Furan-2-carbaldehydes as C1 building blocks for the synthesis of quinazolin-4(3: H)-ones via ligand-free photocatalytic C-C bond cleavage

Article abstract of DOI:10.1039/c8gc00079d

Furan-2-carbaldehydes, as biomass-derived chemicals, are used as efficient green C1 building blocks to synthesize bioactive quinazolin-4(3H)-ones by ligand-free photocatalytic C-C bond cleavage. Notably, protection of hydroxyl, carboxyl, amide, or secondary amino groups is not required. Mechanistic studies suggest that conjugated N,O-tridentate copper complexes act as novel photoinitiators under visible light.

Full text of DOI:10.1039/c8gc00079d

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Furan-2-carbaldehydes as C1 building blocks for the synthesis of
quinazolin-4(3H)-ones via ligand-free photocatalytic C–C bond
cleavage
Received 00th January 20xx,
Accepted 00th January 20xx
Wenjia Yu,a,b Xianwei Zhang,b Bingjie Qin,b Qiyang Wang,a,b Xuhong Rena,* and Xinhua Heb,c,*
DOI: 10.1039/x0xx00000x
www.rsc.org/
Furan-2-carbaldehydes, as biomass-derived chemicals, are used as
efficient green C1 building blocks to synthesize bioactive
quinazolin-4(3H)-ones by ligand-free photocatalytic C–C bond
cleavage. Notably, protection of hydroxyl, carboxyl, amide, or
secondary amino groups is not required. Mechanistic studies
suggest that conjugated N,O-tridentate copper complexes act as
novel photoinitiators under visible light.
The synthesis of quinazolin-4(3H)-ones (Fig. 1) has attracted
the interest of many organic chemists, owing to their
important roles in pharmaceuticals, pesticides, and functional
materials.1 Several traditional C1 building blocks have been
reported for the synthesis of quinazolin-4(3H)-ones, including
formaldehyde/I2, N,N-dimethylformamide/(t-Bu-O)2 or POCl3,
pivalaldehyde/I2, carbon dioxide/poly(methylsiloxane)/1,3-
bis(2,6-diisopropyl-phenyl)imidazol-2-ylidene, formic acid–
Fig. 1 Structures of selected bioactive quinazolinones.
In this study, we employed furan-2-carbaldehydes, which are
biomass agents produced from rice bran or corn hull, as green
and renewable C1 building blocks for the synthesis of
quinazolin-4(3H)-ones via photocatalytic C–C bond cleavage.4,5
Only moderate reaction conditions were required, and the
synthesis could proceed in the presence of various
unprotected active functional groups, including hydroxyl,
carboxyl, and secondary amino groups (Scheme 1).
triethylamine/Pd,
1H-imidazole/C:Cu(OAc)/(t-Bu-O)2,
trimethoxymethane, and ethyl formate.2 However, the use of
these C1 building blocks has many disadvantages, such as the
needs for costly and hazardous materials, moisture-sensitive
agents, non-green solvents, multistep processes, and high
temperatures. For example, trimethoxymethane, which is the
most widely used C1 building block, is moisture-sensitive and
requires complicated and energy-intensive preparation.3 (t-Bu-
O)2 and POCl3 are hazardous materials. Moreover, the reaction
yields of these C1 building blocks are sometimes unsatisfactory
(27%–55%).2
NH2
R'
N
R
O
O
N
HN
R'
Ar
Ar
R
t
a
O
e
h
previous work6
O
O
CuX2
Cu(I)*
light
1/2O2
Cu(I)
Cu(III)
R'
H
H
O
N
N
N
O
Cu
O
Xn
Air
light, r.t.
H
R
R
R
N
N
Ar
Ar
HN
O
Ar
photoinitiator
this work
Scheme 1 Furan-2-carbaldehydes as C1 feedstocks via photocatalytic C–C bond
cleavage, and the proposed reaction mechanism.7,8
Photoredox catalysis has emerged as a powerful method
for initiating radical reactions under mild conditions using low-
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energy irradiation.9 However, photocatalysis usually relies on
heavy metal-based photocatalysts, e.g. ruthenium,10 iridium,11
copper,7 gold,12 or cobalt13 complexes with complicated
ligands. For green synthesis, it is essential to develop ligand-
free photocatalytic methods.8,14
Table 1 Optimization of the reaction conditions
Recently, we found that conjugated N,O-bidentate
copper(II) complexes act as photoinitiators for intramolecular
C–H bond activation via a free radical mechanism.8 Herein, we
envisioned that complexes between conjugated N,O-tridentate
copper and furan-2-carbaldehydes15 could function as novel
photoinitiators for C1 building blocks in the synthesis of
quinazolin-4(3H)-one derivatives via a C–C bond cleavage.
