Copper-catalyzed aerobic oxidative carbocyclization-ketonization cascade: Selective synthesis of quinolinones

Article abstract of DOI:10.1002/adsc.201300160

A new thematic extension method is described for the carbocyclization of α-C(sp³)-H bonds of amides with alkynes followed by ketonization of the alkynes that utilizes the inexpensive copper(II) acetoacetonate [Cu(acac)₂] as catalyst

Full text of DOI:10.1002/adsc.201300160

FULL PAPERS
DOI: 10.1002/adsc.201300160
Copper-Catalyzed Aerobic Oxidative Carbocyclization–
Ketonization Cascade: Selective Synthesis of Quinolinones
Peng Xie,a,b Zhi-Qiang Wang,a Guo-Bo Deng,a Ren-Jie Song,a Jia-Dong Xia,a,b
Ming Hu,a and Jin-Heng Lia,*
a
State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan
University, Changsha 410082, Peopleꢀs Republic of China
Fax : (+86)-731-8871-3642, phone: (+86)-731-8871-3642; e-mail: jhli@hnu.edu.cn
Key Laboratory of Chemical Biology & Traditional Chinese Medicine Research, Hunan Normal University, Changsha
b
410081, Peopleꢀs Republic of China
Received: February 17, 2013; Revised: May 19, 2013; Published online: August 9, 2013
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201300160.
Abstract: A new thematic extension method is de- noteworthy that the oxygen atom of the newly
3
À
scribed for the carbocyclization of a-C
G
of amides with alkynes followed by ketonization of lar oxygen.
the alkynes that utilizes the inexpensive copper(II)
ACHUTGTNRNE(UNG acac)2] as catalyst under an Keywords: carbocyclization; copper; CCAHTUNGTREN(NGUN sp ) H func-
oxygen atmosphere to synthesize quinolinones. It is tionalization; ketonization; quinolinones
acetoacetonate [Cu
Introduction
for quinolinone synthesis using CuCl2 combined with
O2 as the terminal oxidants: without Ru catalysts the
Quinolinones are important structural motifs in reaction could not take place even in the presence of
a great number of bioactive natural products, pharma- CuCl2 and O2, and the oxygen atom in the newly
ceuticals, and organic functional materials.[1] For these formed carbonyl group of quinolinones is from water
reasons, great interest has been directed to the direct by hydration (Scheme 1).[10] However, the chemical
construction of the quinolinone skeleton.[2–4] To date, disadvantages of this protocol center around using Ru
3
À
the cyclization approaches have been the major focus catalysts as well as special a-C
G
of study in this area,[3–5] such as classic base-catalyzed amides adjacent to a nitrogen atom. An alternative
3
Friedlꢁnder reaction,[3] acid-catalyzed Knorr reac- catalytic system for the a-C
(sp ) H bonds in common
À
tion,[4] the Baylis–Hillman reaction,[5] and recent tran- amides with more sustainable perspectives is there-
sition metal-catalyzed cyclization of acyclic precur- fore highly appealing. Herein we report a novel
sors.[6] However, the transition metal-catalyzed ap- Cu
ACHTUNGTREN(NNUG acac)2-catalyzed aerobic oxidative carbocycliza-
3
proaches are much less abundant, and many are fo- tion and oxygenation of an alkyne with two a-CACHTUNGTRENNUNG(sp )
cused on the “prefunctionalization” strategy that re- H bonds in a common amide with the aid of a base
stricts it to the use of expensive substrates (often aryl (Scheme 1). Notably, this work represents a different
halides) and catalytic systems (often Pd combined thematic extension of the metal-catalyzed oxidative
3
À
with a ligand). A fascinating strategy for quinolinone
C
(sp ) H functionalization–carbocyclization–ketoni-
À
synthesis is metal-catalyzed C H functionalization– zation cascade for quinolinone synthesis, and the
cyclization cascade, but unfortunately, the reported oxygen atom of the newly formed carbonyl group is
step- and atom-economic methods have been typically incorporated from atmospheric molecular oxygen.
