3
interacted with Cu2+
3
ions and during this interaction Cu2+ ions were reduced to
CuNPs in mixed aqueous media. We also carried out the UV-vis
1
Scheme 1. Synthesis of PBI based derivative 3.
studies of derivative
of Cu2+ ions but no LSPR band was observed which clearly
in THF exhibited one showed that the non-aggregated form of derivative
did not
3 in its molecular form in THF in presence
The UV-vis spectrum of derivative
3
3
absorption band at 325 nm due to π-π* transition and two act as reactors for the generation of CuNPs (Fig. S6, ESI†).
bands at 480 and 540 nm due to to n-π* transitions. On To examine the in situ reduction of Cu2+ ions to CuNPs, we
addition of water content up to 60% (volume fraction) to the carried out spectroelctrochemical studies of aggregates of
THF solution of
3
, all the three absorption bands were derivative
3
in presence of Cu2+ ions. The cyclic voltammogram
in H2O:CH3CN (1:9) (15 µL THF to dissolve)
broadened and their intensity decreased (Fig. S1, ESI†). The of derivative
3
fluorescence spectrum of compound
3
in THF exhibited two showed reversible reduction potential at -0.14 and -0.45 eV,
2 | J. Name., 2012, 00, 1-3
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and irreversible oxidation potential at 0.21 and 0.47 eV, The selected area electron diffraction (SAED) pattern showed
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respectively.17 In the spectroelctrochemical studies, upon three distinct diffraction rings correspoDnOdIi:n1g0.1t0o39(/1C161G)C,0(1272080B)
addition of 30 equiv. of Cu2+ ions to derivative
band was observed at 500 nm which suggest the formation 3-
3
, an absorption and (220) indices which suggest the fcc phase of Cu(0) state
(Fig. 3C).13b,20 The powder X-ray diffraction (XRD) studies of the
Cu2+ complex. Further, tail in the region of 700-900 nm was precipitates showed the presence of diffraction peaks located
observed which indicates the presence of Cu2+ ions.18 When at 2θ values of 43.4, 50.5 and 74.5 which suggested the
the reduction potential (-0.45 eV) was applied, the intensity of formation of fcc lattice of Cu(0) state (Fig. S10, ESI†).20 The
band at 500 nm and tail in the region of 700-900 nm was above studies clearly suggest the formation of CuNPs.
gradually decreased and
a new band was observed In the next part of our work, we examined the effect of
corresponding to LSPR band of CuNPs at 590 nm (30 min) (Fig. concentration of aggregates of derivative
3 upon size and
S7, ESI†). These spectroelctrochemical studies19 suggest the shape of the in situ generated CuNPs. We prepared
reduction of Cu2+ ions to CuNPs in presence of aggregates of supramolecular ensemble by mixing different amounts of
derivative
In the fluorescence spectrum, upon addition of Cu2+ ions (30 scattering (DLS) studies of supramolecular ensemble prepared
equiv.) to the solution of aggregates of derivative in mixed by mixing aggregates of derivative
(5 µM) and Cu2+ ions (30
3
.
aggregates of derivative 3
and Cu2+ ions. Dynamic light
3
3
aqueous media (H2O/THF, 6:4, v/v), a significant quenching equiv.) showed the formation of CuNPs having average
(92%) of the emission bands at 537 and 574 nm was observed diameter in the range of 8-20 nm (Fig. S11A, ESI†). On
(Fig. 2). Further addition of Cu2+ ions (> 30 equiv.) did not increasing the concentration of aggregates of derivative
3 from
affect the emission behaviour of aggregates of derivative
3
.
5 to 10 µM, a decrease in size (from 8-20 to 5-8 nm) of the
The detection limit of aggregate of derivative
3
for Cu2+ ions CuNPs was observed (Fig. S11B, ESI†) whereas CuNPs having
was found to be 37 nM (Fig. S8, ESI†).
size in the range of 30-60 nm were obtained on decreasing the
concentration of aggregates of
ESI†). We believe that the presence of aggregates of derivative
in higher amount restricts the growth of nanoparticles due to
3 from 5 to 2.5 µM (Fig. S11C,
537 nm
Cu2+ (equiv.)
0
3
their greater surface adsorption. TEM studies show that
change in concentration of aggregates had no effect on shape
of in situ generated CuNPs (Fig. 4A-B).
574 nm
30
Fig. 2 Fluorescence spectra of compound 3 (5 µM) showing the response to
the Cu2+ ion (0-30 equiv.) in H2O/THF (6:4, v/v) mixture buffered with
HEPES; pH = 7.05, λex = 485 nm.
Under the same set of conditions as used above for Cu2+ ions,
we also tested the fluorescence response of derivative
3
Fig. 4: TEM images of CuNPs prepared by mixing (A) aggregates of derivative
3 (10 µM) and Cu2+ ions (30 equiv.); (B) aggregates of derivative 3 (2.5 µM)
and Cu2+ ions (30 equiv.).
toward other metal ions such as (Ag+, Hg2+, Au3+, Zn2+, Cu2+,
Fe2+, Fe3+, Co2+, Pb2+, Ni2+, Pd2+, Cd2+, Ba2+ and Mg2+) but no
significant change in emission behaviour was observed in the
presence of these metal ions (Fig. S9A-B, ESI†).
In the absorption spectra the red shifting of LSPR band (from
586 to 595 to 598 nm) of CuNPs was observed with the
increase in size of the CuNPs (from 5-8 to 8-20 to 30-60 nm
size) (Fig. S12, ESI†).16 Thus, by adjusting the amount of
Characterization and photophysical behaviour of CuNPs:
The transmission electron microscope (TEM) image of
derivative
3, the surface plasmon resonance of CuNPs could be
derivative
3 in the presence of copper ions (30 equiv.) showed
the presence of spherical shaped nanoparticles (Fig. 3A).13b, 20
The high-resolution TEM (HR-TEM) image showed the d-
spacing of 2.09 Å corresponding to the (111) plane bearing
face-centred cubic (fcc) crystal lattice fringes of CuNPs (Fig.
3B).13b, 20
fine-tuned. Furthermore, the emission spectra showed
decrease in emission intensity of aggregates of derivative
3
with increase in the particle size of CuNPs (Fig. S13, ESI†).21
To get insight into the mechanism of formation of CuNPs, we
slowly evaporated the solution of aggregates of derivative
3
containing CuNPs, precipitates were observed after two days
1
which were filtered and washed with CHCl3 and THF. The H
NMR spectrum of the residue obtained after evaporation of
the solvent showed downfield shift of triazole C-H protons and
upfield shift of aromatic protons (Fig. S14, Table S5, ESI†). We
believe that the aggregates of derivative
CuNPs and during this process themselves got oxidized. To get
insight into the oxidation of aggregates of derivative , we
3
reduced Cu2+ ions to
3
Fig. 3: (A) TEM image of CuNPs prepared by mixing aggregates of derivative 3
(5 µM) and Cu2+ ions (30 equiv.): Scale bar 50 nm; (B) HR-TEM image showing
the interplanar spacing; (C) SAED pattern of CuNPs.
