[3+2] Cyclization of Azidotrimethylsilane with Quinoxalin-2(1H)-Ones to Synthesize Tetrazolo[1,5-a]quinoxalin-4(5H)-Ones

Article abstract of DOI:10.1002/adsc.201801076

A convenient and efficient protocol for the synthesis of thetetrazolo[1,5-a]quinoxalin-4(5H)-ones via copper-catalyzed [3+2] cyclization of azidotrimethylsilane with quinoxalin-2(1H)-ones under mild conditions has been disclosed. This practical protocol is compatible with a variety of functional groups and provides an access to functionalized tetrazolo[1,5-a]quinoxalin-4(5H)-ones from readily available and safe starting materials. (Figure presented.).

Full text of DOI:10.1002/adsc.201801076

Title: [3+2] Cyclization of Azidotrimethylsilane with Quinoxalin-2(1H)-
ones to Synthesize Tetrazolo[1,5-a]quinoxalin-4(5H)-ones
Authors: Qiming Yang, yuecheng Zhang, Qian Sun, Kun Shang, Hong-
Yu Zhang, and Jiquan Zhao
This manuscript has been accepted after peer review and appears as an
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201801076
Link to VoR: http://dx.doi.org/10.1002/adsc.201801076

10.1002/adsc.201801076
Advanced Synthesis & Catalysis
COMMUNICATION
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
[3+2] Cyclization of Azidotrimethylsilane with Quinoxalin-
2(1H)-ones to Synthesize Tetrazolo[1,5-a]quinoxalin-4(5H)-ones
Qiming Yang, Yuecheng Zhang, Qian Sun, Kun Shang, Hong-Yu Zhang* and Jiquan
Zhao*
School of Chemical Engineering and Technology, Hebei Provincial Key Lab of Green Chemical Technology & High
Efficient Energy Saving, Hebei University of Technology, Tianjin 300130, P. R. China.
Phone: 86-22-60204726, E-mail: zhanghy@hebut.edu.cn; jqzhao@hebut.edu.cn
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
azidotrimethylsilane (TMSN3).[5] After that Jiao and
Abstract. A convenient and efficient protocol for the
synthesis of thetetrazolo[1,5-a]quinoxalin-4(5H)-ones via Shi groups cooperatively reported a remarkable gold-
copper-catalyzed [3+2] cyclization of azidotrimethylsilane
with quinoxalin-2(1H)-ones under mild conditions has been
disclosed. This practical protocol is compatible with a
variety of functional groups and provides an access to
functionalized tetrazolo[1,5-a]quinoxalin-4(5H)-ones from
readily available and safe starting materials.
catalyzed nitrogenation of alkynes employing TMSN3
as the nitrogen source for the synthesis of 5-amino-
tetrazoles (Scheme 1, b).[6] Subsequently, Zhu group
demonstrated an elegant copper-catalyzed cyclization
of TMSN3 with aldehyde hydrazones to form 1-
amino-tetrazoles (Scheme 1, c).[7] Despite significant
achievements have been made, the scope of
cyclization of TMSN3 is still limited, and the novel
and practical method for synthesis of fused tetrazole-
quinoxalin-2(1H)-ones and analogues from simple
and safe starting materials under mild conditions
remains rarely.
Keywords: Cyclization; Copper-catalyzed;
Azidotrimethylsilane; Quinoxalin-2(1H)-one; Tetrazole
Multi-nitrogen-containing heterocycles, especially
tetrazoles and quinoxalines derivatives, are important
scaffolds featured in diverse pharmaceutically and
biologically active compounds.[1] Particularly,
tetrazolo[1,5-a]quinoxalines, the combination of the
two well-known tetrazole and quinoxaline moieties
into the fused bis-heterocyclic systems have revealed
potential application in agrochemistry and medicinal
chemistry fields.[2] However, these heterocycles have
been rarely reported, due to limitations in
straightforward and convenient routes to synthesize
them. A traditional procedure for synthesizing
tetrazolo[1,5-a]quinoxalin-2(1H)-ones
is
the
nucleophilic substitution of 3-chloroquinoxalin-
2(1H)-one with sodium azide.[2a,
Another
2c]
alternative process is based on the reaction of 3-
chloroquinoxalin-2(1H)-one with hydrazine, followed
2d]
by treatment with nitrous acid.[2b,
But both the
aforementioned synthetic routes suffered from the
requirement of pre-functionalized starting materials,
tedious operation procedures, and utilization of
explosive and poisonous reagents (Scheme 1, a).
