Synthesis of Functionalized Cyclobutane-Fused Naphthalene Derivatives via Cascade Reactions of Allenynes with tert-Butyl Nitrite

Article abstract of DOI:10.1002/adsc.201801439

A novel synthesis of cyclobutanol-fused 2-nitronaphthalen-1-ols and nitrocyclobutane-fused naphthalene-1,2-diones through cascade reactions of benzene-linked allenynes with tert-butyl nitrite is presented. The formation of the title compounds involves a tandem process including allenyne [2+2] cycloaddition, radical addition onto the in situ formed cyclobutenyl moiety followed by radical coupling/oxidation. Interestingly, different kinds of functionalized naphthalene derivatives could be obtained selectively from the same substrates, and the selectivity was easily controlled by finely tuning the reaction conditions. (Figure presented.).

Full text of DOI:10.1002/adsc.201801439

Title: Synthesis of Functionalized Cyclobutane-Fused Naphthalene
Derivatives via Cascade Reactions of Allenynes with tert-Butyl
Nitrite
Authors: Tian Feng, Yan He, Xinying Zhang, and Xuesen Fan
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10.1002/adsc.201801439
Advanced Synthesis & Catalysis
COMMUNICATION
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Synthesis of Functionalized Cyclobutane-Fused Naphthalene
Derivatives via Cascade Reactions of Allenynes with tert-Butyl
Nitrite
Tian Feng,a Yan He,a,* Xinying Zhang,a and Xuesen Fana,*
a
Henan Key Laboratory of Organic Functional Molecules and Drug Innovation, Key Laboratory of Green Chemical
Media and Reactions, Ministry of Education, Collaborative Innovation Center of Henan Province for Green
Manufacturing of Fine Chemicals, School of Chemistry and Chemical Engineering, School of Environment, Henan
Normal University, Xinxiang, Henan 453007, P.R. of China
Fax: (86)-373-332-6336; E-mail: xuesen.fan@htu.cn; heyan@htu.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######.
nitronaphthalen-1-ol (A, Scheme 1). This envisioned
synthesis is based on a proposed cascade reaction of a
benzene-linked allenyne with TBN through the
formation of two C–C bonds and two C–N bonds as
shown in Scheme 1. Herein, we report our detailed
results in this regard.
Abstract: A novel synthesis of cyclobutanol-fused 2-nitro-
naphthalen-1-ols and nitrocyclobutane-fused naphthalene-
1,2-diones through cascade reactions of benzene-linked
allenynes with tert-butyl nitrite is presented. The formation
of the title compounds involves a tandem process including
allenyne [2+2] cycloaddition, radical addition onto the in
situ formed cyclobutenyl moiety followed by radical
coupling/oxidation. Interestingly, different kinds of
functionalized naphthalene derivatives could be obtained
selectively from the same substrates, and the selectivity
was easily controlled by finely tuning the reaction
conditions.
Keywords: Cyclobutanol-fused 2-nitronaphthalen-1-ols;
Nitrocyclobutane-fused naphthalene-1,2-diones, Benzene-
linked allenynes; tert-Butyl nitrite; Cascade reactions
Nitroalkane and nitroarene scaffolds constitute the key
subunits of many natural products, pharmaceuticals
and functional materials. Moreover, both aromatic and
aliphatic nitro compounds are versatile intermediates
frequently used in synthetic chemistry.[1,2] In addition,
the nitro unit itself can be easily transformed into
other functional groups such as amino, diazo, halides,
etc.[1,2] Due to their importance, a number of methods
for the preparation of nitroalkanes and nitroarenes
have been developed.[3,4] Conventional methods for
this purpose usually use nitric acid as the nitrating
reagent and another strong acid as the catalyst, which
often cause poor selectivity and produce corrosive
wastes. Therefore, recent studies have focused on
finding more sustainable and milder nitrating reagents
such as tert-butyl nitrite (TBN),[5] etc.[6]
Allene derivatives are highly valuable in synthetic
chemistry owing to their rich reactivity and ready
availability.[7] In this regard, Jiang and co-workers
have recently disclosed some interesting domino
transformations of allenynes.[8] Inspired by those
pioneering studies and as a continuation of our own
interests in allene derivatives[7c,9] and TBN,[10] we
envisioned a synthesis of nitrocyclobutane-fused 2-
Scheme 1. Envisioned Synthesis of Nitrocyclobutane-
Fused 2-Nitronaphthalen-1-ol (A)
Initially, 1-(2-(phenylethynyl)phenyl)buta-2,3-dien-
1-one (1a) was treated with TBN (2) in CH3CN at
50 °C under air for 3 h. To our surprise, the
envisioned product A as shown in Scheme 1 was not
obtained. On the other hand, 3-nitro-1-phenyl-1,2-
dihydrocyclobuta[a]naphthalene-1,4-diol (3a) was
obtained in 50% yield (Table 1, entry 1). Another
unexpected
product,
1-nitro-1-phenyl-1,2-
dihydrocyclobuta[a]naphthalene-3,4-dione (4a), was
also isolated in a yield of 10%. Although A was not
obtained, the unprecedented formation of 3a and 4a
from the reaction of 1a with 2 is no less interesting.
