Synthesis of 1,2-Dihydrocyclobuta[b]quinoline Derivatives from Isocyanophenyl-Substituted Methylenecyclopropanes

Article abstract of DOI:10.1002/adsc.201700509

A new protocol to synthesize 1,2-dihydrocyclobuta[b]quinoline derivatives from isocyanophenyl-substituted methylenecyclopropanes via a formal insertion of isocyanide carbon into a C?C bond has been developed. The reaction proceeds smoothly in the presence of silver carbonate (5 mol%) upon heating in a highly atom economic manner and exhibits broad substrate scope, giving the desired products in moderate to excellent yields. Furthermore, several transformations of the obtained products have been also demonstrated. (Figure presented.).

Full text of DOI:10.1002/adsc.201700509

Title: Synthesis of 1,2-Dihydrocyclobuta[b]quinoline Derivatives from
Isocyanophenyl-Substituted Methylenecyclopropanes
Authors: Min Shi, Hou-Lu Liu, Yu-Chao Yuan, and Yin Wei
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201700509
Link to VoR: http://dx.doi.org/10.1002/adsc.201700509

10.1002/adsc.201700509
Advanced Synthesis & Catalysis
Update
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Synthesis of 1,2-Dihydrocyclobuta[b]quinoline Derivatives from
Isocyanophenyl-Substituted Methylenecyclopropanes
Hou-Lu Liu,a,b Yu-Chao Yuan,a Yin Wei,a Min Shi*a,b
a
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese
Academy of Sciences, 345 Lingling Road, Shanghai 200032 China.
b Department of Chemistry, Shanghai University, 99 Shangda Road, Shanghai 200444, China.
Fax: (+86)-21-6416-6128; e-mail: mshi@mail.sioc.ac.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))
Especially, MCPs could be used as a C3 synthon to construct
polycyclic systems, which have attracted a lot of attention from
Abstract.
dihydrocyclobuta[b]quinoline
A
new protocol to synthesize 1,2-
derivatives from
]
organic chemists in the past decades.[13 More recently, several
isocyanophenyl-substituted methylenecyclopropanes via a
formal insertion of isocyanide carbon into a C-C bond has
been developed. The reaction proceeds smoothly in the
presence of silver carbonate (5 mol%) upon heating in a
highly atom economic manner and exhibits broad substrate
scope, giving the desired products in moderate to excellent
yields. Furthermore, several transformations of the
obtained products have been also demonstrated.
novel formal intramolecular [3+2] cascade cycloadditions of
MCPs with alkynes or the in situ generated ketenimines,
isocyanates and isothiocyanates have been also developed for the
]
diversified synthesis of fused polycyclic compounds.[14 For
example, we have previously reported a visible-light-induced
trifluoromethylation
of
isocyanophenyl-substituted
alkylidenecyclopropanes to access 2-trifluoromethylquinoline
derivatives using Togni reagent via an intramolecular radical
Keywords: isocyanide; methylenecyclopropane; quinoline;
aromatic heterocycles
]
cyclization with arene.[15 This interesting transformation
.
encouraged us to further explore the new chemistry of
isocyanophenyl-substituted
alkylidenecyclopropanes
or
methylenecyclopropanes in the construction of heterocycles.
Isocyanides as pivotal species in organic chemistry have been
widely used to synthesize a diversity of nitrogen-containing
compounds, especially in the preparation of aromatic
heterocycles.[1] They have exhibited versatile reaction properties
in organic synthesis. For example, the α proton next to isocyano
moiety has high acidity due to the electron-withdrawing effect of
the isocyano moiety,[2] and thus isocyanides can serve as nitrilium
ylides after abstraction of the α-H group.[3] Moreover, they can
also undergo radical insertion,[4] form metal carbenes with a
transition metal catalyst,[5] insert into a C-heteroatom bond,[6]
undergo dimerization,[7] and act as a zwitterion to accept
nucleophilic attack,[8] or even function as a cyanide resource in
further chemical transformations.[9] Among these interesting
transformations, the insertion into a C-heteroatom bond has been
well investigated, but the insertion into a C-C bond is still
undeveloped due to the unpolarized high C-C bond energy.[10]
During the past decades, multi-component reactions have been
developed significantly and utilized as a powerful protocol to
rapidly construct complex molecules.[11] Alternatively, employing
mono-component intramolecular cyclization reactions is also a
good strategy to effectively construct polycyclic structural motifs.
Methylenecyclopropanes (MCPs), classical highly strained
small ring compounds, are efficient building blocks in organic
synthesis due to their ready accessibility as well as diverse
reactivity driven by the relief of ring strain. The ring opening
reactions of MCPs are synthetically useful in the construction of
Figure 1. 1,2-Dihydrocyclobuta[b]quinoline structural motifs
found in biologically active molecules.