Azides, as important nitrogen sources,[3] have been
widely used in cyclization reaction with organic
nitriles to construct tetrazoles.[4] In 2013, Echavarren
Scheme 1. Active tetrazolo[1,5-a]quinoxalin-4(5H)-ones
and different strategies for the synthesis of tetrazoles.
group
disclosed
a
novel
gold-catalyzed
transformation of alkynes to tetrazoles with
1
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10.1002/adsc.201801076
Advanced Synthesis & Catalysis
In recent years, the modification of available
quinoxalin-2(1H)-ones based on direct C3-H
functionalization has drawn significant attention,
because this strategy provides an efficient and
practical access to 3-functional quinoxalin-2(1H)-
ones. Several exciting achievements have been made
in succession, such as C3-H amination[8],
substrate, TMSN3 as a nitrogen source, Cu(OAc)2 as
catalyst and CH3CN as a solvent to optimize the
reaction conditions. In the beginning, we chose
PhI(OAc)2 as an oxidant based on the optimal
conditions for cyclization of TMSN3 with aldehyde
hydrazones (Table 1, entries 1-2).[7] Unfortunately, no
target product was isolated. This result implied that
the cyclization of TMSN3 with quinoxalin-2(1H)-
ones was clearly different from that with aldehyde
hydrazones. Subsequently, we tested almost all
oxidants. To our delight, the target product (2a) was
obtained in 49% yield in the case of KMnO4 as an
oxidant (Table 1, entry 7). Other oxidants such as
(NH4)2S2O8 and CAN were not as efficient as KMnO4,
and organic peroxides including TBHP and DTBP
were invalid for this cyclization (Table 1, entries 3–6).
Encouraged by these results, we evaluated the
loading of KMnO4 and found that 1.5 equiv. of
KMnO4 was appropriate for this transformation and
the yield of 2a was promoted from 49% to 55%
(Table 1, entries 7-8). Next, various acids or bases
were screened as additives, such as CH3COOH,
PivOH, and K2CO3. It was found that PivOH was
most favorable and the target molecule (2a) was
obtained in 74% yield (Table 1, entries 9-11). Further
screening of different copper catalysts showed that
Cu(eh)2 was better than Cu(OAc)2, improving the
yield of 2a distinctly to 81% (Table 1, entries 12-14).
Other low-cost metal catalysts, such as
Co(OAc)2▪4H2O and Fe(OAc)2 were inefficient or
invalid for this reaction (Table 1, entries 15-16).
Finally, the solvents screening revealed that CH3CN
was the most appropriate solvent (Table 1, entries 17-
19). Overall, the reaction progressed efficiently under
an argon atmosphere in the presence of 1a (0.4
mmol), TMSN3 (3.0 equiv.), Cu(eh)2 (20 mol %),
KMnO4 (1.5 equiv.) and PivOH (1.0 equiv.) in
CH3CN (4.0 mL) at room temperature.
phosphonation[9],
alkylation[10]
,
arylation[11]
,
heterocyclization[12], and acylation[13] of quinoxalin-
2(1H)-ones. Recently, we have accomplished the
original C3-H trifluoromethylation of quinoxalin-
2(1H)-ones with CF3SO2Na as the trifluoromethyl
source under metal-free conditions.[14] However, all
of these works focused on C-H functionalization,
nevertheless, and other types of reactions including
annulation reaction are still scarce and challenging.
Hence, we develop the first example for [3+2]
cyclization of quinoxalin-2(1H)-ones with TMSN3.
This reaction employs low-cost copper salt as the
catalyst and easily available potassium permanganate
as the oxidant. A series of tetrazolo[1,5-a]quinoxalin-
4(5H)-ones with different functional groups are
obtained in moderate to excellent yields under mild
conditions.