This is mainly due to the fact that compounds
containing either the cyclobutanol moiety as
embedded in 3a[11,12] or the naphthalene-1,2-dione unit
as present in 4a are useful precursors toward various
kinds of fine chemicals.[13,14] In addition, they are also
prevalent in naturally occurring and man-made
compounds with potent biological activities. A
literature search revealed that reliable and sustainable
1
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10.1002/adsc.201801439
Advanced Synthesis & Catalysis
methods for their synthesis are very limited.[11-14] To
improve its efficiency and selectivity, several
parameters possibly affecting this reaction were
screened. Toluene, dioxane, DCE or THF was tried to
replace CH3CN as the reaction medium (entries 2-5).
Among them, DCE gave the best result (entry 4).
Further studies showed that decreasing or increasing
the reaction temperature could not improve the
efficiency (entries 6-7). Next, the reaction was run
under O2 instead of air, from which 3a and 4a were
obtained in yields of 38% and 33%, respectively
(entry 8). Moreover, several oxidants (di-tert-butyl
peroxide (TBP), tert-butyl hydroperoxide (TBHP) and
Table 2. Substrate Scope for the Synthesis of 3[a,b]
3a, 58%
3e, 56%
3i, 48%
3b, 54%
3f, 64%
3j, 65%
3d, 72%
3h, 60%
3c, 65%
3g, 62%
3k, 0%
2,2,6,6-tetramethylpiperidin-1-yloxy
(TEMPO)),
frequently used in nitration reactions with TBN as a
nitro source, were tried. It turned out that the presence
of TBHP or TEMPO amplified the selectivity toward
4a significantly (entries 9-11). In the presence of
TEMPO, 4a was obtained in 66% yield while 3a was
formed only in a trace amount (entry 11). Further
studies in varying the loadings of TEMPO and TBN
did not give more positive results (entries 12-15).
With the establishment of the optimum reaction
conditions, the substrate scope for the synthesis of 3
was explored. It was observed that benzene-linked
allenynes 1 bearing a chloro on the 4-position, or a
methyl or methoxy group on the 5-position of the
linking phenyl unit reacted with 2 smoothly to give
3b-3d in yields of 54%, 65% and 72%, respectively
(Table 2). Next, 1 containing different alkynyl units
was studied. It was thus found that the R2 unit
attached on the triple bond of 1 could be a phenyl ring
[a]
Reaction conditions: 0.5 mmol of 1, 1.5 mmol of 2,
DCE (3 mL), 50 °C, air, 3 h. [b] Isolated yields.
bearing chloro or methyl unit on different positions to
afford products 3e-3i in yields ranging from 48-64%.
Interestingly, when the R2 unit was a 3-thioenyl group,
product 3j was obtained in 65% yield. On the other
hand, with R2 as a cyclopropyl unit, the corresponding
reaction gave a complicated mixture and the desired
product 3k was not obtained. Notably, the structure of
3f was confirmed by its X-ray single crystal
diffraction analysis.[15]
Table 1. Optimization Studies for the Formation of 3a[a]
Then, the substrate scope for the synthesis of 4 was
studied. First, a number of 1 bearing different R1 were
tried to react with 2 under the optimized reaction
conditions as shown in Table 1, entry 11. It turned out
that the corresponding reactions proceeded smoothly
to afford 4a-4g in moderate to good yields (Table 3).