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carried out the reaction between derivative
hydroperoxide, a strong oxidant, in H2O/THF (6:4, v/v) under activation reactions in presence of visible light. We chose
3
and tert-butyl situ generated supramolecular ensemble 4:CuNPs in the C-H
View Article Online
DOI: 10.1039/C6GC01728B
lab conditions (Scheme 2). After the completion of the ortho-C-H alkynylation reaction between oxazoline substituted
reaction (TLC), the oxidized product was isolated and its benzamide derivative (5) and phenylacetylene (6a) as a model
1
structure was confirmed by spectroscopic methods. The H reaction. A 60 W tungsten filament bulb was used as the
NMR spectrum of the oxidized species was same as that of the visible light irradiation source and the round bottom flask was
organic residue obtained after the formation of CuNPs (Fig. immersed in a water bath at room temperature to inhibit the
S15, Table S6, ESI†). The FT-IR spectrum of the residue showed photo-heating effect. We carried out reaction between
stretching band at 1170 cm-1 corresponding to triazole N-oxide 6a using supramolecular ensemble 4:CuNPs (1.0 mol % with
moiety (Fig. S16, ESI†).22 The ESI-MS mass spectrum showed a
respect to copper) (prepared by mixing 9.0 mL of 0.033 M
peak at m/z = 1668.9878 [Mox+H]+ corresponding to the solution of
and 1.0 mL of 1.0 M solution of CuCl2) in DMSO (2
oxidized species (Fig. S17, ESI†). These spectroscopic data mL) under photocatalytic conditions in presence of K2CO3 (1
5 and
3
4
corroborate structure
4
for this compound.
mmol) to furnish the product 7a in 72% yield (Scheme 3)
(Table 1, entry 1). Same reaction was also carried out in
different solvents such as toluene, ethanol, THF and DCM at
room temperature under photocatalytic conditions, however,
in presence of all these solvents, the desired product was
obtained in lower yield (Table 1, entry 2-5) while under neat
condition; no product formation was observed (Table 1, entry
6). Interestingly, presence of K2CO3 in higher amount had no
effect on the rate as well as the yield of the reaction (Table 1,
entry 7-9). However, in absence of K2CO3 the desired product
was not obtained which suggests that basic medium is
essential for reaction (Table 1, entry 10). To study the effect of
nature of base on the reaction, we carried out model reaction
t-BuOOH
3
4
Scheme 2: Oxidation of derivative 3 by using t-BuOOH to yield N-oxide
derivative 4.
The fluorescence spectrum of oxidized species
4 (5 μM) in using different bases such as Na2CO3, Cs2CO3, NaOAc and
H2O/THF (6:4, v/v) solvent mixture exhibited two emission NaHCO3. In all these cases, the desired product was obtained
bands at 540 and 578 nm (Fig. S18, ESI†). A strong overlap was in comparable yield (Table 1, entry 11-14). These studies
observed between emission spectrum of oxidized species
and absorption spectrum of CuNPs which suggests the selected K2CO3 as the base and DMSO as solvent for carrying
possibility of energy transfer from oxidized species to CuNPs out further reactions.
(Fig. S19, ESI†). To confirm the possibility of energy transfer
from oxidized species to in situ generated CuNPs, we carried
out fluorescence studies of oxidized species in presence of
4
suggest that reaction is not dependent on nature of base. We
4
4
4
6a
5
bare CuNPs. The bare CuNPs were prepared by following
procedure reported in the literature.11e Upon addition of bare
CuNPs (100 μL, 0.01 M) to this solution 78% decrease in
intensity of both the emission bands was observed (Fig. S20,
ESI†). We also examined the effect of Cu2+ ions on the
7a, yield: 72%
Scheme 3: C(sp2)-H alkynylation reaction between oxazoline substituted
benzamide (5) and phenyl acetylene (6a) under photocatalytic conditions.
Table 1: C-H alkynylation reactions between oxazoline substituted benzamide
(5) and phenyl acetylene (6a) with different solvents (2 mL) and bases under
photocatalytic conditions.
emission behaviour of oxidized species 4; however, only 8%
decrease in emission intensity of both the bands was observed
(Fig. S21, ESI†). These studies clearly show that oxidized
Entry
Solvent
Base
Yield (%)
species
4
is interacting more with CuNPs. The time resolved
in H2O/THF (6:4, v/v)
fluorescence studies of oxidized species
4
1
2
3
DMSO
THF
K2CO3 (1 mmol)
K2CO3 (1 mmol)
K2CO3 (1 mmol)
72
30
25
showed average decay time of 2.98 ns, however, in presence
of bare CuNPs (100 μL, 0.01 M), the average decay time is
decreased to 0.16 ns (Fig. S22, ESI†). Further, a significant
increase in non-radiative decay constant (from 2.6×108 to
DCM
4
5
Ethanol
Toluene
Neat
K2CO3 (1 mmol)
K2CO3 (1 mmol)
K2CO3 (1 mmol)
K2CO3 (1 mmol)
K2CO3 (1.5 mmol)
K2CO3 (3 mmol)
-
15
20
-
58×108 s-1) (Table S7, ESI†) of oxidized species
4 in presence of
6
CuNPs was observed. All the above studies support the
possibility of energy transfer23 from the oxidized species
4 to
7
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
72
72
74
-
8
CuNPs.
Catalytic Reactions:
C(sp2)-H alkynylation reactions:
The possibility of energy transfer from perylene dye stuff to
9
10
11
12
13
14
Na2CO3
68
70
72
45
Cs2CO3
CuNPs encouraged us to examine the catalytic activity of the in
NaOAc
NaHCO3
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Table 2: Screening of C-H alkynylation reactions between oxazoline substituted
Further, the model reaction between
5 and 6a in presence of
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benzamide (5) and phenyl acetylene (6a) in K2CO3 (1 mmol) and DMSO (2 mL)
DOI: 10.1039/C6GC01728B
supramolecular ensemble :CuNPs in dark furnished the
4
under different photocatalytic conditions.
desired product in <20% yield (Table 2, entry 1) which
suggested that the high catalytic efficiency of the system for
the C(sp2)-H alkynylation reaction resulted from the visible
light irradiation in presence of air (Table 2, entry 2). Under
similar set of conditions, the model reaction under inert
atmosphere (N2) furnished the desired product in 42% yield
(Table 2, entry 3). This result highlights the role of air act as an
oxidant in C-H functionalization reaction. We also prepared
S.No.
Control experiment
Time (h) Yield (%)
1
supramolecular ensemble
24
< 20
4:CuNPsa
2
3
4
supramolecular ensemble
4:CuNPsb
8
72
42
63
supramolecular ensemble by mixing derivative
3 (5µM) and
Cu2+ ions (15 equiv.). The absorption studies of this solution
show the band corresponding to CuNPs but no saturation
point was achieved (Fig. S23, ESI†). We utilized this system as
catalyst in the model reaction. The reaction was completed in
11 h and desired product was obtained in 63% yield (Table 2,
entry 4). Thus, presence of 30 equiv. of Cu2+ ions is optimum
to achieve the good catalytic activity.
supramolecular ensemble
4:CuNPsc
24
11
3
+ 15 equiv. Cu2+ ionsb
5
6
only oxidized species 4b
24
24
No reaction
18
Cu2+ (copper chloride)
Further, no reaction product was obtained using only oxidised
derivative 4 as the photocatalyst (Table 2, entry 5). In presence
7
8
Cu2+ + oxidized species 4b
Cu2++ derivative 3d
11eBare CuNPsb
24
24
20
18
30
20
25
28
of CuCl2 as a catalyst, the desired product was obtained in 18%
yield (Table 2, entry 6). On the other hand, when Cu2+ ions and
9
oxidised derivative
4 were used as catalyst, the desired
10
Bare CuNPs+ aggregates of
derivative 3b
product was obtained in 30% yield (Table 2, entry 7). To
investigate the role of Cu2+ ions as a catalyst in the C(sp2)-H
activation reaction, we prepared a catalytic system consisting
11
12
Bare CuNPs +4b
15
24
55
3
and Cu2+ ions in THF. The catalytic system (1
5asupramolecular ensemble
~10
of derivative
mol %) so prepared was used to carry out the above
mentioned reaction under photocatalytic conditions in DMSO
(2 mL) and the desired product was obtained in 20% yield
(Table 2, entry 8). This study clearly showed that CuNPs are
catalytically more active than Cu2+ ions in C(sp2)-H activation
reactions. Under same set of conditions, we evaluated the
catalytic efficiency of bare CuNPs as catalyst in the C(sp2)-H
activation of model reaction; the desired product 7a was
obtained only in 25% yield (Table 2, entry 9). Further, we
examined the same reaction in presence of bare CuNPs and
PBI derivative 8:Cu2ONPsb
a: in dark, b: under light irradiation, c: under inert atmosphere, d:
derivative 3:Cu2+ in THF
aggregates of derivative
3, the reaction took 18h for
completion to furnish the desired product 7a in 28% yield
(Table 2, entry 10). Interestingly, bare CuNPs in presence of
Fig. 5 Structure of PBI derivative 8.
