Silver(I)- and Base-Mediated formal [4+3] Cycloaddition of in Situ generated 1,2-Diaza-1,3-dienes with C,N-Cyclic Azomethine Imines: An Efficient Protocol for the Synthesis of Tetrazepine Derivatives

Article abstract of DOI:10.1002/adsc.202000398

A silver(I)- and base-mediated formal [4+3] cycloaddition reaction of in situ generated 1,2-diaza-1,3-dienes with in situ formed C,N-cyclic azomethine imines has been developed. This protocol provided an efficient method for the synthesis of biologically important 1,2,4,5-tetrazepine derivatives with a wild substrate scope and excellent functional group tolerance in moderate to excellent yields. (Figure presented.).

Full text of DOI:10.1002/adsc.202000398

Title: Silver(I)- and Base-Mediated 1,3-Dipolar [4+3] Cycloaddition of in
Situ generated 1,2-Diaza-1,3-dienes with C,N‑Cyclic Azomethine
Imines: An Efficient Protocol for the Synthesis of Tetrazepine
Derivatives
Authors: Zefei Li, Shuaikang Li, Tianjiao Kan, Xinyue Wang, Xin Xin,
Yunlei Hou, and Ping Gong
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.202000398
Link to VoR: https://doi.org/10.1002/adsc.202000398

10.1002/adsc.202000398
Advanced Synthesis & Catalysis
COMMUNICATION
DOI: 10.1002/adsc.202((will be filled in by the editorial staff))
Silver(I)- and Base-Mediated formal [4+3] Cycloaddition of in
Situ generated 1,2-Diaza-1,3-dienes with C,N‑ Cyclic
Azomethine Imines: An Efficient Protocol for the Synthesis of
Tetrazepine Derivatives
Zefei Li, Shuaikang Li, Tianjiao Kan, Xinyue Wang, Xin Xin, Yunlei Hou* and Ping
Gong*a
a
School of Pharmaceutical Engineering, Shenyang Pharmaceutical University, 103 Wenhua Road, Shenhe District,
Shenyang, 110016, China.
E-mail: houyunlei901202@163.com and gongpinggp@126.com
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))
undergo
[4+1][8],
[4+2][9]
and
[4+3][10-11]
Abstract. A silver(I)- and base-mediated formal [4+3]
cycloaddition reaction of in situ generated 1,2-diaza-1,3-
dienes with in situ formed C,N‑ cyclic azomethine imines
has been developed. This protocol provided a efficient
method for the synthesis of biologically important 1,2,4,5-
tetrazepine derivatives with a wild substrate scope and
excellent functional group tolerance in moderate to
excellent yields.
cycloadditions with structurally different dienophiles
and form structurally diverse N-containing
heterocycles. For instance, Wang and co-workers
realized
the
synthesis
of
5‑ (trifluoromethyl)pyrazolines by formal [4+1]
annulation of fluorinated sulfur ylides and α-halo
hydrazones in good yields without any catalysts
(Scheme 1a).[12] The Yao research group designed an
isothiourea catalyzed formal [4+2] cycloaddition of α-
halo hydrazones with arylacetic acids in a racemic
version (Scheme 1b).[13] The Zhao research group
reported the construction of 2,3,4,7-tetrahydro-
1,2,4,5-oxatriazepines via [4+3] cycloadditions of α-
halo hydrazones with nitrones (Scheme 1c).[14]
Keywords: Silver, 1,2-Diaza-1,3-dienes, Azomethine
imines, [4+3] Cycloaddition, Tetrazepine derivatives
Nitrogen-containing seven-membered heterocyclic
ring moieties exist extensively in many bioactive
natural products, pharmaceuticals, agrochemicals and
materials. Therefore, the chemical synthesis has
received considerable attention from organic chemists
worldwide.[1] However, compared with the well-
established methodologies for the construction of five-
membered and six-membered heterocyclic ring, the
construction of seven-membered heterocycle is much
less favourable. The main challenges are driven by the
entropic factors derived from the changing of the
rotation/translation of chemical bonds during the
cyclization process and the non-bonding interactions
in the transition states.[2] So far, the representative
methods to construct seven-membered ring include
[4+3] cycloaddition[3], [5+2] cycloadditions[4] and
ring-closing metathesis[5]. As one of the useful and
efficient protocols, the [4+3] cycloadditions have
found many applications in the preparation of
structurally complex and diverse seven-membered
rings. In [4+3] cycloaddition, it is significant to design
four-atom components to form dienes and three-atom
dienophiles which undergo cycloadditions with the
dienes.[6]
α-Halo hydrazones, as powerful and versatile
building blocks, can generate electron-deficient dienes
(1,2-diaza-1,3-dienes) in situ under basic reaction
conditions.[7] In general, α-halo hydrazones can
Scheme 1. Representative cycloadditions
1
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10.1002/adsc.202000398
Advanced Synthesis & Catalysis
On the other hand, it is well known that azomethine
then screened. The yield was increased to 84% when
the base was changed to K2CO3 (Table 1, entry 9).
