A five coordination Cu(II) cluster-based MOF and its application in the synthesis of pharmaceuticals: Via sp3 C-H/N-H oxidative coupling

Article abstract of DOI:10.1039/c7cy00882a

Herein, a copper metal-organic framework, termed as VNU-18, containing penta-coordinated sites was successfully synthesized and fully characterized. This material was demonstrated to be an efficient heterogeneous catalyst for the oxidative C-H activation via N-H bonds. The optimized conditions are applicable for the synthesis of pharmaceuticals constructed by α-amino carbonyl skeletons.

Full text of DOI:10.1039/c7cy00882a

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Five coordination Cu(II) cluster-based MOF and its application in
synthesis of pharmaceuticals via Sp3 C-H/N-H oxidative couplings
Thuan V. Tran,[a] Hanh T. N. Le,[b] Hiep Q. Ha,[a] Xuan N. T. Duong,[a] Linh H-T. Nguyen,[c] Tan L. H.
Doan,[c,d] Ha L. Nguyen,*[c] and Thanh Truong*[a]
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
A copper metal-organic framework containing penta-coordinated materials have emerged as promising heterogeneous catalysts for
sites, termed VNU-18, was successfully synthesized and fully valuable organic reactions due to their pore size controllability,
characterized. This material was demonstrated to be an efficient facile modification of starting components, and fine tunable
heterogeneous catalyst for the oxidative C-H activation by N-H structure.9 In particular, copper-based MOFs with open metal sites
bonds. The optimized conditions are applicable for the synthesis have been commonly utilized as catalysts for various
of pharmaceuticals constructed by α-amino carbonyl skeletons.
transformation.10 In all reported Cu-MOFs catalysts synthesized
using sole copper salt and carboxylate organic linkers, Cu-oxo
α-Amino carbonyls is the skeletons that are often found in variety of cluster existed in tetrahedral, distorted tetrahedral, or square
valuable compounds such as amino acids, pharmaceuticals, and planar with 4 coordination sites.11 This results in low chemical
biologically active natural products.1 Therefore, methodology stability of these Cu-MOFs toward moisture and harsh chemical
development for approaching α-aminated carbonyls has gained environment especially with high chelating affinity reagents and
much attention. In particular, traditional strategy involved the utility strong oxidants.12 To partially overcome this limitation, an aromatic
of pre-functionalized α-halogenated carbonyls in nucleophilic a or tertiary nitrogen containing ligand such as 1,4-
Finkelstein substitution reactions.2 Metal-free or organocatalytic diazabicyclo[2.2.2]octane (DABCO) or 4,4’-bipyridine (BP) was often
routes suffered from limited scope and additional steps to prepare introduced to form the vulnerable and thermally reversible fifth
the starting materials or/and generate the desired products.3 coordination.13 Though remarkable improvement in chemical
Reports in transition metal catalysis disclosed the two-step catalytic durability was reported, the ligand exchange between these ligands
pathway starting with the electrophilic 2π-electrophile aza- and strong chelating starting materials such as ketones or
substrates and enolates followed by reduction.4 Recently, a novel primary/secondary amines was observed during reactions.14 With
direct introduction of amine nitrogen adjacent to a carbonyls in a literature precedents, we hypothesized that copper-oxo clusters
catalytic manner was disclosed by MacMillan group.5 Besides the possessing
5 permanent bound molecules would own higher
the reaction scope is limited to secondary amines, the use of chemical resistance.15 Within this aspect, the synthesis and
homogeneous catalysts, especially in pharmaceutical industry, often characterization of copper-based MOF, term VNU-18, constructed
represent a major problems regarding contaminated metal removal by using 3,5-pyridinedicarboxylic acid (PDC) linker was herein
from final product.6 Therefore, the development of more practical presented. Furthermore, the chemical stability and catalytic activity
protocols catalyzed by heterogeneous catalysts remains demanding. of VNU-18 possessing copper cluster with five coordination sites
One can argue that increased efficiency makes the chemical was investigated in the oxidative C-H/N-H couplings between
processes more "green" by reducing amount of step in purification ketones and amines. Indeed, high efficiency in conjunction with
process and recycling the catalyst.7
excellent heterogeneity of VNU-18 was detected while other Cu-
Metal-organic frameworks (MOFs) serve as new class of porous MOFs with 4 coordination sites were structurally damaged or/and
materials which possess versatility in connecting metal-containing inactive.
nodes with a variety of organic bridges.8 Consequently, these VNU-18 was solvothermally synthesized by the reaction of 3,5-
pyridinedicarboxylic acid (PDC) and coppernitratetrihydrate
.