oxidised species
4 showed better catalytic efficiency in the
above mentioned reaction to furnish the desired product 7a in
55% yield (Table 2, entry 11). We believe that light harvesting
capability of CuNPs is enhanced in the presence of oxidised
To expand the scope of this photocatalytic system with regard
to terminal alkynes, we carried out reactions between
compound
optimized reaction conditions. Oxazoline substituted
benzamide derivative ( ) undergoes reaction smoothly with
5 and different terminal alkynes (6a-m) under the
species
increased electron density on CuNPs in supramolecular
ensemble via electron transfer from oxidised species
Recently, we reported the development of supramolecular
ensemble of aggregates of PBI derivative (Fig. 5) and Cu2O
4. The enhanced catalytic activity may be attributed to
5
4
.
aryl alkynes (6b-e) bearing electron withdrawing substituents
to furnish the desired products in excellent to good yields (7b-
8
e
(
h
) (Table 3). Aryl alkynes having electron donating substituents
6f-h) furnished the target compounds in moderate yields (7f-
) (Table 3). Alkynes 6i and 6j bearing heterocyclic ring such as
NPs which acted as photocatalytic system in Suzuki coupling
reactions.5a We also utilized same photocatalytic system for
carrying out C(sp2)-H activation, however, the result was not
encouraging (Table 2, entry 12). We believe that in presence of
CuNPs the Lewis acidity of catalytic system is enhanced more in
comparison to that in case of Cu2O NPs. This type of CuNPs
induced enhancement of Lewis acidity of catalytic materials is
already reported in literature.24
thiophene and pyridine moieties reacted smoothly with
alkynes to furnish the desired products (7i-j) in 52% and 60%
yields, respectively (Table 4). Importantly, aliphatic alkynes
(6k-m) were found to be compatible to the C-H alkynylation
reaction under given set of conditions to furnish the products
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Table 5: Scope of aliphatic alkynes
(
7k-m) in good yields (Table 5). All the products were
View Article Online
DOI: 10.1039/C6GC01728B
1
characterized by H NMR, 13C NMR and mass spectra (Fig. S31-
S45, ESI†).
Table: 3 Scope of terminal aromatic alkynes
7k-m
6k-m
6k, R3 = C5H11; 6l, R3=C6H13; 6m, R3=Me2COH.
5
7b-h
5
6b-h
6b, R1= PhNO2; 6c, R1=PhBr; 6d, R1=PhCl; 6e, R1=PhCHO; 6f, R1=PhNH2;
6g, R1=PhOMe; 6h, R1=PhMe.
7k
7l
7m
Time: 10h
Yield: 50%
Time: 10h
Yield: 58%
Time: 10h
Yield: 56%
Reaction conditions: Oxazoline substituted benzamide 5 (1 mmol),
terminal alkynes 6k-m (1 mmol), K2CO3 (1 mmol), DMSO (2 mL), visible
light, 1.0 mol % 4:CuNPs catalyst, under air.
7c
7d
7b
Time: 7h
Yield: 72%
Time: 6h
Yield: 75%
Time: 6h
Yield: 78%
The efficiency of supramolecular ensemble
tested for reaction between and 6a as model reaction. When
the amount of supramolecular ensemble :CuNPs is 1.0 mole
%, the yield is 72% in 8h against 0% when the reaction is
conducted without supramolecular ensemble :CuNPs (Table
S8, ESI†). Such an extremely low quantity of catalyst has never
been successfully utilized for C-H activation of C(sp2)-H
alkynylation reactions under photocatalytic conditions before
the present study.
4:CuNPs was also
5
4
4
7f
7g
7e
Time: 9h
Yield: 52%
Time: 9h
Yield: 50%
Time: 7h
Yield: 65%
(A)
(B)
7h
Time: 8h
Yield: 55%
Reaction conditions: Oxazoline substituted benzamide 5 (1 mmol),
terminal alkynes 6b-h (1 mmol), K2CO3 (1 mmol), DMSO (2 mL), visible light,
1.0 mol % 4:CuNPs catalyst, under air.
Table 4: Scope of hetero-aromatic alkynes
Fig. 6: (A) Recyclability of supramolecular ensemble 4:CuNPs catalyst for
reaction 5 and 6a; (B) TEM image of spherical supramolecular ensemble
4:CuNPs; recovered after photocatalytic for C(sp2)-H reaction. Scale bar 50
nm.
6i-j
5
7i-j
In the next part of our work, we selected the model reaction to
examine the reusability of the catalyst. The in situ generated
supramolecular ensemble 4:CuNPs could be reused upto 4
times. After 4 cycles the yield was reduced to 56% (Fig. 6A).
The TEM image of recycled CuNPs obtained after recycling
revealed small variation in size and morphology of the
nanoparticles (Fig. 6B).
To find out the amount of copper leached into the residual
solution, we carried out the atomic absorption spectroscopic
(AAS) studies of the residual solution remained after the
recycling of the catalyst and it was found that 0.55 ppm of
copper leached through the solution after 4th catalytic cycle
(Fig. S24, ESI†). We believe that leaching of CuNPs is the
reason behind the decrease in the catalytic efficiency of the
reaction.
6i, R2 = C4H3S; 6j, R2=C5H4N.
7j
7i
Time: 8h
Yield: 60%
Time: 9h
Yield: 52%
Reaction conditions: Oxazoline substituted benzamide 5 (1 mmol),
hetero-aromatic alkynes 6i-j (1 mmol), K2CO3 (1 mmol), DMSO (2 mL),
visible light, 1.0 mol % 4:CuNPs catalyst, under air.
6 | J. Name., 2012, 00, 1-3
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To evaluate the practical applicability of the supramolecular
DOI: 10.1039/C6GC01728B
ensemble 4:CuNPs, we also carried out the reaction of oxazoline
We also studied the same reaction using 1.0 mol % of
supramolecular ensemble prepared by mixing higher amount
of aggregates of derivative
View Article Online
3
(10 µM) and Cu2+ ions (30 equiv.)
substituted benzamide derivative,
5 and perylene bisimide
to furnish the desired product 7a in 69 % yield in 11 h. We also
examined the recyclability of the catalytic system for this
reaction. A small decrease (7 %) in the yield of the product (62
%) was observed after 4th catalytic cycle (Table S9, ESI†). The
AAS studies showed 0.11 ppm leaching of copper after 4th
catalytic cycle (Fig. S25, ESI†). These results show that by
derivative, 6n. The reaction went smoothly to furnish the desired
product 7n in 52% yield (Scheme 5). This study demonstrates the
practical utility of supramolecular ensemble 4:CuNPs for carrying
out C(sp2)-H activation reactions.
increasing the concentration of supramolecular aggregates 3 in
the catalytic system, the CuNPs are more stabilized, hence
leaching of metal nanoparticles was reduced.
5
Reaction Mechanism:
To get insight into the mechanism of supramolecular ensemble
4
7n, yield = 52%
6n
:CuNPs photcatalyzed C(sp2)-H activation reaction, we
Scheme 5: C(sp2)-H alkynylation reaction between oxazoline substituted
benzamide (5) and PBI derivative (6n) under photocatalytic conditions.
investigated the model reaction between oxazoline
substituted benzamide substrate ( ) and phenyl acetylene (6a
5
)
C(sp2)-H amination reaction:
Encouraged by successful C(sp2)-H functionalization reaction,
we were interested in knowing the applicability of
in the presence of the well-known radical scavenger 2,2,6,6-
tetramethyl-1-piperidinoxyl (TEMPO, 1 equiv.). The reaction
was completely inhibited in the presence of TEMPO confirming
that a free radical is generated under our standard reaction
conditions.25 On the basis of above results, we propose a
plausible radical/single electron transfer (SET) mechanism as
shown in scheme 4. We believe that initially the photo-excited
supramolecular ensemble
4:CuNPs as catalyst in carbon
heteroatom bond formation reactions. We planned to examine
C(sp2)-H amination reaction for the formation of C-N bonds.