achieved by rare and noble transition metal catalysts
Generally, activation of the a-positioned carbon of
(e.g. Pd, Pt, Ru, and Au), and are limited to the sp2 a carbonyl system requires a base to deprotonate it
À
C H bond functionalization, including (i) arylation of leading to a carbon nucleophile or an enol intermedi-
N-arylpropiolamides[7] or N-(2-haloaryl)-benzamides[8] ate followed by complexation of a metal and addition
and (ii) amidation of 3-arylacrylamides.[9]
to an electrophile (aryl halide and pseudohalide)[11a,b]
We recently reported the first example of an or a carbon-carbon multiple bond.[11c] Although the
RuCl3-catalyzed carbocyclization–hydration cascade Cu-catalyzed cyclization of an alkyne with an a-
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Table 1. Screening for optimal conditions.[a]
Entry [Cu]
Base
Solvent Temp. Yield
[oC]
[%][b]
1
2
CuCl2 (2)
CuCl2 (5)
CuCl2 (1)
–
–
–
–
–
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Et3N
DMF
DMF
DMF
DMF
DMF
DMF
110
110
110
110
110
110
110
110
110
110
110
110
110
110
110
110
65
59
61
20
<5%
0
3[c]
4[d]
5[e]
6
7
8
9
DABCO DMF
0
0
P4-t-Bu
Cs2CO3
Cs2CO3
DMF
DMF
DMF
DMF
DMF
DMF
DMF
CuCl (2)
CuBr2 (2)
58
53
64
68
41
54
67
16
73
9
10
11
12
13
14
15
16
17
18
19
20
Cu
Cu
Cu
Cu
Cu
Cu
Cu
Cu
Cu
Cu
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
3
À
Scheme 1. Synthesis of quinolinones through CACTHNUTRGENUG(N sp ) H bond
functionalization.
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
T
AHCTUNGTRENNUNG
T
AHCTUNGTRENNUNG
carbon of a carbonyl system has been illustrated, the
in-situ generated carbon nucleophile A in this cycliza-
tion process required another electron-withdrawing
group to stabilize it and the vinyl-Cu(II) intermediate
DMSO 110
toluene 110
DMSO 95
DMSO 125
DMSO 110
70
61
19
B is readily protonated (Scheme 2).[11c] Therefore, the 21[f]
CuACHTUNTGRENNUNG
development of a new strategy to trap the vinyl-
[a]
Reaction conditions: 1a (0.3 mmol), [Cu], O2 (1 atm),
base (2 equiv.) and solvent (2 mL) for 14 h. P4-t-Bu is
phosphazene base solution and the purity of Cs2CO3 is
about 99% w/w.
Isolated yield.
For 24 h.
Some unidentified products together with traces of 4-
benzyl-1-methyl-3-phenylquinolin-2(1H)-one (3a) were
observed by GC-MS analysis. There are about 0.005%
w/w of Cu in Cs2CO3 (purity: 99% w/w) by ICP-MS anal-
ysis: 0.05 mol% Cu (2 equiv. Cs2CO3) vs. substrate 1a.
99.999% w/w Cs2CO3 (2 equiv.) was used.
Under an air atmosphere.
Cu(II) intermediate for valuable synthetic utilization
is highly desirable. To the best of our knowledge,
however, trapping of the vinyl-Cu(II) intermediate
with atmospheric molecular oxygen through the sp3-
[b]
[c]
carbon cyclization with alkynes has not been estab-
[d]
lished.[12]
Results and Discussion
[e]
[f]
Our study began to examine the feasibility of the pro-
posed carbocyclization–oxygenation cascade using
N-methyl-2-phenyl-N-[2-(phenylethynyl)phenyl]acet-
ACHTUNGTRENNUNGamide (1a), O2, a series of copper catalysts and bases (entry 1). This finding prompted us to examine the
(Table 1). Gratifyingly, the amide 1a was successfully amount of CuCl2: identical results were achieved at
reacted with O2, CuCl2 and Cs2CO3 in DMF at 1108C, a loading of either 5 mol% or 1 mol% CuCl2, but the
affording the desired product
2 in 65% yield latter (1 mol% CuCl2) required a prolonged reaction
Scheme 2. Cu-catalyzed carbocyclization–protonation cascade.