Remarkably, functional groups such as methyl,
methoxy, fluoro and chloro were well tolerated, thus
allowing for further structural elaborations possible.
Promisingly, naphthalene-linked allenyne could also
take part in this reaction to afford 4h in 41% yield.
yield (%)[b]
entry
oxidant (equiv)
solvent
T/°C
3a
50
4a
10
1
2
CH3CN
toluene
dioxane
DCE
50
50
50
50
50
30
70
50
50
50
50
50
50
50
50
32
6
3
40
8
4
58
12
Second, the reactions of
1 bearing diversely
5
THF
25
trace
trace
10
substituted alkynyl moieties were investigated. It was
thus found that the R2 unit attached on the triple bond
could be a phenyl ring bearing various functional
groups, from the electron-donating methyl and
methoxy to the electron-withdrawing fluoro and
chloro, on the para-, meta-, or ortho-position of the
phenyl ring, to give 4i-4o in yields ranging from 55%-
81%. In addition, the R2 unit could also be a 3-
thioenyl group to afford 4p in 76% yield. Third, 1
bearing an ethyl unit on the external position of the
allenic moiety (R3) were found to react with 2
smoothly to afford 4q and 4r in moderate yields.
Delightfully, 1 with an ester group as the R3 unit could
also take part in this cascade reaction to give 4s in
42% yield. It is worth to be noted herein that the
structure of 4c has been confirmed by its X-ray single
crystal diffraction analysis.[16]
6
DCE
20
7
DCE
53
8
O2
DCE
38
33
9
TBP (1)
DCE
41
29
10
11
12
13
14
15
TBHP (1)
DCE
20
48
TEMPO (1)
TEMPO (0.5)
TEMPO (1.5)
TEMPO (2)
TEMPO (1)
DCE
trace
trace
trace
trace
trace
66
DCE
45
DCE
61
DCE
48
DCE
65[c]
[a] Reaction conditions: 0.5 mmol of 1a, 1.5 mmol of 2, 3
mL of solvent, air, 3 h. [b] Isolated yields. [c] 2 mmol of 2.
2
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10.1002/adsc.201801439
Advanced Synthesis & Catalysis
Table 3. Substrate Scope for the Synthesis of 4 [a,b]
reaction 5).
4b, 62%
4f, 81%
4d, 88%
4h, 41%
4a, 66%
4e, 64%
4c, 75%
4g, 75%
Scheme 2. Control Experiments
4k, 81%
4o, 55%
4i, 72%
4j, 76%
4n, 67%
4l, 79%
4p, 76%
4m, 70%
Scheme 3. Proposed Mechanism for the Formation of 3a
Based on previous reports[8] and our observations, a
plausible mechanism accounting for the formation of
3a from 1a and 2 is proposed in Scheme 3. Initially,
1a undergoes [2+2] cycloaddition to give intermediate
4s, 42%
4q, 64%
4r, 62%
[a] Reaction conditions: 0.5 mmol of 1, 1.5 mmol of 2, 0.5
mmol of TEMPO, DCE (3 mL), 50 °C, air, 3 h. [b] Isolated
yields.
t
A. Subsequently, the in situ generated BuOO·, which
is plausibly more nucleophilic than NO2·, undergoes a
conjugate addition onto A to provide intermediate B.
Next, B couples with NO2· togive C. Protonation of C,
most likely by solvent, affords D. Finally,
tautomerization of D affords 3a.
To gain some insights into the reaction mechanism,
the following control experiments were performed.
First, 2,6-di-tert-butyl-4-methylphenol (BHT) as a
radical scavenger was added to the standard reaction
system for the synthesis of 3a and 4a. As a result, the
formation of 3a or 4a was not detected (Scheme 2,
reaction 1 and reaction 2), indicating that these
reactions follow a radical pathway. Second, the
synthesis of 3a was carried out in the presence of
As for the formation of 4a, it should also involve an
initial generation of A. In the presence of TEMPO, the
t
formation of the proposed reactive BuOO· as shown
in Scheme 3 might be inhibited. In this case, A
chooses to react with NO2· to form intermediate E,
which is captured by TEMPO to form intermediate
18
H2 O (Scheme 2, reaction 3), from which [18O1]-3a
and [16O]-3a were formed in a ratio of 1:18, and the
formation of [18O2]-3a was not observed. Third, the
preparation of 3a was run under 18O2 instead of air.