Among various methods reported in literature for the
formation of C-N bonds, the Buchwald Hartwig amination
reaction between aryl halides and amines have been
extensively studied.28 However, this strategy involves
utilization of catalytic systems based on costly transition metal
ions like Pd.28 We examined the reaction between p-nitro
CuNPs interact with substrate
5 . The
to form complex A 26
electrons on the surface of CuNPs assist the cleavage of C-H
bond of benzamide,7a-b thus, generating the free radical
intermediate
intermediate
the next step, complex
B
B
. Further, terminal alkyne (6a) react with
in presence of K2CO3, to form the complex . In
is formed which is transformed into
C
aniline (9a) in presence of supramolecular ensemble 4:CuNPs
D
under photocatalytic conditions. To our pleasure, reaction
proceeded smoothly to furnish the ortho aminated product
10a in 86% yield (Table 6). To widen the scope of
photocatalytic C(sp2)-H amination reaction, we carried out the
reaction of aryl amines (9b-c) bearing electron withdrawing
substituents which furnished the target compounds (10b-c) in
good yield (Table 6). However, aniline (9d) furnished the target
compound (10d) in lower yield (Table 6). Further, the
the desired alkynylated product 7a with the elimination of
hydrogen atoms in the form of water in the presence of air as
an oxidant.27
-
-
-
e e e
CB
VB
+
+
+
h
h h
amination reaction of aliphatic secondary amines (9e-9g
(Table 7) and aromatic heterocyclic amines (9h-9k) furnished
the desired products in excellent to good yields (10e-10k
)
)
(Table 8). The structure of these products were confirmed
1
from their H NMR, 13C NMR and mass spectra (Fig. S46-S57,
ESI†).
.
Table 6: Scope of substituted anilines
5
9a-d
10a-d
9a, R4= NO2; 9b, R4= Cl; 9c, R4=Br; 9d, R4= H.
Scheme 4: Probable schematic mechanism of C(sp2)-H alkynylation reaction
between oxazoline substituted benzamide derivative (5) and phenyl
acetylene (6a) under photocatalytic conditions.
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:CuNPs
Further, in situ generated supramolecular ensemble
4
View Article Online
could be reused upto 3 times in case DoOfI:d1e0r.1iv0a39ti/vCe6G9Ca01w72i8thB
slight loss of catalytic activity (after three cycles 72%) (Fig. S26,
ESI†). The efficiency of the supramolecular ensemble
4
:CuNPs
and 9a. When the
:CuNPs is 5.0 mol %
10b
Time: 4h
Yield: 76%
10a
Time: 4h
Yield: 86%
was also tested for reaction between
amount of supramolecular ensemble
5
4
with respect to copper (prepared by mixing 9.0 ml of 0.033 M
solution of and 1.0 ml of 1.0 M solution of CuCl2), the yield is
3
86% in 4h against 0% when the reaction is conducted without
supramolecular ensemble 4:CuNPs (Table S10, ESI†). Such an
extremely low quantity of catalyst has never been utilized for
C-H activation of C(sp2)-H amination reactions under
photocatalytic conditions before the present study.
10c
Time: 4h
Yield: 64%
10d
Time: 5h
Yield: 20%
To examine the practical utility of supramolecular ensemble
4:CuNPs, we also carried out the amination reaction of a
compound
reaction went smoothly to furnish the desired product 10l in
46% yield (Scheme 6). This study demonstrates the practical
utility of supramolecular ensemble 4:CuNPs for carrying out
C(sp2)-H amination reactions.
Reaction conditions: Oxazoline substituted benzamide 5, 1 mmol),
amines (9a-d, 1 mmol), K2CO3 (1 mmol), DMSO (2 mL), visible light, 5.0 mol
% 4:CuNPs catalyst, under air.
5
with perylene bisimide derivative 9l.5e The
Table 7: Scope of substituted secondary aliphatic amines
5
9e-g
10e-g
5
9e, n=2, X=CH2 piperidine; 9f, n=1, X=CH2 pyrrolidine; 9g, n=2, X=O
morpholine.
9l
10l, Yield: 46%
Scheme 6: C(sp2)-H amination reaction between oxazoline substituted
benzamide (5) and perylene bisimide derivative (9l) under photocatalytic
condition.
10g
10f
Time: 5h
Yield: 77%
10e
Time: 4h
Yield: 88%
Time: 4h
Yield: 87%
Directing Group Cleavage
The directing group was readily removed by carrying out the
amide hydrolysis of compound 10a under standard conditions
to furnish the corresponding benzoic acid derivative (11) and
amine (12) (Scheme 7) (Fig. S58-59, ESI†).
Reaction conditions: Oxazoline substituted benzamide 5, 1 mmol),
aliphatic amines (9e-g, 1 mmol), K2CO3 (2 mmol), DMSO (2 mL), visible
light, 5.0 mol % 4:CuNPs catalyst, under air.
Table 8: Scope of substituted heterocyclic amines
5
9h-k
10h-k
9h, R5=R6=Ph, Y=C, carbazole; 9i, R5=Ph, R6=H, Y=C, indole; 9j, R5=R6=H,
Y=CH, pyrrole; 9k, R5=H, R6=Ph, Y=N, imidazole.
Scheme 7. Removal of the Directing Group.
Conclusions
In conclusion, we designed and synthesised supramolecular
10i
Time: 7h
Yield: 64%
10k
Time: 7h
Yield: 60%
10j
Time: 7h
Yield: 65%
10h
Time: 8h
Yield: 62%
aggregates of triazole appended PBI derivative
3 which served
as reactors and stabilizers for the preparation of CuNPs at
room temperature. During this process, the aggregates of
derivative
species
3 themselves got oxidized to triazole N-oxide
. Interestingly, the in situ generated supramolecular
Reaction conditions: Oxazoline substituted benzamide 5, 1 mmol),
heteroamines (9h-k, 1 mmol), K2CO3 (2 mmol), DMSO (2mL) visible light,
5.0 mol % 4:CuNPs catalyst, under air.
4
8 | J. Name., 2012, 00, 1-3
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ensemble :CuNPs acted as efficient and reusable with water, dried over anhydrous sodium sVuielpwhAartticele Oannlinde
4
photocatalytic system for i) alkynylation of arenes with removed under reduced pressure to givDeOaI: 1s0o.l1i0d39r/eCs6idGuCe0.17T2h8eB
terminal alkynes and ii) amination of arenes with activated desired product was isolated by column chromatography using
aromatic amines via C(sp2)-H activation. In contrast to the 90:10 (CHCl3:hexane) as an eluent followed by recrystallization
traditional approaches, this photocatalytic system is with 5:1 (CHCl3:MeOH) to give 0.59 g (72%) of compound
economical and easy to prepare.
3
as
red solid; mp: 220°C. 1H NMR (500 MHz, CDCl3) δ = 8.55 (d, J =
5 Hz, 2H), 8.13 (d, J = 5 Hz, 2H), 7.81 (t, J = 10 Hz, 2H), 7.75 (s,
2H), 7.67 (t, J = 10 Hz, 2H), 7.47 (s, 4H, triazole C-H), 7.06 (d, J =
10 Hz, 2H), 5.38 (s, 8H, O-CH2-), 4.40 (t, J = 7.5 Hz, 8H, triazole-
N-CH2-), 4.33 (t, J = 7.5 Hz, 4H, -N-CH2-), 1.95 (t, J = 5 Hz, 8H,
triazole-N-CH2-CH2-), 1.87 (t, J = 7.5 Hz, 4H, -N-CH2-CH2-), 1.42-
1.25 (m, 60H), 0.87 (t, J = 7.5 Hz, 18H, -CH3). 13C NMR (125
MHz, CDCl3, ppm) δ = 163.2, 150.4, 145.2, 143.7, 138.6, 133.9,
132.6, 130.3, 129.2, 127.8, 127.5, 125.0, 120.2, 116.4, 115.4,
82.0, 60.1, 45.8, 29.7, 27.7, 25.8, 22.6, 19.3, 14.1. MALDI-TOF
Calcd for C96H126N14O8 [M]: 1603.9917, Found: 1604.0645 [M].