Table 1. Selected reaction conditions optimization.a)
Entr
y
1
2
3
4
5
6
7
yield
(%)b)
N.D.d)
N.D.
40
trace
trace
42
49
55
43
74
33
64
78
81
N.D.
61
21
30
catalyst
oxidant
additive
solvent
c)
c)
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(BF4)2▪6H2O
Cu2O
PhI(OAc)2
PhI(OAc)2
-
K2CO3
-
-
-
-
-
-
CH3COOH
PivOHh)
K2CO3
PivOH
PivOH
PivOH
PivOH
PivOH
PivOH
PivOH
PivOH
PivOH
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
EtOAc
c)
(NH4)2S2O8
TBHPc), e)
DTBPc), f)
CANc), g)
c)
KMnO4
With the optimal reaction conditions in hand, the
substrate scope was explored by using an array of
quinoxalin-2(1H)-one derivatives (Table 2). Initial
8
9
KMnO4
KMnO4
KMnO4
KMnO4
KMnO4
KMnO4
KMnO4
KMnO4
KMnO4
KMnO4
KMnO4
KMnO4
KMnO4
10
11
12
13
14
15
16
17
18
19
20j)
studies were focused on
methylquinoxalin-2(1H)-ones.
a
series of 1-
The reactions
i)
Cu(eh)2
progressed smoothly and provided the desired
products in moderate to good yields (2a-2h).[15] Next,
various N-protected quinoxalin-2(1H)-ones were also
examined. The substrates with ethyl and benzyl
protecting groups are more suitable for the
transformation than substrates with methyl acetate
and tert-butyl acetate groups (2i-2l). It is notable that
N-SEM protected quinoxalin-2(1H)-one was well
compatible with this reaction, affording the target
product in 71% yield (2m). The SEM protecting
group was easily removed by treatment with boron
trifluoride in dichloromethane.[16] We also tested the
quinoxalin-2(1H)-ones without a protecting group
and found that the target tetrazolo[1,5-a]quinoxalin-
4(5H)-one was gained in moderate yield (2n).
Considering the case that N-ethyl protected
quinoxalin-2(1H)-one provided a higher yield than N-
methyl protected quinoxalin-2(1H)-one, we chose a
variety of 1-ethylquinoxalin-2(1H)-ones as substrates
Co(OAc)2▪4H2O
Fe(OAc)2
Cu(eh)2
Cu(eh)2
Cu(eh)2
Cu(eh)2
THF
Acetone
CH3CN
34
75
a)
Unless specifically noted otherwise, reaction conditions:
1a (0.4 mmol), TMSN3 (3.0 equiv.), catalyst (20 mol %),
oxidant (1.5 equiv.), additive (1.0 equiv.) and solvent (4
mL), stirred at room temperature under an argon
b)
c)
atmosphere for 10 hours. Yield of isolated product.
d)
e)
Oxidant (2.0 equiv.). N. D. = no detected. TBHP =
tert-butyl peroxybenzoate (70% solution in H2O). f) DTBP
= di-tert-butyl peroxide. g) CAN = ceric ammonium nitrate.
h)
i)
PivOH = pivalic acid.
Cu(eh)2 = copper bis(2-
ethylhexanoate). j) under an air atmosphere.
Initially, we started our exploration with 1-
methylquinoxalin-2(1H)-one (1a) as the model
2
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10.1002/adsc.201801076
Advanced Synthesis & Catalysis
and found that the correspondingly annulate products
were obtained in moderate to excellent yields (2o-2z).
Finally, 4-ethylpyrido[2,3-b]pyrazin-3(4H)-one and
1-methylpyrazin-2(1H)-one were examined as a
representative approximate substrates of quinoxalin-
2(1H)-ones, and the expected products were obtained
in moderate yields (2aa-2ab).
standard conditions, the N3-trapped compound 3a
was detected by LCMS (Equation 2). These results
suggested that a radical progress might be involved in
the transformation. On the other hand, the effects of a
copper catalyst and KMnO4 oxidant on the reaction
were also investigated. The target molecule 2a was
obtained in only 45% yield under standard conditions
in the absence of a copper catalyst (Equation 3).
However, no desired product was detected, when 3.0
equivalents of Cu(eh)2 were used under standard
conditions in the absence of KMnO4 (Equation 4).