Therefore, the application of 5-methylfuran-2-carbaldehyde as
a C1 building block via ligand-free photocatalytic C–C bond
cleavage was first investigated using 2-amino-N-
Entry
Solvent
acetone
ethanol
THF
Base
Catalyst
Time (h)
Yield (%)a
61
1
2
3
4
5
6
7
8
9
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
20% CuCl2
20% CuCl2
20% CuCl2
20% CuCl2
20% CuCl2
20% CuCl2
20% CuCl2
20% CuCl2
20% CuCl2
20% CuCl2,
No light
4
4
84
4
65
CH3CN
EtOAc
4
68
4
83
ethanol
ethanol
ethanol
ethanol
0.5
1
64
77
2
81
5
87
phenylbenzamide (
1) as a model substrate. Compound 1 was
reacted with 5-methylfuran-2-carbaldehyde to obtain 2-[(5-
10
ethanol
Cs2CO3
5
0
methyl-furan-2-ylmethylene)-amino]-N-phenylbenzamide
(
2
).
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
ethanol
ethanol
ethanol
ethanol
ethanol
ethanol
ethanol
ethanol
ethanol
ethanol
ethanol
ethanol
ethanol
ethanol
ethanol
ethanol
ethanol
ethanol
No base
CsOAc
K2CO3
20% CuCl2
20% CuCl2
20% CuCl2
20% CuCl2
20% CuCl2
20% CuCl2
20% CuCl2
20% CuCl2
20% CuCl2
20% CuCl2
20% CuCl2
20% CuCl
20% CuBr
20% CuI
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
68
91
87
90
82
74
63
17
89
86
81
79
84
73
84
88
90
60
Based on our previous study, the photoinitiator complex of
2
and copper(II) forms in solution by activating the C–C bond of
the furan-2-ylmethylene motif when irradiated by light from a
high-voltage mercury lamp commonly used in industry. The
TEAb
NMMc
pyridine
DMAPd
HOBTe
KOH
desired product
3 was then successfully obtained by
intramolecular cyclization, and its structure was characterized
using single-crystal X-ray diffraction (Fig. S1).
Encouraged by this result, we optimized the reaction
conditions by varying the base, solvent, catalyst, and reaction
time. As shown in Table 1, the highest yields of about 90%–
91% were obtained when ethanol was used as the solvent,
CuCl2 as the catalyst, and CsOAc or TEA as the base. Notably,
when CsOAc was used as the base, the reaction was easy to
handle.
DIPEAf
NaOH
CsOAc
CsOAc
CsOAc
CsOAc
CsOAc
CsOAc
CsOAc
20% CuBr2
10% CuCl2
5% CuCl2
Further, we examined other green and renewable furan-2-
carbaldehydes as potential C1 building blocks. In order to
identify abundant, green C1 feedstocks for ligand-free
photocatalytic C–C bond cleavage, the comparative cost and
availability were considered, and furan-2-carbaldehyde and 5-
methylfuran-2-carbaldehyde were chosen as good candidates.
To evaluate the effect of electron-withdrawing groups, 5-
nitrofuran-2-carbaldehyde was also tested. Kinetic studies
showed that 5-methylfuran-2-carbaldehyde and furan-2-
carbaldehyde gave similarly high yields and reaction rates. In
contrast, the yield of quinazolin-4(3H)-one was only about 20%
when 5-nitrofuran-2-carbaldehyde was employed instead,
although the starting material was almost completely
consumed within 6 h (Fig. 2). Hence, both 5-methylfuran-2-
carbaldehyde and furan-2-carbaldehyde proved to be excellent
C1 building blocks. However, the former, which is used as for
food flavoring and hence very safe, has the advantage of
reacting with 2-amino-N-phenylbenzamides to form easy-to-
handle imines in high yields. Therefore, 5-methylfuran-2-
carbaldehyde was determined to be an excellent green C1
feedstock candidate.