FT-IR: 1695 (triazole C=N) and 3120 cm−1 (triazole C-H).
Elemental analysis: Calcd for C96H126N14O8: C, 71.88; H, 7.92; N,
12.22; O, 7.98. Found: C, 71.86; H, 7.94; N, 12.23; O, 7.97.
Experimental Section
General Experimental methods and materials:
General experimental methods, quantum yield calculations
and materials used in the present work are same as reported
earlier by us.29,5b Cyclic Voltammetry studies were carried out
on CH Instruments CH1660D in H2O:ACN (2:8) solution (15 µL
THF to dissolve) with 0.1M tetrabutylammonium
hexafluorophosphate (TBAPF6) as supporting electrolyte. Glass
carbon electrode was used as working electrode, Ag/AgCl as
reference electrode and platinum wire as counter electrode.
The scans were performed at the rate of 50mV/sec at room
temperature. Spectroelectrochemical studies were done in K-
MAC SV-2100 spectra academy instrument to record the UV-
vis spectra.
General procedure for Photocatalytic C-H alkynylation catalysed
by supramolecular ensemble 4:CuNPs:
1.0 mol % of supramolecular ensemble 4:CuNPs as a
photocatalyst was added to a reaction mixture of oxazoline
UV-vis and Fluorescence studies:
substituted benzamide derivative
case of 6n 532 mg,
6a/6b/6c/6d/6e/6f/6g/6h/6i/6j/6k/6l/6m/6n
5
, (266 mg, 1.0 mmol; in the
mmol), terminal alkyne
mmol),
A 10-3 M stock solution was prepared by dissolving 16.03 mg of
,
2
compound
3 in 10.0 mL of dry THF. 15 µl of this stock solution
(
,
1
was further diluted with 1185 µl of dry THF and 1800 µL of
water/HEPES buffer (0.05 M, pH = 7.05) to prepare 3.0 mL of
K2CO3 (276 mg, 2 mmol) and DMSO (2.0 mL). The reaction
mixture was irradiated under 60 W tungsten filament bulb at
room temperature for 6-10 h. After completion of the reaction
(TLC), the reaction mixture was extracted with
dichloromethane (3×20 mL). The combined organic layer was
then washed with water, dried over anhydrous Na2SO4 and
distilled under reduced pressure to give crude product
5.0 µM solution of derivative
3 which was used for each UV-vis
and fluorescence studies. The aliquots of freshly prepared
standard solutions of metal perchlorates [M(ClO4)x; M = Ag+,
Hg2+, Au3+, Zn2+, Cu2+, Fe2+, Fe3+, Co2+, Pb2+, Ba2+, Ca2+, Ni2+, Pd2+
and Mg2+; X = 1-3] and chloride (MClY; Y = 1-3) (10-1M to 10-3M)
in distilled water were added to 3.0 mL solution of compound
(7a/7b/7c/7d/7e/7f/7g/7h/7i/7j/7k/7l/7m/7n
) which was
3
taken in quartz cuvette and spectra were recorded.
recrystallized from EtOAc/Hexane (1:1) solvent mixture.
Compound 7a.3a The 1H NMR (500 MHz, CDCl3, ppm) δ = 12.22
(s, 1H), 8.35 (d, J = 10 Hz, 1H), 8.04 (t, J = 7.5 Hz, 2H), 7.53 (d, J
= 5 Hz, 5H), 7.39-7.34 (m, 4H), 7.06 (t, J = 10 Hz, 1H), 4.58 (t, J =
15 Hz, 2H), 3.91 (t, J = 15 Hz, 2H).
Synthesis of supramolecular ensemble [4:CuNPs]:
1.0 mL aqueous solution of 1.0 M CuCl2 was mixed with 9.0 mL
of 0.033 M solution of compound
3 in H2O/THF (6:4, v/v)
mixture. The resulting solution was stirred at room
temperature for 10 min and the color of the solution mixture
changed from colorless to yellow, which gradually darkened to
brick red within 20 min, and thereafter formation of red
coloured CuNPs takes place. 100/500 µl of this solution
(1.0/5.0 mol % with respect to copper) was used as such in
C(sp2)-H alkynylation and amination catalytic reactions,
respectively.
1
Compound 7b. The H NMR (500 MHz, CDCl3, ppm) δ = 12.21
(s, 1H), 8.82 (d, J = 5 Hz, 2H), 8.06 (d, J = 5Hz, 2H), 7.60 (d, J =
7.5 Hz, 1H), 7.52 (dd, J =7.5, Hz, 3H), 7.40 (t, J = 7.5 Hz, 1H),
7.12 (d, J = 5 Hz, 1H), 6.62 (d, J = 10 Hz, 2H), 4.02 (dd, J = 5 Hz,
2H), 3.87 (dd, J = 5 Hz, 2H). 13C NMR (125 MHz, CDCl3, ppm) δ =
182.3, 147.1, 144.8, 138.2, 134.6, 131.2, 129.3, 129.0, 124.4,
123.2, 120.6, 118.1, 90.1, 85.3, 50.7, 41.0. ESI-MS Calcd For
C24H17N3O4: 434.1117 [M + Na]+, Found: 434.1154
1
Compound 7c. The H NMR (300 MHz, CDCl3, ppm) δ = 12.31
Synthesis of Derivative 3:
(s, 1H), 8.86 (d, J = 6 Hz, 1H), 8.09-7.96 (m, 3H), 7.60-7.52 (m,
3H), 7.37 (t, J = 9 Hz, 4H), 7.10 (d, J = 6 Hz, 1H), 4.57 (t, J = 6 Hz,
2H), 3.87 (m, J = 4.5 Hz, 2H). ). 13C NMR (75 MHz, CDCl3, ppm) δ
= 178.4, 147.1, 140.0, 136.7, 133.4, 131.8, 129.0, 125.0, 120.6,
116.1, 90.9, 84.0, 56.3, 48.7. ESI-MS Calcd For C24H17BrN2O2:
445.0552 [M+H]+, Found: 445.0589
To a solution of
1 (0.40 g, 0.452 mmol) and 2 (0.77 g, 1.357
mmol) in 20.0 mL THF were added K2CO3 (0.5 g, 3.360 mmol)
distilled H2O (1.5 mL) followed by [Pd(PPh3)2Cl2] as catalyst
(0.190 g, 0.271 mmol) under N2 atm. The reaction mixture was
refluxed at 80°C for 24 h and thereafter it was cooled to room
temperature, treated with water (20 mL) and extracted with
CHCl3 (3×20 mL). The combined organic layer was then washed
1
Compound 7d. The H NMR (500 MHz, CDCl3, ppm) δ = 11.96
(s, 1H), 8.03 (d, J = 10 Hz, 2H), 7.81 (d, J = 10 Hz, 2H), 7.59 (t, J =
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7.5 Hz, 1H), 7.46 (t, J = 7.5 Hz, 1H), 7.42 (d, J = 5 Hz, 2H), 7.38 26.0, 21.1, 13.5. ESI-MS Calcd For C24H26N2O2: 375.2073
View Article Online
DOI: 10.1039/C6GC01728B
(t, J = 7.5 Hz, 1H), 7.33 (t, J = 5 Hz, 1H), 7.26 (d, J = 10 Hz, 2H), [M+H]+, Found: 375.2072.
