Ligand-Free Copper-Manganese Spinel Oxide-Catalyzed Tandem One-Pot C–H Amidation and N-Arylation of Benzylamines: A Facile Access to 2-Arylquinazolin-4(3H)-ones

Article abstract of DOI:10.1002/adsc.201600549

An efficient ligand-free copper-manganese (Cu-Mn) spinel oxide-catalyzed direct tandem C?H oxygenation and N-arylation of benzylamines has been developed. The method has been utilized for the synthesis of medicinally important 2-arylquinazolin-4(3H)-ones. Salient features of this method include recyclable catalyst, no ligand, excellent product yields, shorter reaction times and a broad substrate scope. (Figure presented.).

Full text of DOI:10.1002/adsc.201600549

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DOI: 10.1002/adsc.201600549
Ligand-Free Copper-Manganese Spinel Oxide-Catalyzed Tandem
One-Pot C–H Amidation and N-Arylation of Benzylamines: A
Facile Access to 2-Arylquinazolin-4(3H)-ones
Rohit Sharma,a,b Ram A. Vishwakarma,a,b and Sandip B. Bharatea,b,*
a
Medicinal Chemistry Division, CSIR – Indian Institute of Integrative Medicine, Canal Road, Jammu – 180001, India
Fax : (+91)-191–258–6333; phone: (+91)-191–258–5006; e-mail: sbharate@iiim.ac.in
Academy of Scientific & Innovative Research (AcSIR), CSIR – Indian Institute of Integrative Medicine, Canal Road,
b
Jammu – 180001, India
Received: May 23, 2016; Revised: June 28, 2016; Published online: && &&, 0000
Supporting information for this article can be found under: http://dx.doi.org/10.1002/adsc.201600549.
Abstract: An efficient ligand-free copper-manga-
a-methylene group of an amine has been a challenging
task and it requires transition metal catalysts.[9b] Fur-
thermore, the direct synthesis of N-arylamides via
coupling of benzylamines with aryl halides in one-pot
requires a metal catalyst, a base and a ligand.[10] The
N-arylation of amides with aryl halides/nonaflates[11]
has been reported. However, for a one-pot synthesis
of N-arylated amides directly from benzylamine and
aryl iodide, only one report is available in the litera-
ture which requires harsh reaction conditions (high
temperature, long reaction time) and use of the ligand
1,10-phenanthroline (shown in Figure 1).[10]
nese (Cu-Mn) spinel oxide-catalyzed direct tandem
À
C H oxygenation and N-arylation of benzylamines
has been developed. The method has been utilized
for the synthesis of medicinally important 2-arylqui-
nazolin-4(3H)-ones. Salient features of this method
include recyclable catalyst, no ligand, excellent
product yields, shorter reaction times and a broad
substrate scope.
Keywords: N-arylation; 2-arylquinazolin-4(3H)-
À
ones; C H oxygenation; copper-manganese (Cu-
Mn) bimetallic catalyst; recyclable catalyst
In recent years, bimetallic catalysts have been ex-
tensively used in various organic transformations[2a]
such as bimetallic palladium(III) for carbon-hetero-
AHCTUNGTRENNUNG
atom bond formation,[12] Ru-Ce for dihydroxylation of
glycals,[13] Ni-Pd for cross-coupling of two different
Amide bonds are not limited to biological systems aryl electrophiles,[14] Cu-Mn for Huisgen [3+2]-cyclo-
and are present in a huge array of chemical com- additions,[15] for the synthesis of imidazopyridines,[16]
pounds, including marketed drugs,[1] polymers,[2] and regioselective halogenations of phenol,[17] and for C
À
natural products.[3] Therefore the synthesis of amide
N
bond formation from arylboronic acids and
bonds continues to be important task in organic amines.[18] In continuation of our interest in the devel-
chemistry. Amide bonds are typically synthesized by opment of new protocols for the synthesis of
the condensation of carboxylic acids with amines; amides[19] and quinazolinones,[20] herein we have de-
however, this coupling does not happen spontaneous- veloped the bimetallic Cu-Mn spinel oxide-catalyzed
ly at ambient temperature, and it typically requires synthesis of N-arylated amides 1 directly via coupling
higher temperatures. Therefore, usually it is necessary of benzylamines 3 with aryl halides 2 without use of
to first activate the carboxylic acid using coupling re- a ligand under mild reaction conditions (Figure 1).