1% CuCl2
aHPLC yields. bTEA, triethylamine. cNMM, 4-methylmorpholine. dDMAP, 4-
dimethylaminopyridine. eHOBT, 1-hydroxybenzotriazole. fDIPEA, N,N-
diisopropylethylamine.
Fig. 2 Kinetic data of various furan-2-carbaldehydes used as C1 building blocks. The
yields were determined by HPLC using an internal standard.
With the optimized conditions and C1 feedstock candidates
in hand, the substrate scope of the reaction was investigated
(Fig. 3). Notably, quinazolin-4(3H)-ones with an alkyl, fluorine,
2 | Green Chem., 2012, 00, 1-3
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Fig. 4 Reaction kinetics using different light sources (300 W). The yields were
determined by HPLC. The curves of are surplus ratio–time curves.
2
N
N
N
14, 72%
13, 67%
15, 81%
N
N
N
O
O
N
O
N
N
N
N
N
19, 70%
17
, 66%
18
, 89%
Cl
O
O
O
N
O
N
O
N
N
N
N
23
, 81%
22
, 76%
21, 79%
CF3
O
O
O
N
N
N
CF3
O
N
N
N
Fig. 5 UV-visible absorption spectrum of a mixed solution of 2 (2 × 10-5 mmol/mL) and
CuCl2 (2 × 10-5 mmol/mL) in ethanol (red curve). The blue curve was the sum of
absorbances of 2 (2 × 10-5 mmol/mL) and CuCl2 (2 × 10-5 mmol/mL) in ethanol alone.
25
, 76%
26
, 83%
27, 72%
H
O
O
O
N
N
OH
N
N
OH
OH
N
N
absence of UV light (the lamp was equipped with an optical
filter to remove UV light, < 420 nm). Therefore, the reaction
kinetics was compared to that under a metal halide lamp
(thallium, ~530 nm). As shown in Fig. 4, similar yields and
reaction rates were obtained with the two light sources,
indicating that this reaction can be initiated by visible light
irradiation.
29, 51%
30, 69%
31, 73%
O
O
N
S
N
N
N
O
NH2
2
, 63%
33, 59%
Fig. 3 Reaction scope and isolated yields for the conditions in Table 1, entry 27.
Next, the reaction mechanism was investigated. UV-visible
and IR spectra were recorded to confirm the successful
or alkoxy substituent on the phenyl ring were obtained in
isolated yields of 59%–82%. Moreover, quinazolin-4(3H)-ones
with a phenyl, pyrazol-4-yl, or alkyl substituent at the N3-
position were also obtained in good to excellent yields. In
particular, for substrates with hydroxyl or secondary amino
groups, traditional C1 feedstocks require an additional step to
complex formation between compound 2 and copper(II) in
solution, as suggested in our previous study.8 As shown in Fig.
5, the absorption bands observed at around 212 and 300 nm
could not be accounted for by summing the spectra of
CuCl2, suggesting the association between these two species.
Moreover, the IR peaks (Fig. S3) of at around 768.8, 1405.8,
and 1666.9 cm-1, which correspond to the copper(II)-chelating
functionalities, were weaker for the mixture of and CuCl2. In
2 and
2
protect
these
groups,16 whereas
5-methylfuran-2-
carbaldehyde can be used directly.
2
In the aforementioned experiments,
a
high-voltage
particular, the N–H out-of-plane bending vibration (δN–H
:
1551.3 cm-1) observed for the mixture was not detected for
the individual solutions (Fig. S4).
mercury lamp was used because of its low cost and durability.
However, its spectrum contains some UV light (Fig. S2),
therefore, the role of UV light played in the reaction was then
explored. Interestingly, the reaction proceeded even in the
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Fig.
7 Kinetics of the two possible reaction pathways. Pathway 1 starts from
Fig. 6 Electron paramagnetic resonance spectra of (a) 2 in ethanol and (b) the complex
of 2 and copper(II) in ethanol. The solutions were irradiated using a high-voltage
mercury lamp, and the signals were collected after 0, 45, 90, 135, 180, 225, and 270 s.
intermediate 34, and pathway 2 from intermediate 2. The curves of 34 and 2 are
surplus ratio–time curves. The yields were determined by HPLC using an internal
standard.