3.90 (t, J = 7.5 Hz, 2H), 3.82 (t, J = 7.5 Hz, 2H). 13C NMR (125 Compound 7m. The H NMR (500 MHz, CDCl3, ppm) δ = 12.22
1
MHz, CDCl3, ppm) δ = 183.5, 147.2, 140.0, 136.7, 133.4, 131.8, (s, 1H), 9.58 (s, 1H, OH), 7.83 (d, J = 10 Hz, 1H), 7.62 (t, J = 7.5
129.1, 126.2, 125.0, 120.4, 117.6, 116.2, 91.0, 84.2, 56.4, 48.8. Hz, 2H), 7.52 (t, J = 5 Hz, 1H), 7.46 (t, J = 7.5 Hz, 1H), 7.41 (t, J =
ESI-MS Calcd For C24H17ClN2O2: 401.1057 [M+H]+, Found: 7.5 Hz, 2H), 7.29 (t, J = 7.5 Hz, 1H), 4.10 (t, J = 7.5 Hz, 2H), 3.96
401.1048.
(t, J = 7.5 Hz, 2H), 1.54 (s, 6H). 13C NMR (125 MHz, CDCl3, ppm)
1
Compound 7e. The H NMR (500 MHz, CDCl3, ppm) δ = 12.21 δ = 166.8, 154.1, 139.8, 136.5, 132.9, 131.1, 129.0, 123.5,
(s, 1H), 10.50 (s, 1H), 8.03 (t, J = 7.5 Hz, 2H), 7.52 (d, J = 5 Hz, 121.1, 118.9, 95.5, 81.8, 72.0, 68.8, 50.7, 41.0. ESI-MS Calcd
4H), 7.38-7.32 (m, 5H), 7.08-7.03 (m, 1H), 4.57 (t, J = 15 Hz, For C21H20N2O3: 349.1552 [M+H]+, Found: 349.1516.
2H), 3.94-3.86 (m, 2H). 13C NMR (125 MHz, CDCl3, ppm) δ = compound 6n: 1H NMR (500 MHz, CDCl3) δ = 8.56 (d, J = 10 Hz,
187.3, 170.4, 143.2, 141.3, 141.0, 137.0, 134.6, 129.2, 127.6, 2H), 8.45 (s, 2H), 8.25 (d, J = 10 Hz, 2H), 3.95 (t, J = 7.5 Hz, 4H),
123.3, 117.1, 113.9, 112.5, 98.8, 89.6, 52.7, 46.0. ESI-MS Calcd 3.28 (s, 2H), 1.39 (t, J = 7.5 Hz, 4H), 1.30-1.18 (m, 36H), 0.93 (t,
For C25H18N2O3: 417.1215 [M+Na]+, Found: 417.1235.
Compound 7f. The H NMR (500 MHz, CDCl3, ppm) δ = 11.99 131.3, 129.7, 128.7, 128.4, 127.4, 126.6, 84.7, 45.1, 31.7, 31.2,
(s, 1H), 8.40 (d, J = 10 Hz, 1H), 7.83 (d, J = 10 Hz, 1H), 7.72–7.63 29.7, 22.6, 14.1. ESI-MS Calcd For C52H58N2O4: 775.4475
(m, 2H), 7.60 (d, J = 7.5 Hz, 1H), 7.47 (t, J = 7.5 Hz, 1H), 7.38 [M+H]+, Found: 775.4430.
J = 5 Hz, 6H). 13C NMR (125 MHz, CDCl3, ppm) δ = 162.4, 140.2,
1
1
(dd, J = 7.5 Hz, 2H), 7.27 (d, J = 7.5 Hz, 2H), 6.54 (d, J = 7.5 Hz, Compound 7n. The H NMR (500 MHz, CDCl3, ppm) δ = 12.23
2H), 4.11 (t, J = 7.5 Hz, 2H), 3.87 (s, 2H), 3.77 (t, J = 7.5 Hz, 2H). (s, 2H), 8.82 (d, J = 10 Hz, 2H), 8.12 (s, 2H), 8.04 (t, J = 10 Hz,
13C NMR (125 MHz, CDCl3, ppm) δ = 179.2, 161.6, 147.1, 139.9, 2H), 7.68 (d, J = 10 Hz, 4H), 7.62 (d, J = 10 Hz, 2H), 7.53-7.47
135.5, 134.0, 131.5, 128.4, 124.3, 119.0, 114.2, 88.5, 83.2, (m, 6H), 7.40 (t, J = 7.5 Hz, 2H), 7.12 (t, J = 7.5 Hz, 2H), 3.87 (d, J
60.7, 56.0. ESI-MS Calcd For C24H19N3O2: 420.1114 [M+K]+, = 12.5 Hz, 4H), 3.66–3.56 (m, 4H), 3.32–3.13 (m, 4H), 2.29 (t, J
Found: 420.1175.
= 7.5 Hz, 4H), 1.33–1.22 (m, 36H), 0.88 (t, J = 5 Hz, 6H). 13C
Compound 7g.3a The 1H NMR (500 MHz, CDCl3, ppm) δ = 11.92 NMR (125 MHz, CDCl3, ppm) δ = 167.0, 166.2, 159.5, 145.7,
(s, 1H), 8.82-8.78 (m, 1H), 8.10-7.98 (m, 3H), 7.66-7.46 (m, 4H), 145.1, 144.3, 142.7, 142.3, 140.7, 137.7, 137.3, 136.2, 133.3,
7.24-7.05 (m, 2H), 6.62 (dd, J = 10 Hz, 2H), 3.96-3.82 (m, 2H), 132.8, 132.0, 129.7, 128.7, 128.4, 127.3, 127.1, 121.5, 99.3,
3.34-3.26 (m, 2H), 2.99 (s, 3H, OMe).
94.5, 63.4, 56.9, 46.1, 30.9, 29.6, 26.0, 23.3, 16.9. ESI-MS Calcd
Compound 7h.3a The 1H NMR (500 MHz, CDCl3, ppm) δ = 11.99 For C84H82N6O8: 1325.6092 [M+Na]+, Found: 1325.5253
(s, 1H), 8.78 (d, J = 15 Hz, 1H), 8.03 (t, J = 12.5 Hz, 4H), 7.74 (d, Elemental analysis Calcd for C84H82N6O8: C, 77.39; H, 6.34; N,
J = 15Hz, 1H), 7.60 -7.50 (m, 3H), 7.37 (t, J = 10 Hz, 2H), 7.14 (d, 6.45; O, 9.82. Found: C, 77.38; H, 6.36; N, 6.43; O, 9.83.
J = 10Hz, 1H), 4.54 (t, J = 10 Hz, 2H), 3.83 (t, J = 10 Hz, 2H), 2.41
General procedure for Photocatalytic C-H amination catalysed by
supramolecular ensemble 4:CuNPs:
(s, 3H, Me).
1
Compound 7i.3a The H NMR (500 MHz, CDCl3, ppm) δ = 12.24
(s, 1H), 8.04 (t, J = 7.5 Hz, 4H), 7.63 (d, J = 5 Hz, 1H), 7.51 (dd, J
= 10 Hz, 4H), 7.39 (t, J = 7.5 Hz, 1H), 7.12 (t, J = 7.5 Hz, 1H),
4.57 (t, J = 5.0 Hz, 2H), 3.88 (t, J = 15 Hz, 2H).