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Copper-Catalyzed Aerobic Oxidative Carbocyclization–Ketonization Cascade
Table 2. Cu-catalyzed oxidative cyclization of N-(2-ethynylaryl)acetamides (1).[a]
[a]
Reaction conditions: 1 (0.3 mmol), CuACTHUNGTREN(NUNG acac)2 (2 mol%), O2 (1 atm), Cs2CO3 (2 equiv.)
and DMSO (2 mL) at 1108C for 14 h.
time (entries 2 and 3). To our surprise, in the absence catalysts, CuCl, CuBr2, Cu
of Cu catalyst product 2 could form in the presence of tested (entries 9–12): all displayed high reactivity for
99% purity Cs2CO3, albeit with a low yield (entry 4). the reaction, and Cu(acac)2 was superior. Therefore,
We deduced that Cs2CO3 might contain some copper Cu(acac)2 was employed to evaluate the effect of
ACHUTGTNERN(NGU OTf)2 and CuACHTUNGTNER(NUGN acac)2 was
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
to realize the reaction, which was supported by the bases and solvents (entries 13–18). Screening revealed
ICP-MS analysis results. To verify it, both 99.999% that the reaction using Cs2CO3 as base in DMSO
purity Cs2CO3 and organic bases were inversigated medium gave the best results (entry 17). It is notewor-
without Cu catalysts (entries 5–8): the yield of 2 was thy that CuACTHNURGTENUNG(acac)2 conbined with Et3N can furnish the
lowered to <5% with 99.999% purity Cs2CO3, and desired product 2 in 16% yield (entry 16). Among the
the use of organic bases, such as Et3N, DABCO or P4- reaction temperatures examined, the reaction at 958C
t-Bu, resulted in no detectable formation of product offered an identical result to that at 1108C (entry 19),
2. In the light of these results, a number of other Cu but a higher temperature (1258C) had a negative
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Peng Xie et al.
FULL PAPERS
effect (entry 20). However, substrate 1a displayed
a rather low reactivity under an air atmosphere
(entry 21).
We next turned our attention to the scope of N-[2-
(ethynyl)aryl]acetamides 1 for the carbocyclization–
ketonization cascade under the optimal reaction con-
ditions, and the results are summarized in Table 2.
While 2-phenyl-N-[2-(phenylethynyl)phenyl]acetam-
ACHTUNGTRENNUNGide was not viable for this reaction (product 3), when
the N-H group was replaced by benzyl or allyl groups
the respective substrates were found to furnish the
corresponding products 4 and 5 in good yields, while
replacement by an acetyl group resulted in a trace of
the desired product 6. Subsequently, substituents at
the terminal alkyne were examined in the presence of
O2, CuACHTUNGTRENNUNG(acac)2 and Cs2CO3: a variety of aryl groups,
such as 2-BrC6H4, 4-MeC6H4, 4-MeOC6H4, 4-ClC6H4,
4-BrC6H4, naphthalen-1-yl and even thiophen-2-yl
groups, at the terminal alkyne were well-tolerated
(products 7–13), but an aliphatic group displayed less
reactivity (product 14). Importantly, in these cases
some halo functional groups, Br and Cl, on the aro-
Scheme 3. Control experiments.
matic ring were compatible with the optimal condi- lecular oxygen, and the reaction includes a Cu-peroxo
tions, thereby facilitating additional modifications at species-forming process. Notably, cyclization of sub-
the halogenated positions (products 7, 10 and 11).
strate 26 was not observed [Eq. (3)], which ruled out
Gratifyingly, substrates with several substituents, the mechanism including the ketone intermediate 26
3
À
like alkyl, F, CF3 and Cl, on the aryl ring of the N-[2- from the first oxidation of the a-C
(ethynyl)aryl]acetamide moiety displayed sufficient
G
As outlined in Scheme 4, a possible mechanism is
reactivity for the carbocyclization–oxygenation cas- proposed on the basis of the results described above.
cade in the presence of O2, Cu(acac)2 and Cs2CO3 Initially, complexation of Cu(II) with an a-carbon nu-
AHCTUNGTRENNUNG
(products 15–20). For example, the CF3-substitued cleophile, which is generated by deprotonation of the
3
À
amide offered the desired quinolinone 17 in 77% a-C
(sp ) H bond in amide 1 by Cs2CO3, yields inter-
yield. Using a di-Cl-substitued amide, a good yield mediate A.[11] Nucleophilic cyclization with alkyne in
was still achieved (product 19). It was noted that intermediate A takes place to afford intermediate B,
hetreo- or carbocyclic rings were consisitent with the followed by oxidation of intermediate B with O2
optimal conditions, making this methodology more which forms a CuACHTNUTGRNEUNG
(III) peroxo species C.[12,13] Reduc-
useful in organic synthesis (products 13 and 20). tive elimination of intermediate C furnishes a peroxide
Fianlly, a number of substrates with a-carbon in the intermediate D.[12] Finally, The peroxide intermediate
À
amides were tested, and the results disclosed that the D undergoes sequentially the O O bond cleavage, re-
a-carbon atom joined to either an aryl group or an ductive elimination and isomerization to construct
aliphatic group was also highly effective in the reac- quinolinone 2 and the Cu(I) species.
