Copper-catalyzed aerobic oxidative annulation and carbon-carbon bond cleavage of arylacetamides: Domino synthesis of fused quinazolinones

Article abstract of DOI:10.1002/adsc.201300818

An efficient copper-catalyzed tandem aerobic oxidative annulation and carbon-carbon bond cleavage reaction was developed from easily accessible arylacetamides, which provides a direct approach for the domino synthesis of a vast array of tricyclic or tetracyclic fused quinazolinone alkaloid structures. A plausible reaction mechanism is proposed involving an aerobic benzylic oxidation/ cyclization/decarbonylation cascade.

Full text of DOI:10.1002/adsc.201300818

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DOI: 10.1002/adsc.201300818
Copper-Catalyzed Aerobic Oxidative Annulation and Carbon-
Carbon Bond Cleavage of Arylacetamides: Domino Synthesis of
Fused Quinazolinones
Jie Sun,a Qitao Tan,a Wusong Yang,a Bingxin Liu,a and Bin Xua,b,c,
Department of Chemistry, Shanghai University, Shanghai 200444, Peopleꢀs Republic of China
*
a
Fax : (+86)-21-6613-4594; phone: (+86)-21-6613-2830; e-mail: xubin@shu.edu.cn
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of
Sciences, Shanghai 200032, Peopleꢀs Republic of China
Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Department of Chemistry, East China Normal
University, Shanghai 200062, Peopleꢀs Republic of China
b
c
Received: September 8, 2013; Revised: November 6, 2013; Published online: February 2, 2014
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201300818.
Abstract: An efficient copper-catalyzed tandem
aerobic oxidative annulation and carbon-carbon
bond cleavage reaction was developed from easily
accessible arylacetamides, which provides a direct
approach for the domino synthesis of a vast array
of tricyclic or tetracyclic fused quinazolinone alka-
loid structures. A plausible reaction mechanism is
proposed involving an aerobic benzylic oxidation/
cyclization/decarbonylation cascade.
tions of ketones and aldehydes.[8] Although significant
progresses have been achieved with this strategy,
most of the C C bond cleavages were catalyzed by
noble metals such as palladium, rhodium and rutheni-
um, while use of the cheaper and ubiquitous copper
for such transformations is quite rare.[9]
Nitrogen-containing heterocycles are found in nu-
merous natural products and pharmaceutical drugs.
Among these azaheterocycles, quinazolinone scaffolds
are privileged structures in medicinal chemistry which
show a broad spectrum of potent biological activi-
ties[10,11] and serve as a crucial category of anticancer
agents as exemplified by marketed drugs such as Ral-
titrexed for colorectal cancer, Tempostatin for bladder
cancer, and Ispinesib for solid tumours in its clinic
trails. Typically, quinazolinones are constructed from
À
Keywords: copper; cyclization; decarbonylation;
quinazolinone; tandem reaction
À
Cleavage of C C bonds poses great challenges to 2-aminobenzoic acids or their derivatives via a se-
chemists mainly due to the inherent inertness of C C quence of acylation and condensation reactions under
À
s bonds (ca. 350 kJmolÀ1),[1] which partially makes acidic or basic conditions.[12,13] Although several other
their cleavage thermodynamically less favoured than methods have been developed to prepare quinazolin-
the opposite formation process.[2] In order to facilitate
ACHTUNGTRENoNUNG nes including transition metal-catalyzed reac-
such a transformation, generally two strategies have tions,[14,15] the development of novel synthetic methods
been exploited to provide the driving forces. One is to for quinazolinones as well as their fused derivatives is
raise the energy state of the starting materials, for ex- still highly demanded in term of efficiency and availa-
ample, by using strained small-membered ring sys- bility of starting materials. Herein, we report an effi-
tems.[3] The other is to lower the energy states of the cient copper-catalyzed tandem aerobic oxidative an-
À
C C bond cleavage intermediates, such as through nulation and carbon-carbon bond cleavage reaction,
À
À
formation of a stable organometallic intermediate by whereby in sequence one C O bond and two C N
chelating assistance.[4,5] Despite the remarkable bonds are formed followed by two C C bond cleavag-
À
achievements to date,[6] new strategies for C C bond es for decarbonylation. To the best of our knowledge,
À
cleavage of unstrained linear substrates have received the given approach features a novel protocol for se-
sustained interest. Alternatively, release of a stable quential chemical bond formation and cleavage of
small molecule such as CO or CO2 could compensate arylacetamides, which provides an efficient approach
the demanded energy, which is demonstrated by the for the domino synthesis of a vast array of tricyclic or
rapidly growing field of decarboxylative cross-cou- tetracyclic fused quinazolinones from easily available
pling reactions[7] and metal-catalyzed decarbonyla- arylacetamides (Scheme 1).