A mixture of oxazoline substituted benzamide derivative
(266 mg, 1 mmol; in the case of 9l, 532 mg, 2 mmol), amine
9a/9b/9c/9d/9e/9f/9g/9h/9i/9j/9k/9l, 1 mmol), K2CO3 (276
mg, 2 mmol) in DMSO (2.0 mL), in the presence of
supramolecular ensemble 4:CuNPs (5 mol %) as
5,
(
Compound 7j. The 1H NMR (500 MHz, CDCl3, ppm) δ = 12.29 (s,
1H), 8.81 (s, 1H), 8.47 (d, J = 10 Hz, 1H), 8.06 (d, J = 15 Hz, 2H),
7.68 (d, J = 5 Hz, 2H), 7.59-7.46 (m, 4H), 7.38 (t, J = 7.5 Hz, 1H),
7.12 (d, J = 5 Hz, 1H), 4.60-4.56 (m, 2H), 3.91-3.82 (m, 2H). 13C
NMR (125 MHz, CDCl3, ppm) δ = 180.5, 151.7, 147.2, 139.9,
135.4, 134.4, 132.3, 131.3, 127.3, 126.3, 124.5, 120.2, 114.4,
88.7, 81.4, 61.7, 55.4. ESI-MS Calcd For C23H17N3O2: 368.1399,
[M+H]+, Found: 368.1328.
a
photocatalyst was stirred at room temperature under 60 W
tungsten filament bulb for 4-8 h. After completion of the
reaction (TLC), the reaction mixture was extracted with
dichloromethane (3×20 mL) and the combined organic layer
was then washed with water, dried over anhydrous Na2SO4
and distilled under reduced pressure to obtain crude product
Compound 7k.3a The 1H NMR (500 MHz, CDCl3, ppm) δ = 12.26
(s, 1H), 8.02 (t, J = 5.0 Hz, 1H), 7.66 (dd, J = 5 Hz, 2H), 7.55 (t, J
= 7.5 Hz, 2H), 7.52-7.46 (m, 3H), 4.58 (dt, J = 5 Hz, 2H), 3.87
(dd, J = 5 Hz, 2H), 2.99 (t, J = 12.5 Hz, 2H), 2.42-2.34 (m, 6H),
1.37 (t, J = 5 Hz, 3H).
(10a/10b/10c/10d/10e/10f/10g/10h/10i/10j/10k/10l) which
was recrystallized from EtOAc/Hexane (2:1) solvent mixture.
1
Compound 10a.4a The H NMR (500 MHz, CDCl3, ppm) δ =
12.21 (s, 1H), 11.94 (s, 1H), 8.81 (t, J = 7.5 Hz, 1H), 8.05 (t, J =
7.5 Hz, 4H), 7.52 (t, J = 7.5 Hz, 1H), 7.42-7.32 (m, 3H), 7.30–
7.29 (m, 1H), 6.63 (d, J = 5 Hz, 2H), 4.58 (t, J = 5 Hz, 2H), 3.87 (t,
J = +5 Hz, 2H).
Compound 7l. The 1H NMR (500 MHz, CDCl3, ppm) δ = 11.92 (s,
1H), 7.83 (t, J = 7.5 Hz, 2H), 7.61 (d, J = 10 Hz, 1H), 7.53 (t, J =
7.5 Hz, 1H), 7.48–7.36 (m, 3H), 7.28 (t, J = 7.5 Hz, 1H), 4.07 (t, J
= 7.5 Hz, 2H), 3.92 (t, J = 7.5 Hz, 2H), 2.25 (t, J = 5 Hz, 2H),
1.61–1.47 (m, 2H), 1.44–1.26 (m, 6H), 0.99 (t, J = 7.5 Hz, 3H).
13C NMR (125 MHz, CDCl3, ppm) δ = 167.1, 143.5, 139.2, 136.8,
131.2, 127.1, 122.7, 118.2, 98.4, 63.7, 52.8, 35.7, 31.7, 31.1,
1
Compound 10b.4a The H NMR (500 MHz, CDCl3, ppm) δ =
12.21 (s, 1H), 8.03 (d, J = 10 Hz, 1H), 7.76 (d, J = 5 Hz, 1H), 7.54-
7.42 (m, 3H), 7.29–7.23 (m, 4H), 7.08-7.01 (m, 3H), 4.17 (t, J =
7.5 Hz, 2H), 4.05 (t, J = 7.5 Hz, 2H).
1
Compound 10c.4a The H NMR (300 MHz, CDCl3, ppm) δ =
12.14 (s, 1H), 11.67 (s, 1H), 8.45 (d, J = 15 Hz, 1H), 7.61 (d, J =
10 | J. Name., 2012, 00, 1-3
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ARTICLE
7.5 Hz, 2H), 7.55–7.51 (m, 1H), 7.20 (d, J = 5 Hz, 2H), 6.85 (dd, J Compound 10k. 1H NMR (500 MHz, CDCl3) δ = 11.98 (s, 1H),
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= 10 Hz, 3H), 6.24 (d, J = 15 Hz, 3H), 3.78 (t, J = 7.5 Hz, 2H), 3.02 8.26 (d, J = 10 Hz, 1H), 8.12 (d, J = 10 Hz, D1OHI):,170..180139(d/C,6JG=C101072H8zB,
(t, J = 7.5 Hz, 2H).
1H), 7.67 (d, J = 10 Hz, 1H), 7.62–7.53 (m, 2H), 7.47 (t, J = 12.5
The H NMR (500 MHz, CDCl3, ppm) δ = Hz, 2H), 7.35–7.27 (m, 4H), 7.20 (t, J = 7.5 Hz, 1H), 4.05 (t, J =
1
Compound 10d 4a
.
13.04 (s, 1H), 12.19 (s, 1H), 8.11 (d, J = 10 Hz, 1H), 8.05 (d, J = 15 7.5 Hz, 2H), 3.49 (t, J = 7.5 Hz, 2H). 13C NMR (125 MHz, CDCl3,
Hz, 1H), 7.93 (d, J = 5 Hz, 2H), 7.56–7.49 (m, 4H), 7.18-7.10 (m, ppm) δ = 168.2, 145.4, 143.8, 139.4, 135.6, 134.0, 131.1,
2H), 6.79–6.67 (m, 3H), 4.44 (t, J = 10 Hz, 2H), 4.23 (t, J = 10 Hz, 130.3, 127.3, 125.5, 123.8, 123.0, 117.1, 110.9, 64.3, 52.2. ESI-
2H).
MS Calcd For C23H18N4O2: 383.1508 [M+H]+, Found: 383.1587.
1
Compound 10e. 1H NMR (300 MHz, CDCl3) δ = 12.31 (s, 1H),
8.03 (t, J = 7.5 Hz, 3H), 7.52 (d, J = 9 Hz, 3H), 7.12 (d, J = 9 Hz,
2H), 4.56 (t, J = 12 Hz, 2H), 3.85 (d, J = 9 Hz, 2H), 3.46 (d, J = 6
Hz, 2H), 3.30 (d, J = 6 Hz, 2H), 1.55 (d, J = 6 Hz, 6H). 13C NMR
(75 MHz, CDCl3, ppm) δ = 173.0, 161.4, 145.2, 138.9, 134.6,
132.0, 129.7, 128.7, 128.4, 127.3, 123.3, 121.4, 118.7, 60.4,
56.0, 29.8, 22.3. ESI-MS Calcd For C21H23N3O2: 350.1869
[M+H]+, Found: 350.1873.
Compound 10l. The H NMR (500 MHz, CDCl3, ppm) δ = 12.16
(s, 2H), 11.91 (s, 2H), 8.83 (t, J = 10 Hz, 2H), 8.04 (t, J = 7.5 Hz,
2H), 8.00 (s, 2H), 7.61 (d, J = 10 Hz, 4H), 7.53 (t, J = 7.5 Hz, 6H),
7.40 (t, J = 7.5 Hz, 6H), 7.16–7.05 (m, 2H), 6.92 (d, J = 7.5 Hz,
2H), 6.87–6.81 (m, 2H), 6.59 (t, J = 20 Hz, 2H), 3.88 (t, J = 5.0
Hz, 4H), 3.66 (t, J = 5.0 Hz, 4H), 3.18 (t, J = 7.5 Hz, 4H), 1.83 (t, J
= 7.5 Hz, 4H), 1.27-1.25 (m, 36H), 0.87 (t, J = 5 Hz, 6H). 13C
NMR (125 MHz, CDCl3, ppm) δ = 162.7, 162.6, 154.4, 149.4,
139.1, 134.8, 133.4, 132.1, 128.5, 127.9, 126.5, 123.1, 122.2,
119.3, 117.7, 65.0, 60.1, 42.7, 36.5, 31.5, 27.1, 22.7, 22.3, 18.0.