agents. Moreover, this approach lacks atom-econo- The utility of the developed protocol for the construc-
my.[4,2b] Therefore, over the years several new methods tion of medicinally important quinazolinones 6 has
have been reported for amide synthesis, including also been demonstrated.
aminocarbonylation of aryl halides,[5] coupling of
Our work started with the reaction of aryl iodide
amines and alcohols through dehydrogenation,[6] and 2a with benzylamine 3a in the presence of various cat-
oxime rearrangement,[7] as well as direct coupling of alysts, bases and solvents. To our surprise, in the pres-
alcohols and nitroarenes,[8] oxygenation of benzyl- ence of Fe2O3, the desired N-phenylbenzamide 1a was
ACHTUNGTRENNUNG
amines[9] and many more. One of the straightforward formed in 30% yield (Table 1, entry 1). After screen-
approaches for amide synthesis is the direct oxygena- ing various other catalysts available with us, a bimetal-
tion of benzylamines;[9] however, oxygenation of the lic Cu-Mn B (Cu: Mn=1:0.25)[16] was found to pro-
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À
Figure 1. Previous and present work on metal-catalyzed tandem C H oxygenation/N-arylation of benzylamines to produce
N-arylamides.
Table 1. Optimization of the reaction conditions for amidation followed by N-arylation.[a,b]
Entry
Catalyst (% w/w)
Temp. [8C]
Base (equiv.)
Ligand (equiv.)
Time [h]
Yield [%]of 1a[c]
1
2
3
Fe2O3 (10)
110
110
110
110
110
110
80
110
110
110
110
110
110
110
110
110
110
K2CO3 (2)
none
none
none
none
none
none
none
none
none
none
none
none
none
l-proline (2)
none
none
none
none
6
30
0
60
traces
94
50
30
5
traces
0
0
10
90
10
5
85
trace
Cu-Mn B (10)
Cu-Mn B (10)
Cu-Mn B (10)
Cu-Mn B (10)
Cu-Mn B (5)
Cu-Mn B (10)
Cu-Mn A (10)
Cu-Mn C (10)
CuO (10)
10
12
10
5
5
5
10
10
10
10
10
10
10
10
5
K3PO4 (2)
NaOBt (2)
K2CO3 (2)
K2CO3 (2)
K2CO3 (2)
K2CO3 (2)
K2CO3 (2)
K2CO3 (2)
K2CO3 (2)
K2CO3 (2)
K2CO3 (2)
K3PO4 (2)
K3PO4 (2)
K2CO3 (2)
K2CO3 (2)
4
5[d]
6
7
8
9
10
11
12
13[e]
14
15
16[e]
17
MnCl2 (10)
CuCl2 (10)
Cu-Mn B (10)
CuO (I) (10)
MnCl2 (10)
Cu-Mn B (10)
Cu(OAc)2 (10)
10
[a]
For a 100 mg scale (of 2a) reaction, 5 mL of solvent DMSO were used.
All reactions were carried out under an air atmosphere.
Isolated yields.
Optimized reaction conditions.
Reaction under an N2 atmosphere.
[b]
[c]
[d]
[e]
duce an excellent yield of desired product 1a and C. When an SEM of Cu-Mn B was recorded, it
(entry 5). Two other bimetallic catalysts Cu-Mn A showed the presence of a large number of adsorption
(2:0.25) and Cu-Mn C (Cu: Mn=3:0.25) produced sites in the materials which in part contribute to the
product 1a only in traces (entries 8 and 9). The higher high catalytic activity.[15–18] Furthermore, in order to
yield in the presence of Cu-Mn B was presumed to be understand the efficiency of the catalytic activity of
due to its higher surface area compared to Cu-Mn A Cu-Mn B catalyst over Cu-Mn A, Cu-Mn C and indi-
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vidual metals (Cu and Mn), the powder X-ray diffrac- and Cu-Mn C (46.62 m2 gÀ1). The oxidation states of
tion (XRD) spectra of the samples were recorded both metals in Cu-Mn catalyst B were determined by
(Figure S1 in the Supporting information). Cu-Mn B XPS analysis (Supporting Information, Figure S2).