388
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Copper-Catalyzed Aerobic Oxidative Annulation
din-2-yl)acetamide (1b) in the presence of CuACHTUNGTRENNUNG(OAc)2
in dioxane using KOAc as a base in order to synthe-
size an N-pyridyl-substituted isatin. To our surprise,
the reaction afforded an unexpected product – 6-
methyl-11H-pyridoACHTNUGRTENUNG[2,1-b]quinazolin-11-one (2b) – in
58% yield (Table 1, entry 1). An extensive screening
concerning copper sources (entries 2–5), bases (en-
tries 6–9), ligands (entries 10–16), additives (en-
tries 17–19) and solvents (entries 20–22) revealed that
the use of CuI and 1,10-Phen as catalyst, KOAc as
base and TBAB as additive in DMF at 1008C under
air was the best choice and resulted in 2b in 87%
yield (entry 22). It is worth noting that decreased
yields were obtained in the absence of TBAB
(entry 23), which was supposed to act as a phase-
transfer catalyst for the copper ions by transmitting
them in the form of complexes to the organic phase
Scheme 1. Copper-catalyzed
ACHTUNGTRENNUNGacetamides to fused quinazolinones, and the X-ray structure
of product 2a. Thermal ellipsoids are set at 50% probability,
rendered with POV-Ray. Hydrogen and chlorine atoms are
omitted for clarity.
transformation
of
aryl-
Our preliminary investigation started by examining where the reaction takes place[16] or be involved in
the reaction of 2-(2-bromophenyl)-N-(3-methylpyri- the benzylic oxidation reaction by adjusting the solu-
Table 1. Optimization of reaction conditions.[a]
Entry
Cu Source
Base
Solvent
Additive
Ligand
Yield[b] [%]
1
2
3
4
5
6
7
8
Cu
Cu
N
KOAc
KOAc
KOAc
KOAc
KOAc
NaOAc
Cs2CO3
t-BuOK
Et3N
KOAc
KOAc
KOAc
KOAc
KOAc
KOAc
KOAc
KOAc
KOAc
KOAc
KOAc
KOAc
KOAc
KOAc
KOAc
KOAc
KOAc
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
DMSO
anisole
DMF
TBAB
TBAB
TBAB
TBAB
TBAB
TBAB
TBAB
TBAB
TBAB
TBAB
TBAB
TBAB
TBAB
TBAB
TBAB
TBAB
Bu4NCl
Bu4NOAc
Et4NBr
TBAB
TBAB
TBAB
–
1,10-Phen
1,10-Phen
1,10-Phen
1,10-Phen
1,10-Phen
1,10-Phen
1,10-Phen
1,10-Phen
1,10-Phen
bipyridine
l-proline
glycine
DMEDA
PPh3
IMes·HCl
–
1,10-Phen
1,10-Phen
1,10-Phen
1,10-Phen
1,10-Phen
1,10-Phen
1,10-Phen
–
58
36
65
58
84
trace
36
55
trace
51
80
trace
55
58
29
40
44
36
36
CuCl
CuBr
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
–
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25[c]
26
65
62
87
76
71
trace
trace
DMF
DMF
DMF
dioxane
–
TBAB
TBAB
1,10-Phen
1,10-Phen
[a]
Reaction conditions: 1a (0.3 mmol), [Cu] (10 mol%), ligand (20 mol%), base (3.0 equiv.) and TBAB (1.4 equiv.) in solvent
(2 mL), 10 h, 1008C, open to air, dried through a calcium chloride tube. DMEDA=N,N’-dimethylethylenediamine, 1,10-
Phen=1,10-phenanthroline, TBAB=tetrabutylammonium bromide.