tion (products 21–25).
The results in Table 1 disclosed that the yield was
lowered sharply when using air instead of O2 (en- Conclusions
tries 17 vs. 21, Table 1), suggesting that the source of
the oxygen atom in the newly formed carbonyl group In summary, we have illustrated a new thematic ex-
is from atmospheric molecular oxygen. To understand tension route to quinolinone synthesis by the Cu-cata-
3
À
of the mechanism of the carbocyclization–oxygena- lyzed oxidative C
tion cascade, some control experiments were carried
G
clization–ketonization cascade. Most importantly, this
out. As shown in Scheme 3, in the presence of H218O present protocol provides an alternative to implant an
treatment of amide 1a with 16O2, Cu
ACTHNUTRGNEU(NG acac)2 and oxygen atom from molecular oxygen into the quinoli-
Cs2CO3 only afforded the 16O-labelled product 2. In none framework, establishing a new synthetic utility
contrast, the presence of 18O2 resulted in highly 18O- for both copper catalysts and molecular oxygen. Ap-
labelled product 2-18O as determined by GC-MS, plications of this Cu-catalyzed oxidative carbocycliza-
HMRS and NMR analysis (see the Supporting Infor- tion–ketonization transformation in organic synthesis
mation). These results confirmed that the oxygen are currently under study in our laboratory.
atom was really incorporated from atmospheric mo-
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Copper-Catalyzed Aerobic Oxidative Carbocyclization–Ketonization Cascade
Scheme 4. Possible mechanism.
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Typical Experimental Procedure for the Cu-Catalyzed
carbocyclization-ketonization Reaction
To a Schlenk tube were added amide 1 (0.3 mmol), Cu-
ACHTUNGTRENNUNG(acac)2 (2 mol%), Cs2CO3 (2 equiv.) and DMSO (2 mL).
Then the tube was charged with O2 (1 atm), and the mixture
was stirred at 1108C overnight until complete consumption
of starting material as monitored by TLC analysis. After the
reaction had finished, the reaction mixture was washed with
brine. The aqueous phase was re-extracted with ethyl ace-
tate. The combined organic extracts were dried over
Na2SO4, concentrated in vacuum, and the resulting residue
was purified by silica gel column chromatography (hexane/
ethyl acetate) to afford the desired product.
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4-Benzoyl-1-methyl-3-phenylquinolin-2(1H)-one
(2):
White solid; mp 193.1–194.98C (uncorrected); 1H NMR
(500 MHz, CDCl3): d=7.63 (d, J=8.0 Hz, 2H), 7.52 (t, J=
8.0 Hz, 1H), 7.40–7. 36 (m, 2H), 7.30 (d, J=8.0 Hz, 1H),
7.23–7.18 (m, 4H), 7.12–7.07 (m, 4H), 3.78 (s, 3H);
13C NMR (125 MHz, CDCl3): d=195.6, 161.1, 145.2, 139.6,
136.0, 133.9, 130.8, 130.1, 129.8, 129.2, 128.5, 128.0, 127.7,
126.9, 122.5, 118.2, 114.5, 30.2; IR (KBr): n=1695,
1621 cmÀ1; LR-MS (EI 70 eV): m/z (%)=339 (M+, 76), 310
(100), 262 (56), 105 (56), 77 (79); HR-MS (ESI): m/z=
340.1339, calcd. for C23H18NO2 [M+H]+: 340.1338.
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Acknowledgements
We thank the National Natural Science Foundation of China
(No. 21172060), Specialized Research Fund for the Doctoral
Program of Higher Education (No. 20120161110041) and
Fundamental Research Funds for the Central Universities
(Hunan University) for financial support.
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