catalyst showed tenorite (CuO), copper manganese The XPS analysis indicated that the Cu exists in the
oxide (Cu1.4Mn1.6O4), hausmannite, (Mn3O4), manga- Cu2+ oxidation state and Mn in the multi-states
nese chloride hydrate (MnCl2·2H2O) and crednerite (Mn2+, Mn3+ and Mn4+). Thus, the improved efficien-
(CuMn2O4) phases. However, the activity of the cata- cy of Cu and Mn metals when combined as a bimetal-
lyst was primarily due to the surface interaction of lic catalyst, over individual metals, could be attributed
two bimetallic spinel oxides such as CuMn2O4 (cred- to the existence of these metals in multiple oxidation
nerite) and Cu1.4Mn1.6O4 which are present in this Cu- states (Cu+2, Mn+2, Mn+3 and Mn+4) in bimetallic Cu-
Mn B catalyst. Particularly, the copper manganese Mn catalyst. In a nutshell, the distinct M-C phases
oxide (M-C) phases are essential for the catalytic ac- and Cr phases (of Cu-Mn oxides) along with higher
tivity. Cu-Mn C showed a very small amount of M-C surface area, and phases with less ordered arrange-
phases, and thus has poor catalytic activity. On the ments in Cu-Mn B catalyst resulted in the higher re-
other hand, Cu-Mn B has distinct M-C phases with activity.
a comparatively lower intensity of tenorite; and thus
To know the catalytic activity of individual copper
it displayed excellent catalytic activity. However, and manganese metals, we conducted control experi-
a small increase in the amount of Cu results in lower ments by using Cu(I)O and MnCl2 (Table 1, en-
activity (as observed with Cu-Mn A catalyst – Cu: tries 10–12, 14,15, and 17) but the desired product was
Mn=2:0.25), which may be due to blocking of the not formed. The individual metals were ineffective,
active sites of the spinel.[21] Furthermore, the specific thus bimetallic Cu-Mn spinel oxides (such as
surface area of the Cu-Mn B catalyst was higher CuMn2O4) were found to be important for the catalyt-
(49.79 m2 gÀ1) compared with Cu-Mn A (42.07 m2 gÀ1) ic activity. When the reaction was performed under
Figure 2. Substrate scope of various substituted aryl halides and substituted benzylamines for the synthesis of substituted N-
phenylbenzamides. Reagents and conditions: (a) aryl iodide (1 equiv.), benzylamine (1.2 equiv.), 10% w/w Cu-Mn, 2.5 equiv.
K2CO3, DMSO, 1108C, 5 h, 77–94%. All reactions were carried out on a 100 mg scale (of precursor 2).
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the optimized conditions (entry 5) but under a nitro- tance.[22] Although numerous methods are available in
gen atmosphere (entry 16), the product was still ob- the literature for the synthesis of quinazolin-4(3H)-
tained in good yields. Among various bases investigat- ones, only few reports are available via direct oxida-
[23]
À
ed (entries 3–5), K2CO3 gave good results. DMSO as tive C H amidation in an air atmosphere.
Using
solvent was found to be best among toluene, 1,4-diox- our method, quinazolin-4(3H)-ones 6a–o were pre-
ane, 1,2-dichloroethane. Only up to 5% yield of de- pared in 2 h in 72–98%. Interestingly, after work-up
sired product could be obtained with 1,4-dioxane and of the organic layer followed by evaporation under
1,2-dichloroethane as solvents. The reason for DMSO vacuum, pure products were obtained without the
showing the best results might be due to the fact that need for column chromatography. A series of substi-
DMSO must be acting as a source of oxygen for the tuted 2-phenylquinazolin-4(3H)-ones with various
reaction.