1,2-Dihydrocyclobuta[b]quinolines have recently attracted a lot
of attention because their highly strained heterocyclic systems are
very useful in organic synthesis.[16] Moreover, they are special
building blocks found in a sort of non-imidazole histamine H3
antagonist molecules and chemoattractant receptor-homologous
]
complex product structures, and have been studied extensively.[12
1
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10.1002/adsc.201700509
Advanced Synthesis & Catalysis
molecule expressed on T-helper-type-2-cells (CRTH2) receptor
17
]
modulator (Figure 1).[
In general, the previously reported
preparation methods were carried out under harsh conditions,
giving the products only in low yields.[18] Therefore, the
development of convenient and efficient synthetic methods for
this type of heterocyclic compounds is highly desirable at the
present stage. Herein, we wish to report a formal intramolecular
[3+1]
cyclization
reaction
to
acquire
1,2-
dihydrocyclobuta[b]quinoline derivatives using isocyanophenyl-
substituted methylenecyclopropanes as substrates upon
heating in the presence of metal Lewis acid.
We initiated our investigation by heating a mixture of
isocyanophenyl-substituted methylenecyclopropane 1a and
Ag2CO3 (20 mol%) in 1,4-dioxane at 80 oC and only trace amount
of the desired 1,2-dihydrocyclobuta[b]quinoline derivative 2a was
detected (Table 1, entry 1). To our delight, when the reaction was
carried out at 100 oC and 120 oC, the desired product 2a was
isolated in 23% and 86% yields, respectively (Table 1, entries 2-
3). In the absence of Ag2CO3, the reaction still could proceed
smoothly, giving 2a in 52% yield, but suggesting that the addition
of Ag2CO3 could indeed improve the reaction outcome (Table 1,
entry 4). Concerning the background reaction (entry 4), we have
confirmed that after all of the starting materials were consumed,
the desired product 2a was still provided in only 52% yield. The
higher reaction temperature can also promote the decomposition
of starting materials. Thus, raising the reaction temperature or
prolonging the reaction time can not further enhance the yield of
the desired product, and these operations cannot achieve a highly
effective catalyst-free reaction. In addition, starting materials 1d
and 1i from Table 2 have been also chosen for the reaction carried
out under a catalyst-free condition, but no better result was
obtained either (45% and 50% yields). Next, we screened several
other metal salts such as CuBr, Cu(OTf)2, AgNTf2 and
CF3COOAg, but no better results could be achieved (Table 1,
entries 5-8). Reducing the Ag2CO3 loading to 10 mol% or 5 mol%
gave 2a in 90% and 95% yields, respectively (Table 1, entries 9-
10). The examination of solvent effect revealed that 1,2-
dichloroethane (DCE), acetonitrile and toluene are not suitable for
this reaction (Table 1, entries 11-13). The use of N,N-
dimethylformamide (DMF) also gave 2a in a relatively lower
yield (Table 1, entry 14). We have also used the non-metallic
Table
2.
Reaction
scope:
Synthesis
of
1,2-
dihydrocyclobuta[b]quinoline derivatives.a, b
.
Lewis acid BF3 Et2O (0.2 equiv) as the catalyst in this reaction,
but it only leads to decomposition of the starting materials without
formation of 2a under the standard reaction conditions (entry 15).
Table 1. Optimization of the reaction conditions for the synthesis
of 2a.a, b, c
With the optimal reaction conditions (1.0 equiv. 1, 5 mol%
o
Ag2CO3 in 1,4-dioxane at 120 C under an argon atmosphere) in
2
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10.1002/adsc.201700509
Advanced Synthesis & Catalysis
hand, we next surveyed the substrate scope with a range of
different isocyanophenyl-substituted methylenecyclopropanes in
this reaction. The results are summarized in Tables 2 and 3,
respectively. As for substrates 1b-1m, the reactions proceeded
efficiently regardless of whether the aryl groups contained
electron donating or withdrawing substituents, providing the
corresponding products 2b-2m in good to excellent yields. In
addition, heteroaromatic group was also tolerated in the reaction,
affording the desired product 2n in 42% yield. The lower yield of
2n was mainly due to the instability of thiophene-substituted
substrate 1n under the standard conditions. Nitryl or Cl
substituent could be also introduced at the phenylisocyanide
moiety, giving the corresponding products 2o-2s in good yields.
All these results suggested that the electronic effects on both of
aromatic rings did not have significant impact on the reaction
yield. The structure of 2g was unambiguously confirmed by X-ray
diffraction analysis, and its ORTEP drawing is shown in Table
eq. 2), indicating that the cyclopropane moiety in MCPs is
essential to this transformation.
Scheme 1. Control experiments.
]
On the basis of above results and the previous reports,[20
a