These results indicated that KMnO4 played a crucial
role in the transformation and Cu(eh)2 facilitated this
transformation.
Table 2. Substrate scope.a)
Scheme 2. Control experiments.
According to the above control experiments and
previous reports[7], a presumptive mechanism is
proposed in Scheme 3. Initially, TMSN3 reacts with
KMnO4 to form the azide radical B.[17] Subsequently,
the generated B adds to the C=N bond of 1a to afford
the aminyl radical intermediate C. Next, aminyl
radical C is oxidized by Cu(II) or KMnO4 to provide
the aminyl cation D by single-electron oxidation.[18a-c]
Thereafter, aminyl cation D undergoes intramolecular
cyclization to give the expected product 2a (Path a).
Alternatively, intermediate D is likely to produce 3-
azido-1-methylquinoxalin-2(1H)-one
E
via β-H
a)
Unless specifically noted otherwise, reaction conditions:
elimination and intermediate product E tends to
1a (0.4 mmol), TMSN3 (3.0 equiv.), Cu(eh)2 (20 mol %),
KMnO4 (1.5 equiv.), PivOH (1.0 equiv.) and CH3CN (4
mL), stirred at room temperature under an argon
atmosphere. b) Yield of isolated product.
transform into final product 2a (Path b).[18d-e]
In order to elucidate the preliminary mechanism of
this transformation, several control experiments were
carried out and demonstrated in Scheme 2. It was
found that the reaction was completely suppressed in
the presence of 3.0 equivalent of 2,2,6,6-tetramethyl-
1-piperidinyloxy (TEMPO) as a radical inhibitor
(Equation 1). Besides, when 2,6-di-tert-butyl-p-cresol
(BHT) as anther radical inhibitor was added under
Scheme 3. Presumptive reaction mechanism.
3
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10.1002/adsc.201801076
Advanced Synthesis & Catalysis
To conclude, we have successfully accomplished an
original method for synthesis of functionalized
tetrazolo[1,5-a]quinoxalin-4(5H)-ones based on
[3+2] cyclization of azidotrimethylsilane with
quinoxalin-2(1H)-ones. This protocol utilizes cheap
Cu(eh)2 as a catalyst and safe TMSN3 as azide source,
as well as tolerates a wide range of functional groups
under mild reaction conditions. Therefore, this
method provides a practical approach to prepare
pharmaceutically and biologically interesting
tetrazolo[1,5-a]quinoxalin-4(5H)-ones in moderate to
excellent yields.
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Experimental Section
General procedure for cyclization of quinoxalin-2(1H)-
ones
An oven-dried Schlenk tube was charged with quinoxalin-
2(1H)-one derivatives (1a-1ab) (0.4 mmol), KMnO4 (1.5
equiv., 0.6 mmol), Cu(eh)2 (0.2 equiv., 0.08 mmol), PivOH
(1 equiv., 0.4 mmol) and a magnetic stirring bar, and then
was purged with argon for three times. Anhydrous CH3CN
(4 ml) and TMSN3 (3 equiv., 1.2 mmol) were added in turn
via respective syringes, and the mixture was stirred at
room temperature in water bath under argon atmosphere
until the substrate was consumed (monitored by TLC,
about 10 hours). The mixture was added with CH2Cl2 (20
ml) and saturated aqueous Na2CO3 (20ml). The organic
layer was isolated and the remaining aqueous phase was
further extracted with CH2Cl2 (20 mL × 2). The combined
organic phases were washed with saturated brine (20 mL).
The organic layers were dried over Na2SO4, filtered.
Solvents were evaporated under reduced pressure and the
resulting residue was purified by column chromatography
on neutral aluminum oxide (petroleum ether/ethyl acetate)
to afford the corresponding cyclization products (2a-2ab).
Acknowledgements
We acknowledge the financial support from the National Natural
Science Foundation of China (Grant No. 21776056), the Natural
Science Foundation of Hebei Province (CN) (Grant No.
B2018202253, B2016202393, B2015202284) and the Program
for the Top Young Innovative Talents of Hebei Province (CN)
(Grant No. BJ2017010).
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