substituted benzylamines were prepared as depicted
With the optimized reaction conditions in our hand, in Figure 3. A wide range of functional groups were
we tested various substituted aryl iodides and benzyl- well tolerated on the benzylamines including elec-
amines bearing various functional groups (Figure 2). tron-withdrawing, electron-donating and neutral sub-
Aryl iodides with electron-donating groups such as stituted benzylamines; all producing good yields of
OMe (1l, 1m, 1n), methyl (1o, 1s) and electron-with- the corresponding 2-phenylquinazolin-4(3H)-ones. In
drawing groups such as bromo (1f, 1j), chloro (1g, 1k) order to know the role of oxygen in this reaction,
and fluoro (1p, 1t, 1u) gave the desired products in a control reaction in the presence of a nitrogen at-
good yields (Figure 2). In the case of substituted ben- mosphere was also performed, wherein the desired
zylamines, the reaction proceeded well with electron- product 6a was formed in 80% yield. This clearly indi-
donating groups such as OMe (1c), methyl (1i, 1j, 1k, cated that oxygen is not required for this reaction;
1l, 1t) as well as electron-withdrawing groups such as and the source of oxygen is DMSO.
chloro (1e, 1q, 1s), fluoro (1b, 1n, 1p), OCF3 (1h, 1u)
Next, we investigated the catalytic efficiency of Cu-
and CF3 (1d). Slightly better yields were obtained in Mn B catalyst for multiple use. The catalyst was re-
electron-withdrawing group-containing aryl iodides/ covered by filtration after every reaction and reused
benzylamines compared to electron-donating group- for five successive reactions for the synthesis of N-
containing aryl iodides or benzylamines.
phenylbezamide 1a without loss of significant activity.
The scope of this reaction was further extended for The % yields over 5 cycles were 95, 94, 92, 92 and
the synthesis of 2-arylquinazolin-4(3H)-one deriva- 90%. SEM analysis of the catalyst before (unused)
tives, which are of tremendous medicinal impor- and after use (after 5 cycles) showed that the surface
Figure 3. Substrate scope of substituted benzylamines for the synthesis of substituted 2-phenylquinazolin-4(3H)-ones. Re-
agents and conditions: (a) 10% w/w Cu-Mn B, 2.5 equiv. K2CO3, DMSO, 808C, 2 h, 75–98%. All reactions were carried out
on a 100 mg scale (of precursor 4).
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morphology of catalyst remains unchanged even after
5 runs (Figure 4). This indicated the potential of this
catalyst for the commercial and economical synthesis
of this class of medicinally important heterocycles.
Next in order to check the metal leaching, we ana-
lyzed the recycled catalyst by ICP-MS. The Cu and
Mn contents of the fresh catalyst were found to be
612306 and 49181 mgkgÀ1. The catalyst recycled after
5 runs showed similar metal contents (606179 and
45045 mgkgÀ1 of Cu and Mn, respectively). This clear-
ly indicated that even after recycling the catalyst for 5
times, there was no leaching of metals from the bi-
metallic spinel catalyst.
Towards elucidating the reaction mechanism, we
conducted a few control experiments. The reaction of
aryl iodide 2a with benzylamine 3a under the opti-
mized reaction conditions under a nitrogen atmos-
phere gave the corresponding product 1a in 85%
yield (Figure 5a and entry 16 of Table 1). This shows
that external O2 is not required for the reaction and
DMSO could be the possible source of oxygen. Fur-
thermore, we conducted a reaction without taking the
aryl iodide under the optimized condition which led
to the formation of benzamide 7 (Figure 5b). After
synthesis of amide 7, we then reacted it with aryl
Figure 5. Control experiments (a)–(f) and proposed mecha-
nism (g) for the synthesis of N-phenylbenzamide 1a.
iodide under the optimized reaction conditions, which
resulted in the formation of product 1a in 85% yield
(Figure 5d). Furthermore, we also conducted the reac-
tion of N-benzylidenebenzenamine (N-benzylated
aniline) 8 under the optimized reaction conditions in
order to exclude the possibility of other reaction path-
ways (N-arylation followed by oxidation) (Figure 5e).
In order to check whether DMSO auto-decomposi-
tion follows a radical pathway, the reaction of 3a with
Figure 4. SEM images for catalyst before (a) and after 5
cycles of use (b).