Cu(NO3)2 3H2O in N,N-dimethylformamide (DMF) at 100 °C in 24 h
(Scheme 1). The blue single crystal of VNU-18 has been isolated for
crystal structure elucidation by single crystal X-ray measurement.
The crystal structure of VNU-18 revealed that this material
aFaculty of Chemical Engineering, Bach Khoa University, VNU-HCM, 268 Ly Thuong
Kiet, District 10, Ho Chi Minh City, Vietnam. Email: tvthanh@hcmut.edu.vn.
bInstitute of Public Health, Ho Chi Minh City
159 Hung Phu, District 8, Ho Chi Minh City, Vietnam.
cCenter for Innovative Materials and Architectures (INOMAR), VNU-HCM, Ho Chi
Minh City, Vietnam. Email: nlha@inomar.edu.vn, hanguyen@manar.edu.vn
dFaculty of Chemistry, University of Science, VNU-HCM, Ho Chi Minh City, Vietnam.
Electronic Supplementary Information (ESI) available: Synthesis and
characterization of VNU-18, additional catalytic data, and recycling studies. See
DOI: 10.1039/b000000x/
crystallized in the monoclinic P21/m space group with
a =
14.9611(7) Å, b = 18.8833(9) Å, c = 15.2457(8) Å, = 102.2435(18)°.
β
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The three-dimensional structure of VNU-18 was composed by the pressure region, resulting in calculated Brunauer–Emmett–Teller
connection between 3,5-pyridinedicarboxylate linker units, in which (BET) and Langmuir surface areas of 900 and 1200 m2 g-1,
the organic components act as 3-connected of point extension, and respectively (Fig. 2b). The topological analysis for VNU-18 was then
copper building blocks.
studied by TOPOS 4.0 package.18 The linking of pentanuclear Cu
single site and two organic linker based PDC had been simplified as
square planar connection. Another square linking unit was also
identified based the connection of two PDC units with Cu metal
clusters, in which the carboxylate functionalities chelated to Cu-
paddle wheel at the center, whereas pyridine components
generated the octahedral block (See SI, Section S4). These 4-
connected points combine to each other to result in the three-
dimensional topology of 4, 4, 4 T10.
Scheme 1. Synthetic scheme depicting the generalized formation of VNU-18 (c) via the
combination of 3,5-pyridinedicarboxylate unit (PDC) (a) and three kinds of Cu building
block (b). Color code: Cu, blue; O, red; C, black; N, green; H atoms are omitted for
clarify. The yellow balls display the pore size of 14 Å in calculated of VNU-18.
It is noted that the copper building blocks of VNU-18 are
interestingly found with three kinds of geometrical cluster units,
which is unprecedentedly reported in MOFs chemistry based on Cu-
Figure 2. (a) PXRD analysis showing the experimental pattern (red), as-synthesized
(blue), and simulated pattern (black). (b) N2 adsorption isotherm of VNU-18 at low
pressure and 77 K.
15
oxo cluster (Scheme 1).11, Specially, two carboxylate groups of
PDC connected to Cu-paddle wheel cluster alternatively, generating
the infinitive undulation of paddle wheel blocks. A copper atom of
Cu-paddle wheel links to 2 carboxylates of PDC and one guest
molecule, which will be evacuated by solvent exchange and
activation to form the open copper site. This border of paddle
wheel blocks covers the 1D channel of the pore of VNU-18, whose
size is found to be 14 Å in calculated diameter. Two PDC linking
units locate perpendicularly with the undulate paddle wheels
resulting the single octahedral Cu-building blocks via the connection
of carboxylate functionalities, pyridine-based phenyl rings on PDC,
which connected forming undulate chain of Cu-paddle wheel, and
copper atom. Three pyridine based phenyl rings of PDC linkers are
orthogonal at the penta copper site, which is directly linked to two
hydroxyl groups for charge balancing request (Fig. 1).
As discussed, Cu-oxo clusters in distorted tetrahedral existing in all
reported Cu-MOFs with open Cu sites often showed low stability in
high chelating environment such as N-H amines or carbonyls. This
was herein supported by results of oxidative cross coupling
reactions between ethylphenylketone and morpholine using various
Cu-MOFs with 4 coordination sites under reported homogeneous
conditions and KBr as bromine source (Table 1, entries 2-6). Though
several promising yields were obtained, we observed that all tested
Cu-MOFs catalysts were either dissolved or partially leached by
measuring the soluble copper content in reaction filtrate.