H
Cl
H
O
O
Cu Cl
O
Cl Cu
O
N
N
O
evidence of it was observed. Next, two kinetic assays were
N
Cyclization
N
N
O
O
N
performed: from 34 to
decomposed under irradiation from the mercury lamp, but the
yield of was below 10%. In contrast, was rapidly converted
to at a rate matching that of the free radical formation as
3 and from 2 to 3. As shown in Fig. 7, 34
HN
HN
O
2
34
photoinitiator
photoinitiator
3
2
3
revealed by the EPR study. Hence, we concluded that the
reaction proceeded via pathway 2.
H
N
N
Cyclization
Pathw
N
O
NH
O
Conclusions
ay 2
3
In summary, we demonstrated two renewable green agents, 5-
methylfuran-2-carbaldehyde and furan-2-carbaldehyde, which
can be produced from rice bran or corn hull, as efficient C1
building blocks for the synthesis of quinazolin-4(3H)-ones by
photocatalytic C–C bond cleavage under visible light irradiation.
The reaction conditions were more moderate and greener
than those using traditional C1 building blocks. In particular,
for substrates with hydroxyl, secondary amino, amide, or
carboxyl groups, protection reactions are not required before
using furan-2-carbaldehydes. Importantly, the complex
Scheme 2 Possible reaction pathways.
These findings confirmed the complex formation between 2
and copper(II) in solution.
Electron paramagnetic resonance (EPR) studies were
performed to determine whether the reaction proceeds via a
free radical mechanism. Under light irradiation (high-voltage
mercury lamp), small amounts of free radicals including
superoxide, nitrogen, and carbon radicals were generated in
the solution of
2
(Fig. 6a), whereas the CuCl2 solution gave no
and
between
2-[(5-methylfuran-2-ylmethylene)-amino]-N-
EPR signals (Fig. S5). In contrast, in the mixed solution of
2
phenylbenzamide and copper(II) was found to be a novel
ligand-free photoinitiator that produces a moderate amount of
carbon free radicals. Therefore, this study provides a useful
tool for constructing new skeletons by intermolecular
reactions of in-situ generated carbon radicals.
CuCl2, only carbon free radicals were produced, the amount of
which increased with time (Fig. 6b). These results suggest that
copper(II) ions play a key role in this reaction. The complex of
2
and copper(II) acts as a photoinitiator, and 5-methylfuran-2-
carbaldehyde as a C1 building block via a free radical
mechanism.
Conflicts of interest
Based on these observations, two possible reaction
pathways were proposed (Scheme 2). In pathway 1, compound
There are no conflicts to declare.
2
forms the photoinitiator by chelating copper(II) ions, and the
obtained complex cyclizes to give intermediate 34 (Fig. S6).
Next, 34 chelates copper(II) and its furan ring is decomposed
Acknowledgements
under light irradiation to form 3. In contrast, in pathway 2, the
This work was supported by the National Natural Science
Foundation of China (grant no. 30973615), the National Major
Project of China (grant no. BWS16J010), and the Beijing
Natural Science Foundation (grant no. 7172159).
decomposition of the furan ring of the photoinitiator occurs
before the cyclization. To determine which pathway was
followed, we attempted to monitor the formation of
intermediate 34 by HPLC and LC/MS, but no
4 | Green Chem., 2012, 00, 1-3
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Green Chemistry
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DOI: 10.1039/C8GC00079D
COMMUNICATION
Wenjia Yu, Xianwei Zhang, Bingjie Qin,
Qiyang Wang, Xuhong Ren* and Xinhua He*
Page No. – Page No.
Furan-2-carbaldehydes as C1 building
blocks for quinazolin-4(3H)-ones synthesis
via ligand-free photocatalysis
Simple and inexpensive: The biomass-derived chemicals
furan-2-carbaldehydes are efficient green C1 building blocks
for the synthesis of biologically interesting quinazolin-4(3H)-
ones via ligand-free photocatalytic C-C bond cleavage.