Isolated yield.
Under an N2 atmosphere.
[b]
[c]
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Jie Sun et al.
Table 2. Synthesis of pyridine-derived quinazolines.[a,b]
[a]
Reaction conditions: 1 (0.3 mmol), CuI (10 mol%), 1,10-Phen (20 mol%), KOAc (3.0 equiv.)
and TBAB (1.4 equiv.) in DMF (2 mL), 10 h, 1008C, open to air, dried through a calcium chlo-
ride tube.
Isolated yield.
Run at 1158C.
[b]
[c]
bility of base in the solvent.[17] The absence of ligand (2n) were compatible with this reaction and gave
also led to a diminished yield (entry 24). Trace moderate to excellent yields, regardless of their differ-
amounts of product was detected when the reaction ent electronic properties and substitution positions.
was conducted under
a
nitrogen atmosphere The identity of products, for example 2a and 2n, was
(entry 25) or in the absence of CuI (entry 26), which determined by spectral analysis and further confirmed
implied that atmospheric oxygen and copper salt are by X-ray crystallographic analysis.[18] Substrate 1g
crucial for this transformation.
with a bromo substituent afforded the corresponding
With the optimized conditions in hand, various N- 2g in diminished yield accompanied with a 31% yield
pyridylarylacetamides with different substituents were of the debrominated product 2a. The reaction was not
investigated for the synthesis of fused quinazolinones. limited to simple benzene-containing aromatics, the
As illustrated in Table 2, a wide variety of substitution naphthyl substrate also gave the desired product in
patterns and functionalities could be tolerated. Sub- 69% yield (2s). It should be noted that the less reac-
strates bearing different functional groups on both of tive chloro-substituted substrate, 2-(2-chlorophenyl)-
the phenyl and pyridyl rings, such as alkyl (2b–d), aryl N-(pyridin-2-yl)acetamide (1t), could still afford prod-
(2e, 2f), cycloalkyl (2i), alkoxyl (2k, 2l, 2o, 2p, 2r), uct 2a in 58% yield.
halo (2g, 2m, 2q), nitrile (2j), ester (2h), and tosyl
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Copper-Catalyzed Aerobic Oxidative Annulation
Table 3. Synthesis of quinazolinones from arylacetamides containing various heterocycles.[a,b]
[a]
Reaction conditions: 3 (0.3 mmol), CuI (10 mol%), 1,10-Phen (20 mol%), KOAc (3.0 equiv.)
and TBAB (1.4 equiv.) in DMF (2 mL), 10 h, 1008C, open to air, dried through a calcium chlo-
ride tube.
Isolated yield.
[b]
To further explore the generality and scope of this
In comparison, when 2-bromo-N-(pyridin-2-yl)-ben-
method, other substrates were next examined. To our zamide (3k) was treated under the optimized condi-
delight, reactions of arylacetamides with N-heterocy-
cles other than the pyridyl group proceeded smoothly
under the optimized reaction conditions as illustrated
in Table 3. Substrates bearing thiazole (3a, 3b), benzo-
thiazole (3c), pyrazine (3d), pyrazole (3e), tetrazole
(3f), quinoline (3g, 3h) and 1,8-naphthyridine (3i)
moieties, all gave the desired tricyclic or tetracyclic
fused products in moderate to good yields. Notably,
some of these products have shown potent biological
activities and are difficult to prepare using regular
synthetic methods from easily available substrates.
Dual pyridine-containing substrate 3j also showed
good reactivity and gave 4j in good yield, which is of
good bactericidal activities.[19]
Scheme 2. Scope of arylacetamides.
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Jie Sun et al.