Gratifyingly, VNU-18 maintained its structure after identical
reaction with 42 % yield. Therefore, optimization of the catalytic
activity with respect to solvent, type of bromine sources, and
catalyst was further investigated.
Unlike homogeneous
counterpart, reactions in dimethylformadehyde (DMF) as optimal
solvent offered 86 % yield (entry 9). In particular, <60 % yields were
obtained when 1,4-dioxane, acetonitrile, and toluene were
employed (entries 7, 11, 12). Studies of MacMillan postulated that
the bromine atom in CuBr2 participated in the formation of a
transient α-bromo carbonyl.5 With VNU-18, the presence of KBr
bromine source was showed to be crucial (entry 10). The
replacement of KBr with other halogenated salts such as LiBr, CsBr,
KI, or KCl did not technically or economically improve the efficiency
(entries 13-16). Notably, reactions using metal salt Cu(NO3)2 catalyst
afforded lower yields than those with VNU-18 (entry 17) while
contribution of sole organic linker PDC is unlikely (entry 18). This
supported the synergetic and cooperative effect of linkers on metal
clusters within the VNU-18 structure. Furthermore, other
commonly used heterogeneous systems provided low catalytic
activity or stability (entries 19-21) while other transition metal
bromide salts failed to afford acceptable yields (entries 22-24).
Figure 1. As-symmetry unit of VNU-18 drawn by ORTEP with thermal ellipsoids style at
50% probability.
The powder X-ray diffraction (PXRD) analysis further confirms the
pure phase of VNU-18 showing by the coincidence between the as-
synthesized, the activated and the simulated PXRD pattern (Fig.2.a).
The thermogravimetric analysis (TGA) supports the formulation of
VNU-18 by the residual coincidence of CuO residue between
experimental (35.2%) and theory (37.0%) (see SI, Section S2). The
potential solvent accessible void, as calculated by PLATON,17 is
58.8%. This was supported by N2 adsorption isotherm measured at
77 K, in which VNU-18 exhibited significant uptake in the low-
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Table 1. Optimization of conditionsa
observed in all cases (Table 1). Furthermore, the crystallinity of re-
used catalyst was maintained as compared to that of fresh catalyst.
Table 2. Reaction scope with respect to coupling partnersa
Br-
source
-
KBr
KBr
GC
Yield (%)
78
62
65
[Cu]b
(ppm)
308
56
105
Entry
Catalyst
Solvent
Entry
N-H
C-H
Product
Yield (%)
1
2
3
CuBr2
Cu2(BTC)3
Cu(BDC)
Cu2(BDC)2
(BPY)
Cu2(BDC)2
(DABCO)
Cu2(BPDC)
(BPY)
VNU-18
VNU-18
VNU-18
VNU-18
VNU-18
VNU-18
VNU-18
VNU-18
VNU-18
VNU-18
Cu(NO3)2
PDC
DMSO
DMSO
DMSO
81
1
(76)b
4
5
6
DMSO
DMSO
DMSO
KBr
KBr
KBr
35
56
35
92
87
98
2
3
48
73
7
8
9
DMSO
CH3CN
DMF
KBr
KBr
KBr
-
KBr
KBr
LiBr
CsBr
KI
KCl
KBr
KBr
KBr
KBr
KBr
KBr
KBr
KBr
42
56
86
6
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
315
n.d
162
75
23
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
DMF
1,4-dioxane
Toluene
DMF
40
28
21
76
84
26
71
<2
48
31
22
7
4
5
6
77
76
76
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
Cu/Zeolite X
Cu/ZSM-5
CuFe2O4
FeBr3
DMF
DMF
DMF
CoBr2
NiBr2
<2
5
aVolume of solvent, 2 mL; 0.5 mmol scale.; BDC, benzene-1,4-dicarboxylate; BTC,
1,3,5-benzenetricarboxylate; BPY, 4,4‘-bipyridine; BPDC, biphenyldicarboxylate;
DABCO, 1,4-diazabicyclo[2.2.2]octane. bin reaction filtrate. See Supporting
Information for more details.
7
8
78
To investigate the activity of VNU-18 over wide range of substrates,
optimized conditions were applied for a variety of C-H and N-H
bonds. The isolated product yields are presented in Table 2. In
particular, aromatic and especially aliphatic ketones undergo
coupling efficiently without addition of co-catalyst as reported in
homogeneous conditions (entries 1-4).5 Ester functionality can also
be used as C-H bond starting materials (entries 2, 3, and 5).