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2a was performed in the presence of the free-radical Experimental Section
quencher TEMPO (Figure 5f), wherein the product
1a was not formed, indicating that the reaction pro- General Procedure for the Synthesis of N-Phenyl-
cess involves a free-radical mechanism.
benzamides 1a–u and 2-Phenylquinazolin-4(3H)-ones
On the basis of these control experiments, we pro- 6a–p
pose a reaction mechanism as depicted in Figure 5g.
To a solution of aryl iodide or 2-bromobenzamide (1 equiv.)
Benzylamine 3a gets converted to imine intermediate
I which, on oxygenation in presence of DMSO under
standard reaction conditions, produces amide 7. A
similar type of oxidation of benzylamines to the cor-
responding amides has been reported earlier using
manganese dioxide as catalyst,[9c,24] and a Ru cata-
lyst.[9b] Next, the benzamide 7 on reaction with aryl
iodide (2) undergoes N-arylation through elimination
of HI producing N-arylated benzamide 1a (Figure 5g).
Similarly, a reaction mechanism for the synthesis of 2-
phenylquinazoline-4(3H)-ones 6 from 2-bromobenz-
>amide (4) is depicted in Figure 6.
In conclusion, we have developed an efficient,
scaleable ligand-free Cu-Mn-catalyzed protocol for
the synthesis of N-arylated amides directly from ben-
zylamines. Its utility for the synthesis of medicinally
important quinazolin-4(3H)-ones has also been dem-
onstrated.
in 5 mL of DMSO were added 10% w/w of Cu-Mn B,
2.5 equiv .of K2CO3 and 1.2 equiv. of amine and the mixture
was heated at 808C or 1108C for 2–5 h. After completion of
the reaction, the mixture was filtered to recover the catalyst.
Water was added to the filtrate and the product was extract-
ed with EtOAc. The organic layer was separated, dried over
anhydrous sodium sulfate and concentrated to afford the
crude product. Products 1a–u were purified by silica gel
column chromatography using EtOAc/hexane as eluent.
Products 6a–p were directly obtained as pure products after
recrystallization with acetone.
Spectral data of the representative compound 1a are pro-
vided below. Spectral data of the remaining compounds are
provided in the Supporting Information.
N-Phenylbenzamide (1a): White solid; HPLC: tR =
6.84 min (100% purity); mp 155–1578C; 1H NMR
(400 MHz, CDCl3): d=7.90 (brs, 1H), 7.87 (d, J=8 Hz,
2H), 7.65 (d, J=8 Hz, 2H), 7.54–7.45 (m, 3H), 7.38 (t, J=
8 Hz, 16 Hz, 2H), 7.17 (t, J=8 Hz, 16 Hz, 1H); 13C NMR
(100 MHz, CDCl3): d=165.8, 137.9, 135, 131.8, 129.1, 128.8,
127, 124.6, 120.3; GC-MS (EI): m/z=197 (M+, 100), 181 (7),
180 (39); HR-ESI-MS: m/z=198.0915 calcd for C13H11NO+
H+: 198.0913; IR (CHCl3): nmax =3343, 2923, 2852, 2108,
1654, 1598, 1588, 1525, 1437, 1322, 1216, 1075, 1018 cmÀ1.
Acknowledgements
The authors thank the analytical department, IIIM for NMR
and MS analysis of our compounds. RS is thankful to DST,
New Delhi for the award of a research fellowship. The au-
thors are also thankful to Ms. Parveen Sharma for technical
support. SBB thanks Department of Science and Technology
(DST, Govt. of India) for financial support under Fast-Track
Scheme (grant no. SR/FT/CS-168/2011).
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COMMUNICATIONS
8 Ligand-Free Copper-Manganese Spinel Oxide-Catalyzed
Tandem One-Pot C–H Amidation and N-Arylation of
Benzylamines: A Facile Access to 2-Arylquinazolin-4(3H)-
ones
Adv. Synth. Catal. 2016, 358, 1 – 8
Rohit Sharma, Ram A. Vishwakarma, Sandip B. Bharate*
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8
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!