Scheme 3. Mechanistic studies. Conditions A: CuI (10 mol%), 1,10-Phen (20 mol%), KOAc (3.0 equiv.) and TBAB
(1.4 equiv.), under air.
tions, the reaction could also afford compound 2a in the reason for which may due to the difficult cycliza-
À
40% yield after reaction for 72 h (Scheme 2). The tion through an intramolecular C N bond formation
given result might arise from the iminoketene-benz- [Eq. (3)]. These results indicated that the decarbony-
ACHTUNGTRENNUNGazetinone intermediate formed by direct intramolecu- lation may occur through a cyclic intermediate such
[20]
À
lar C N bond formation of 3k. However, for sub- as isatin 5c during the formation of 2a from inter-
strate 3l with two carbons between the aryl and mediate 6, although no 5c was observed during this
amide groups, no expected cyclic product was ob- transformation. The synthesized 5c could indeed de-
served and the starting material was recovered quan- liver 2a smoothly with or without a copper catalyst
titatively. When we attempted to conduct the reaction (88% and 72% yield, respectively), which indicated
with the one-carbon homologated analogue of 1a, a thermal process for this transformation and strongly
2-(2-bromophenyl)-N-(pyridin-2-ylmethyl)acetamide
suggested that the isatin 5c may be the key intermedi-
(3m), it gave only the isatin product 5a in 28% ate for this reaction [Eq. (4)].
yield,[21] and no corresponding tricyclic fused product
was observed.
On the basis of these investigations, we proposed
a plausible mechanism for this transformation as de-
To define the reaction mechanism, several control picted in Scheme 4. Initially, 1a was aerobically oxi-
reactions were investigated (Scheme 3). Substrate 3n, dized to a-keto amide 6,[17] which gave the isatin
in which the pyridyl substituent in 1a was replaced by product 5c after a copper-catalyzed intramolecular
a phenyl group, afforded the isatin product 5b in 18% amination reaction. Subsequently, the intramoleular
yield under the optimized conditions [Eq. (1)]. This nucleophilic attack of pyridyl to ketone afforded a tri-
result suggested that the isatin product might be the cyclic zwitterionic intermediate A. The extrusion of
intermediate during the formation of quinazolinone carbon monoxide from intermediate A led to the for-
and that the pyridyl substituent played an important mation of quinazolinone 2a.[22] It is worth noting that
role for the subsequent transformation. Treatment of decarbonylation of a zwitterionic intermediate like A
1a at lower temperature in dioxane afforded a mixture is quite unusual, although expulsion of carbon monox-
of 6 and 2a in 49% and 46% yield, respectively. The ide from ketone bridged bicycles by a thermal or pho-
isolated 6 could be further transformed to 2a in 94% tochemical route is not surprising.[23]
yield under the standard conditions, while no reaction
In conclusion, we have successfully demonstrated
happened in the absence of copper catalyst [Eq. (2)]. an efficient copper-catalyzed tandem reaction through
Substrate 3o could only give the corresponding ben- sequential aerobic benzylic oxidation, intramolecular
zylic oxidative product 7 without the detection of 2a, cyclization, and decarbonylation processes. This ap-
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Copper-Catalyzed Aerobic Oxidative Annulation
Scheme 4. Plausible mechanism for the synthesis of 2a from 1a (ligands are omitted for clarity).
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Experimental Section
General Procedure for the Synthesis of Fused
Quinazolinones from Arylacetamides
To a 25-mL round-bottom flask equipped with a drying tube
and a magnetic stirring bar were charged 1b (92.0 mg,
0.30 mmol), CuI (5.7 mg, 0.03 mmol), 1,10-phenantholine
(11 mg, 0.06 mmol), KOAc (88 mg, 0.90 mmol) and TBAB
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column chromatography on silica gel (EtOAc/petroleum
ether=1:5) to afford 2b as a yellowish solid; yield: 55 mg
(87%).
Acknowledgements
We thank the National Natural Science Foundation of China
(No. 21272149), Innovation Program of Shanghai Municipal
Education Commission (No. 14ZZ094) and Science and
Technology Commission of Shanghai Municipality (No.
13ZR1416400) for financial support. The authors thank Prof.
Hongmei Deng (Laboratory for Microstructures, SHU) for
spectral support.
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