ESI-MS Calcd for C92H92N8O8: 1475.6675 [M+K]+, found:
1475.7450. Elemental analysis Calcd for C92H92N8O8: C, 76.85;
H, 6.45; N, 7.79; O, 8.90. Found: C, 76.84; H, 6.44; N, 7.80; O,
8.91.
Compound 10f. 1H NMR (300 MHz, CDCL3) δ = 12.45 (s, 1H),
8.01 (d, J = 3 Hz, 2H), 7.94 (t, J = 3.0 Hz, 2H), 7.78 (d, J = 6 Hz,
1H), 7.37 (d, J = 6 Hz, 2H), 7.15–7.11 (m, 1H), 4.53 (t, J = 6 Hz,
2H), 4.07 (t, J = 9 Hz, 2H), 3.01 (d, J = 6 Hz, 2H), 2.85 (d, J = 6
Hz, 2H), 2.06–1.99 (m, 4H). 13C NMR (75 MHz, CDCl3, ppm) δ =
168.7, 156.1, 141.2, 137.8, 135.2, 131.9, 129.6, 128.7, 128.4,
127.3, 121.5, 118.1, 63.4, 53.0, 51.6, 29.6. ESI-MS Calcd For
C20H21N3O2: 336.1712 [M+H]+, Found: 336.1770.
Typical procedure for directing group removal4a:
In a 25 mL round bottom flask (RBF), compound 10a (40 mg,
0.1 mmol) and KOH (220 mg, 4 mmol) were mixed in 5 mL
EtOH. The reaction mixture was stirred at 80°C for 7 h under
aerial conditions. After completion of the reaction (TLC), the
solvent was removed under reduced pressure to give a residue
to which water (10 ml) was added followed by extraction with
EtOAc (20 x 3 mL). The combined organic layer was was then
washed with water, dried over anhydrous Na2SO4 and distilled
off under reduced pressure to yield a crude product which was
purified by preparative thin layer chromatography (Prep. TLC)
to recover directing group (11) (20 mg) and 2-(4,5-
Compound 10g. 1H NMR (500 MHz, CDCl3) δ = 12.19 (s, 1H),
8.15 (d, J = 10 Hz, 1H), 7.68 (d, J = 10 Hz, 1H), 7.52 (t, J = 10 Hz,
1H), 7.39 (d, J = 5 Hz, 1H), 7.32 (t, J = 7.5 Hz, 1H), 7.26 (t, J = 7.5
Hz, 1H), 6.83 (t, J = 5 Hz, 2H), 4.11 (t, J = 7.5 Hz, 2H), 3.92 (t, J =
7.5 Hz, 2H), 3.78 (t, J = 5 Hz, 4H), 3.51 (t, J = 5 Hz, 2H), 3.30 (t, J
= 5 Hz, 2H). 13C NMR (125 MHz, CDCl3, ppm) δ = 168.8, 156.2,
144.7, 141.2, 137.9, 135.3, 132.0, 129.7, 128.7, 128.4, 127.3,
121.5, 118.2, 64.5, 63.4, 55.2, 53.1. ESI-MS Calcd For
C20H21N3O3: 352.1661 [M+H]+, Found: 352.1636.
Compound 10h. 1H NMR (300 MHz, CDCl3) δ = 11.69 (s, 1H),
7.96 (d, J = 6 Hz, 1H), 7.34 (d, J = 9 Hz, 1H), 7.25-7.15 (m, 4H),
6.99 (d, J = 7.5 Hz, 1H), 6.69 (t, J = 7.5 Hz, 5H), 6.55 (d, J = 6 Hz,
2H), 6.35 (t, J = 6 Hz, 2H), 3.70 (t, J = 9 Hz, 2H), 3.41 (t, J = 9 Hz,
2H). 13C NMR (75 MHz, CDCl3, ppm) δ = 170.4, 141.7, 137.8,
135.9, 134.8, 133.2, 129.5, 128.4, 127.0, 123.9, 121.6, 115.0,
110.9, 68.8, 56.3. ESI-MS Calcd For C28H21N3O2: 432.1712
[M+H]+, Found: 432.1862.
dihydrooxazol-2-yl) aniline (12) (13.3 mg) in a ratio of 60:40.
1
Compound 11. The H NMR (300 MHz, CDCl3, ppm) δ = 12.05
(s, 1H, COOH), 11.51 (s, 1H, NH), 8.36 (dd, J = 9 Hz, 2H), 7.52 (t,
J = 6 Hz, 1H), 7.06 (t, J = 9 Hz, 1H), 7.00-6.85 (m, 2H), 6.10-5.99
(m, 2H). 13C NMR (75 MHz, CDCl3, ppm) δ = 182.2, 147.0, 138.2,
134.6, 131.2, 129.3, 128.9, 126.8, 122.8, 122.7, 119.6, 114.6.
1
Compound 12.The H NMR (300 MHz, CDCl3, ppm) δ = 7.59-
Compound 10i. 1H NMR (300 MHz, CDCl3) δ = 12.32 (s, 1H),
7.73 (t, J = 9 Hz, 3H), 7.38 (d, J = 7.5 Hz, 2H), 7.20 (t, J = 6 Hz,
3H), 6.93 (dd, J = 7.5 Hz, 4H), 6.47 (d, J = 9 Hz, 1H), 6.20 (d, J =
7.50 (m, 2H), 7.38-7.34 (m, 2H), 4.57 (t, J = 10.5 Hz, 2H), 3.87
(t, J = 9 Hz, 2H), 3.56 (brs, 2H, NH2). 13C NMR (75 MHz, CDCl3,
ppm): 164.4, 149.7, 140.0, 132.9, 129.1, 122.8, 119.8, 115.6,
66.4, 50.4.
3 Hz, 1H), 4.25 (t, J = 7.5 Hz, 2H), , 3.87 (t, J = 7.5 Hz, 2H). 13
C
NMR (75 MHz, CDCl3, ppm) δ = 166.7, 155.1, 141.2, 137.1,
131.9, 129.8, 128.7, 128.0, 127.8, 126.4, 123.7, 122.8, 115.7,
111.2, 69.7, 54.7. ESI-MS Calcd For C24H19N3O2: 382.1556
[M+H]+, Found: 382.1535.
Acknowledgements
V. B. is thankful to SERB, New Delhi (ref. no.
EMR/2014/000149) for financial support. We are also thankful
to UGC for ‘‘University with Potential for Excellence’’ (UPE). S.
K. (SRF) is thankful to DST for INSPIRE fellowship.
Compound 10j. 1H NMR (300 MHz, CDCl3) δ = 12.12 (s, 1H),
8.26 (d, J = 6 Hz, 1H), 7.81 (d, J = 6 Hz, 1H), 7.59–7.49 (m, 3H),
6.99 (d, J = 9 Hz, 3H), 6.76 (t, J = 9 Hz, 2H), 6.37–6.30 (m, 2H),
4.02 (dd, J = 6 Hz, 2H), 3.30 (dd, J = 6 Hz, 2H). 13C NMR (75
MHz, CDCl3, ppm) δ = 164.2, 154.7, 140.3, 135.7, 131.4, 129.3,
128.1, 127.0, 121.2, 117.1, 112.8, 69.5, 54.5. ESI-MS: Calcd For
C20H17N3O2: 354.1218 [M+Na]+, Found: 354.1268.
Notes and references
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This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 11
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Green Chemistry
Journal Name
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Green Chemistry
Page 14 of 14
View Article Online
DOI: 10.1039/C6GC01728B
Graphical Abstract
C (sp2)-H Alkynylation
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Inexpensive CuNPs
Room Temperature
Photocatalyst
C(sp2)-H activation
Eco-friendly
CuNPs
C (sp2)-H Amination
Supramolecular ensemble 4:CuNPs
Supramolecular ensemble of triazole appended perylene bisimide (PBI) derivative 4 and
in situ generated copper nanoparticles (CuNPs) serves as a light harvesting antenna in
photocatalytic C(sp2)-H alkynylation and amination reaction of arenes under mild and
eco-friendly conditions.