Other bases such as Cs2CO3, NaHCO3, KOH and t-
BuOK turned out to be less efficient for this
cycloaddition reaction (Table 1, entries 10-13).
Moreover, some organic bases were also examined
(Table 1, entries 14-16). Replacement of K2CO3 to
DIPEA, Et3N and DBU decreased the yield to 72%,
52% and 10%, respectively. A further enhancement in
the yield of 3aa was observed upon varying the ratio
of 1a and 2a (Table 1, entries 17-19). The highest
yield was achieved when 1.2 equiv. of 1a was used
(88%) (Table 1, entry 19). Consequently, the standard
reaction conditions used for further investigations
were 2 (1.0 equiv.) and AgOTf (0.1 equiv.) in MeCN
at 80 °C for 3 h and then adding 1 (1.2 equiv.) and
K2CO3 (2.0 equiv.) at room temperature for 6 h under
the protection of N2.
imines are widely used for the synthesis of diverse N-
containing heterocycles by 1,3-dipolar cycloadditions
under thermal or catalyzed conditions.[15] Among
those azomethine imines, we identified that
C,N‑ cyclic azomethine imine generated in situ from
N'-(2-alkynylbenzylidene)hydrazide is
a
useful
building block for further [3+2][16] and
[3+3][17]cycloadditions. However, in contrast to the
widespread use of the [3+2] and [3+3] cycloadditions,
no work has been reported on the [4+3] cycloadditions
involving N'-(2-alkynylbenzylidene)hydrazides with
the other four-atom component except for a few
examples about NHC-catalyzed [4+3] cycloadditions
of azomethine imines with enals.[11] For instance, the
Xiao research group reported an [4+3] cycloaddition
of in situ generated azoalkenes with C,N-cyclic
azomethine imines without use of any catalyst.[11a]
Encouraged by the above mentioned previously
published works, we tried to develop the [4+3]
Table1. Optimization of reaction conditionsa
cycloadditions
of
N'-(2-
α-halo
alkynylbenzylidene)hydrazides
with
hydrazones to construct the unique and biologically
important 1,2,4,5-tetrazepine derivatives (Scheme 2A,
B and C).[18] In this communication, we present our
recent research on the [4+3] cycloaddition reaction of
in situ generated 1,2-diaza-1,3-dienes with in situ
formed C,N‑ cyclic azomethine imines (Scheme 1d).
To our delight, under the optimized reaction
conditions, the [4+3] cycloaddition product 1,2,4,5-
tetrazepine derivatives could be obtained in
satisfactory yields.
Entry
1
2
3
4
5
6
7
8
Solvent
MeCN
Toluene
DCE
Base
Yieldb
78%
61%
74%
52%
65%
67%
32%
ndf
84%
68%
45%
62%
25%
72%
52%
10%
88%
80%
87%
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
K2CO3
Cs2CO3
NaHCO3
KOH
THF
1,4-Dioxane
EtOAc
DMF
MeOH
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
9
10
11
12
13
14
15
16
17c
18d
19e
Scheme 2. Examples of biologically active compounds
containing 1,2,4,5-tetrazepine core structures
t-BuOK
DIPEA
Et3N
The initial attempt was performed between the
reaction of α-halo hydrazone 1a as the 1,2-diaza-1,3-
diene precursor and N'-(2-alkynylbenzylidene)-
hydrazide 2a as the C,N-cyclic azomethine imine
precursor (Table 1). It was reported that N'-(2-
alkynylbenzylidene)-hydrazide 2a can be easily
transferred to C,N-cyclic azomethine imine with the
assistance of AgOTf.[19] To our delight, the desired
cycloaddition occurred, giving the 1,2,4,5-tetrazepine
3aa in a 78% combined yield by using 10 mol %
AgOTf with Na2CO3 as the base in MeCN (Table 1,
entry 1). The product was carefully characterized by
1H NMR, 13C NMR and HRMS spectral data. Besides,
the chemical structure of 3aa was unambiguously
determined by single crystal X-ray analysis as depicted
in Figure 1.[20] Encouraged by this preliminary result,
other reaction medias were then systematically
investigated. The yield could not be improved in
toluene, DCE, THF, 1,4-dioxane, EtOAc, DMF and
MeOH (Table 1, entries 2-8). Finally, MeCN was
determined to be the best media. As the influence of
base was crucial for the reaction, different bases were
DBU
K2CO3
K2CO3
K2CO3
aReaction conditions: 1a (0.20 mmol), 2a (0.20 mmol),
AgOTf (0.02mmol) and base (0.40 mmol) in solvent (3.0
mL). bIsolated yield. cThe ratio of 1a/2a = 1.2:1. dThe ratio
of 1a/2a = 1:1.2. The ratio of 1a/2a = 1.5:1. nd = not
detected.