Reactions are not limited to morpholine. Subsequently, amination
by 1-methylpiperazine, piperidine and its derivatives, methyl benzyl
amine, and pyrrolidine afforded desired products in good yields
(entries 6-11). Acylic amine such as dimethyl amine is also active
(entry 12). Interestingly, aromatic amine and primary amine, which
were not active under CuBr2 protocol, were successfully introduced
to C-H bonds (entries 13 and 14) demonstrating the excellent
activity of VNU-18 toward oxidative C-H/N-H couplings.
2-Me: 45
3-Me: 74
4-Me: 80
9
82
10
65c
11
12
51
62
To confirm the stability and heterogeneity of VNU-18 during
reaction process, control experiments were subsequently
conducted to ensure the catalysis under leached metal is unlikely
(See SI, Section S7). No further formation of desired product when
catalyst was removed from reaction mixture is supported by the
concentration of Cu2+ in reaction filtrate. Subsequently, the
recycling studies were performed with 6 consecutive times without
remarkable loss in catalytic activity. It is worth mentioning that all
tested Cu-MOFs were vulnerable and leaching of metal species was
13
47d
14
31
aReaction conditions: Volume of solvent, 2 mL; 0.5 mmol scale. Number in
parenthesis indicated the 5.0 mmol scale reaction. ccatalyst (10 mol %). dreactions
were run at 40 °C.
b
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possessing 5 permanent bound molecules are currently conducting.
Vietnam National University-Ho Chi Minh City (VNU-HCM) is
acknowledged for financial support via grant No. B2015-20-04.
Notes and references
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Scheme 2. Tentative reaction mechanism
Subsequently, the reaction mechanism was proposed (Scheme 2).
α-Bromination of carbonyl compounds under copper catalysis to
generate α-bromo carbonyls followed by nucleophilic substitution
by N-H amines. In fact, the synthesized α-bromo ethylphenylketone
facilely reacted with morpholine to afford desired product in
excellent yield (see Supporting Information).
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To highlight the generality of VNU-18 within oxidative amination,
the synthesis of high-profile relevant medicinal agents were carried
out utilizing the optimized conditions. The use of heterogeneous
catalyst in pharmaceutical industry is highly
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conditions under VNU-18 catalyst.
preferred due to the avoid of removal of toxic contaminated metals
in final products and cost reduction.19 Particularly, racemic of
Clopidogrel (Plavix), an agent to prevent blood clot, Amfepramone,
an appetite suppressant, and α-pyrrolidinovalerophenone (α-PVP),
an dopamine transporters (DAT), were achieved in reasonale yields
in one-step manner under VNU-18 catalysis protocol from
commercially available starting materials (eq. 1-3, Scheme 3). The
utility of air atmosphere instead of oxygen, ligand-free, ambient
temperature, and heterogeneous catalyst makes the method more
operational.
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In summary, we have presented the synthesis of copper-based
metal-organic framework, VNU-18, with copper cluster possesses
three kinds of geometrical cluster units, which is unprecedentedly
reported in MOFs chemistry based Cu-oxo cluster. Full
characterization for VNU-18 including the single crystal and powder
X-ray diffraction analysis, thermogravimetrical analysis, and N2
adsorption measurement at low pressure and 77 K were also
disclosed. Furthermore, this material was demonstrated as active
catalyst for direct coupling of wide range of carbonyls and N-H
amines. Leaching test and recycling studies indicated the
heterogeneity of VNU-18 while other reported Cu-MOFs or
common heterogeneous materials were inefficient. Gratifyingly, the
synthesis of prominent pharmaceutical agents was also performed
using optimized conditions. More research to support the chemical
resistance and excellent activity of this copper-oxo cluster
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Five coordination sites of Cu(II)
cluster were found in VNU-18 that
showed highly efficient catalytic
property for the oxidative C-H
activation by N-H bonds.
Thuan V. Tran, Hanh T. N. Nguyen,
Hiep Q. Ha, Xuan N. T. Duong, Linh
H-T. Nguyen, Tan L. H. Doan, Ha L.
Nguyen,* and Thanh Truong*
Page No. – Page No.
Copper
cluster
with
five
coordination sites within Cu-MOFs
and its application in synthesis of
pharmaceuticals via Sp3 C-H/N-H
oxidative couplings.
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