]
2.[19
plausible reaction mechanism for this formal [3+1] cyclization of
isocyanophenyl-substituted methylenecyclopropane to construct
1,2-dihydrocyclobuta[b]quinoline derivative has been outlined in
Scheme 2. Initially, the C=C double bond of MCP in 1 (or its
resonance structure 1’) was activated by silver (I) ion to give an
intermediate A or A’ and there might exist an equilibrium
between the intermediate A and the intermediate A’ (see Page S67
in the Supporting Information). Subsequently, the intermediate A
underwent an intramolecular nucleophilic attack to afford
intermediate B.[21] Then, the elimination of Ag+ and cyclopropane
ring expansion furnished the corresponding product 2.
Table
3.
Reaction
scope:
Synthesis
of
1,2-
dihydrocyclobuta[b]quinoline derivatives.a, b, c
Scheme 2. A plausible reaction mechanism for the formation of 2.
To further illustrate the synthetic utility of product 2, we have
conducted several transformations of 2a, 2l and 2w. Carrying out
the reaction of 2a in H2O2/HOAc at 120 oC afforded the N-
We further investigated substrates 1 containing aliphatic group
or H atom in this reaction. As shown in Table 3, when R2 is H
atom, methyl or butyl group, the desired products 2t-2v were
furnished in moderate yields. For substrates 1w and 1x, in which
R2 is H atom, and the phenylisocyanide moiety was substituted by
Me or Cl at the para-position, the reaction also proceeded
smoothly, giving the desired products 2w and 2x in moderate
yields.
To get more insights into the reaction mechanism of this novel
formal [3+1] cyclization reaction, a well-known radical scavenger
2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO, 1.0 eq) was added
into the reaction of 1a under the standard conditions and the
desired product 2a was obtained in 83% yield along with the
recovery of TEMPO in 94% yield (Scheme 1, eq. 1), suggesting a
non-radical reaction pathway. The use of substrate 1y with
isocyanophenyl- and dimethyl-substituted alkene only gave
complex product mixtures under identical conditions (Scheme 1,
]
oxidation product 3a in 98% yield (Scheme 3, eq. 1).[22 The
reaction of 2l with 4-tolylboronic acid under Suzuki-Miyaura
]
cross coupling reaction conditions[23 produced the corresponding
arylation product 3b in 98% yield (Scheme 3, eq. 2). When
diethyl
1,4-dihydro-2,6-dimethyl-3,5-pyridinedicarboxylate
(Hantzsch ester) was used as a hydride source and binaphthyl
phosphoric acid was used as a Brønsted acid catalyst, the
corresponding reduction product 3c derived from hydrogen
]
transfer was obtained in 91% yield (Scheme 3, eq. 3),[24
providing a key precursor for bioactive molecules.
3
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10.1002/adsc.201700509
Advanced Synthesis & Catalysis
Acknowledgements
We are grateful for the financial support from the National Basic
Research Program of China (973)-2015CB856603, the Strategic
Priority Research Program of the Chinese Academy of Sciences,
Grant No. XDB20000000, the National Natural Science
Foundation of China (20472096, 21372241, 21572052, 20672127,
21421091, 21372250, 21121062, 21302203 and 20732008).
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The formal [3+1] cyclization reaction could also be carried
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Scheme 4. A scale-up reaction of 1p for the synthesis of 2p.
In conclusion, we have developed a novel formal [3+1]
cyclization
reaction
of
isocyanophenyl-substituted
methylenecyclopropanes upon heating in the presence of Ag2CO3
(5 mol%) via the formal insertion of isocyanide carbon into a C-C
bond, affording diversified 1,2-dihydrocyclobuta[b]quinoline
derivatives. The reaction proceeds efficiently through an excellent
atom economic manner and exhibits broad substrate scope under
convenient conditions, giving the desired products in moderate to
excellent yields. Several useful transformations of the
corresponding products have been also demonstrated in this
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reaction mechanism is in progress.
Experimental Section
General Procedure for Synthesis of 2
A 10 mL flame-vacuum dried screwed-tube equipped with a
magnetic stirring bar was charged with 1 (0.2 mmol, 1.0 equiv),
Ag2CO3 (0.01 mmol, 0.05 equiv) and 1,4-dioxane (2.0 mL) under
o
argon atmosphere. The reaction mixture was stirred at 120 C for
8-24 hours in a pre-heated oil bath. After the starting material 1
was consumed completely (using TLC to monitor the reaction
proceeding), the reaction mixture was cooled to ambient
temperature. Then, organic solvent was removed under reduced
pressure and the resulting residue was purified through a silica-gel
column chromatography to provide the desired product.
4
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10.1002/adsc.201700509
Advanced Synthesis & Catalysis
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