e
f
Figure1. X-ray single crystal structure of 3aa
2
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10.1002/adsc.202000398
Advanced Synthesis & Catalysis
With the optimal reaction conditions in hand,
(Scheme 4, 3aa−3ha). These results clearly indicated
that there is no major electronic effect on the
substitution pattern of the benzene ring. For instance,
the electron-rich 3-methoxyl-substituted hydrazone 1b
worked well in this annulation, and the corresponding
product 3ba was obtained in moderate yield (65%).
The electron-deficient 4-fluoro-substituted hydrazone
1d was also compatible with the reaction conditions,
leading to 3da in 88% isolated yield. In addition, some
disubstituted hydrazones 1 were also examined. For
example, N-Boc 3,4-dichloro-substituted hydrazone 1f
was well tolerated in the cycloaddition reaction,
leading to 3fa in 79% yield. Furthermore, when N-acyl
hydrazones were used to replace N-Boc hydrazones,
the cycloaddition reactions also proceeded well in 65%
to 86% yields (Scheme 4, 3ia−3oa). However, N-tosyl
hydrazine 1p gave no product under these optimal
conditions.
further studies were focused on the evaluation of the
substrate scope of this [4+3] cycloaddition process by
reacting various of N'-(2-alkynylbenzylidene)-
hydrazides 2 with α-halo hydrazone 1a, and the results
were summarized in Scheme 3. When there was no
substituent in the benzene ring of the benzenesulfonyl
moiety (R1), the yield of corresponding product 3ab
was 84%. Both electron-donating (−Me, −OMe) and
electron-withdrawing groups (−Br, −F, −Cl) were
successfully introduced to the ortho- or para-positions
of the phenyl ring, affording the corresponding
cycloaddition products (Scheme 3, 3aa, 3ac, 3ad, 3af
and 3ag) in moderate to excellent yields (78−90%). In
addition, when 2,4,6-trimethyl benzenesulfonyl
substituted hydrazide 2h was used as a substrate, the
corresponding product 3ah was afforded in 65% yield.
To our delight, the reaction performed well with 2-
naphthalenesulfonyl
and
2-thiophenesulfonyl
protected hydrazide 2e and 2i to deliver the desired
product 3ae and 3ai in 85% and 64% yield,
respectively. These results clearly indicated that N'-(2-
alkynylbenzylidene)-hydrazides 2 can endure the wide
variation in R1.
Scheme 3. Substrate scope of N'-(2-alkynylbenzylidene)-
a
hydrazide 2a,b. Reaction conditions: 1a (0.24 mmol), 2a
(0.20 mmol), AgOTf (0.02mmol), and K2CO3 (0.40 mmol)
in MeCN (3.0 mL). bIsolated yield.
To further expand the scope of the substrates, the
diversity of α-halo hydrazones 1 were investigated
under optimal conditions. As shown in Scheme 4, both
α-chloro and α-bromo hydrazones 1 proved to be good
1,2-diaza-1,3-diene precursors in this annulation
reaction (Scheme 4, 3aa and 3ca). Regardless of the
electron property (electron-rich, -neutral, or -deficient)
and the substituent pattern (para-, meta-, or ortho-
position) on the benzene ring of α-bromo N-Boc
hydrazones, the corresponding cycloaddition products
3 were obtained in moderate to excellent yields
Scheme 4. Substrate scope of α-halo-hydrazone 2a,b.
aReaction conditions: 1a (0.24 mmol), 2a (0.20 mmol),
3
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10.1002/adsc.202000398
Advanced Synthesis & Catalysis
AgOTf (0.02mmol), and K2CO3 (0.40 mmol) in MeCN (3.0
mL). bIsolated yield. cnd = not detected.