From this reaction, [18O2]-3a, [18O1]-3a and [16O]-3a
were obtained in a ratio of 13:40:47 (Scheme 2,
reaction 4). These 18O-labeling experiments suggest
that the O atom of the OH and the NO2 moieties
embedded in 3a mainly come from molecular oxygen
in air rather than H2O possibly present in solvent.
Fourth, to confirm the crucial role played by TEMPO
in the formation of product 4, the reaction of 1a with 2
was tried under argon instead of air. From this
reaction, 4a was obtained in a yield of 50% (Scheme 2,
t
F.[17] Under the assistance of BuO· and NO·, F
undergoes a N–O bond cleavage to afford 4a and
TEMPNO (Scheme 4). As an evidence for this
proposed pathway, the formation of TEMPNO was
confirmed by a MS analysis of the resulting mixture
(see SI). Alternatively, E might also be trapped by O2
(from air) to afford a superoxide radical, which then
undergoes a O–O bond cleavage to give 4a.[17b]
To see whether these newly developed methods are
suitable for large scale synthesis, the preparations of
3a and 4a were carried out in 5 mmol scale. It turned
out that the corresponding reactions proceeded
3
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10.1002/adsc.201801439
Advanced Synthesis & Catalysis
To a reaction tube equipped with a magnetic bar were
added 1-(2-(phenylethynyl)phenyl)buta-2,3-dien-1-one (1a,
122 mg, 0.5 mmol), DCE (3 mL) and tert-butyl nitrite (2,
178 μL, 1.5 mmol). The resulting mixture was stirred at
50 °C for 3 h. It was then cooled to room temperature, and
concentrated under reduced pressure. The residue was
purified by column chromatography on silica gel with
petroleum ether/ethyl acetate (10:1) as the eluent to give 3a
(89 mg, 58%). 3b-3j were obtained in an analogous manner.
smoothly to afford 3a and 4a in yields of 51% and
54%, respectively (Scheme 5).
Typical Procedure for the Synthesis of 1-Nitro-1-
phenyl-1,2-dihydrocyclobuta[a]naphthalene-3,4-dione
(4a)
To a reaction tube equipped with a magnetic bar were
added 1-(2-(phenylethynyl)phenyl)buta-2,3-dien-1-one (1a,
122 mg, 0.5 mmol), DCE (3 mL), tert-butyl nitrite (2, 178
μL, 1.5 mmol) and TEMPO (78 mg, 0.5 mmol). The
resulting mixture was stirred at 50 °C for 3 h. It was then
cooled to room temperature, and concentrated under
reduced pressure. The residue was purified by column
chromatography on silica gel with petroleum ether/ethyl
acetate (10:1) as the eluent to afford 4a (101 mg, 66%). 4b-
4s were obtained in an analogous manner.
Scheme 4. Proposed Mechanism for the Formation of 4a
Scheme 5. Gram-scale Synthesis of 3a and 4a
Finally, to showcase the usability of the products
obtained above and to develop an alternative synthetic
pathway toward benzo[a]phenazine derivatives, which
are often endowed with significant biological and
fluorescent activities,[18] several naphthalene-1,2-
diones 4 were treated with 1,2-diaminobenzene (5).
From these reactions, benzo[a]phenazines 6a-6d were
obtained in good yields (Scheme 6).
Acknowledgements
We are grateful to the National Natural Science Foundation of
China (21572047, 21702050), Plan for Scientific Innovation
Talents of Henan Province (184200510012) and 111 Project
(D17007) for financial support.
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Experimental Section
Typical Procedure for the Synthesis of 3-Nitro-1-
phenyl-1,2-dihydrocyclobuta[a]naphthalene-1,4-diol (3a)
4
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10.1002/adsc.201801439
Advanced Synthesis & Catalysis
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10.1002/adsc.201801439
Advanced Synthesis & Catalysis
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