Scheme 5. Gram-scale experiment
To show the synthetic applicability of our present
methodology, a gram-scale reaction was performed in
a conventional laboratory. When 6.0 mmol α-halo
hydrazone 1a was reacted with 5.0 mmol N'-(2-
alkynylbenzylidene)-hydrazide 2a, the corresponding
product 3aa was obtained with a satisfactory yield of
75%, which confirmed the practicality of the method
(Scheme 5).
Scheme 7. Plausible mechanism
In summary, an efficient method for the synthesis of
1,2,4,5-tetrazepine derivatives through a silver (I)-
mediated [4+3] cycloaddition reaction between in situ
formed
1,2-diaza-1,3-dienes
and
C,N-cyclic
azomethine imines was devoloped. A variety of α-halo
hydrazones and N'-(2-alkynylbenzylidene)-hydrazides
were compatible under the mild reaction conditions,
affording the corresponding biologically important
and functionalized 1,2,4,5-tetrazepine derivatives in
moderate to excellent yields. The further discovery of
other cycloaddition reactions by using the in situ
generated 1,2-diaza-1,3-dienes with other in situ
formed reactive species is currently underway in our
laboratory.
Experimental Section
General procedure for the synthesis of 4: Under a
nitrogen atmosphere, MeCN (3.0 mL) was added to a sealed
tube charged with 2 (1.0 equiv, 0.2 mmol), AgOTf (0.1
equiv, 0.02 mmol). The reaction mixture was then stirred at
80 °C for 3 h. After cooling to room temperature, 1 (1.2
equiv, 0.24 mmol) and K2CO3 (2.0 equiv, 0.4 mmol) were
added and the mixture was stirred at room temperature for
0.5-6 h. The precipitated solid was filtrated and washed with
water (3 x 3.0 mL) and diethyl ether (2 x 2.5 mL). The
isolated product was dried without further purification (65%
to 90% yield).
Scheme 6. Control experiments
In order to explore the reaction mechanism, several
control experiments were employed under the standard
reaction conditions. When the radical scavengers
butylated hydroxytoluene (BHT) and 2,2,6,6-
tetramethylpiperidine oxide (TEMPO) were added to
the mixture, the reaction proceeded smoothly and was
not inhibited, which indicated that this reaction did not
proceed via a radical mechanism (Scheme 6a and 3b).
To provide further support for the reaction pathway,
treatment with 4 and 1a under standard conditions
gave the desired product 3aa in 90% yield (Scheme
6c), suggesting that the reaction involves the in situ
formation of 4. Based on the above results and
previous literature and studies, a plausible mechanism
for this cyclization reaction was proposed (Scheme 7).
Initially, C,N-cyclic azomethine imine A could be
formed through the silver(I)-mediated 6-endo
cyclization of N'-(2-alkynylbenzylidene)-hydrazide 2a.
α-Halo hydrazone 1a reacted with K2CO3 to generate
the reactive 1,2-diaza-1,3-dienes B. 1,4-Conjugated
addition of C,N-cyclic azomethine imine A to B
produced hydrazine intermediate C. Subsequently,
intramolecular cyclization may be occurred to form
1,2,4,5-tetrazepine 3 from intermediate C.
Acknowledgements
We are grateful to the Program for Innovative Research Team of
the Ministry of Education, The Program of Liaoning Revitalization
Talents Program (XLYC1808037).
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crystallographic data for this paper. These data are
provided free of charge by The Cambridge
Crystallographic
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Centre
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www.ccdc.cam.ac.uk/data_request/cif.
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COMMUNICATION
Silver(I)- and Base-Mediated 1,3-Dipolar [4+3]
Cycloaddition of in Situ generated 1,2-Diaza-1,3-
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Adv. Synth. Catal. Year, Volume, Page – Page
Zefei Li, Shuaikang Li, Tianjiao Kan, Xinyue
Wang, Xin Xin, Yunlei Hou* and Ping Gong*a
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