One-pot synthesis of quinoline derivatives directly from terminal alkynes via sequential ruthenium(II) and acid catalysis

Article abstract of DOI:10.1002/adsc.201000278

A convenient one-pot synthesis of 2,3-di- substituted, 2,3,6- trisubstituted, and 2,3,6,7-tetrasubstituted quinoline analogues from terminal alkynes via sequential ruthenium(II) and para-toluenesulfonic acid (p-TSA) co-catalyzed reactions is described. The catalytic process is shown to take place first via intermediate formation of an allyl ketone and then addition of an aniline derivative to the allyl ketone. The p-TSA is a catalyst for both allyl ketone and quinoline synthetic steps. The method allowed us to synthesize a wide range of quinoline derivatives and introduce different substituents by employing various simple starting materials. The reaction allows the synthesis of halogen-containing products.

Full text of DOI:10.1002/adsc.201000278

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DOI: 10.1002/adsc.201000278
One-Pot Synthesis of Quinoline Derivatives Directly from
Terminal Alkynes via Sequential Ruthenium(II) and Acid
Catalysis
Min Zhang,a,b,* Thierry Roisnel,c and Pierre H. Dixneufc,*
a
School of Chemical and Material Engineering, Jiangnan University, 1800 Lihu Road, Wuxi, Jiangsu Province 214122,
Peopleꢀs Republic of China
E-mail: zm31289@yahoo.com.cn
School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, Peopleꢀs
b
Republic of China
c
Institut Sciences Chimiques de Rennes, UMR 6226 CNRS-Universitꢁ de Rennes1, Campus de Beaulieu, 35042 Rennes,
France
Fax : (+33)-22-2323-6939; e-mail: pierre.dixneuf@univ-rennes1.fr
Received: April 9, 2010; Revised: June 11, 2010; Published online: August 16, 2010
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/adsc.201000278.
Abstract: A convenient one-pot synthesis of 2,3-di-
ACHTUNGTRENNUNGsubstituted, 2,3,6-trisubstituted, and 2,3,6,7-tetrasub-
duced for applications as thermally stable transparent
materials in the fields of electronics, optoelectronics
and non-linear optics.[10] Sugar-quinoline fluorescent
chemosensors can be used for selective detection of
Hg2+ ions in water.[11]
stituted quinoline analogues from terminal alkynes
via sequential ruthenium(II) and para-toluenesul-
fonic acid (p-TSA) co-catalyzed reactions is de-
scribed. The catalytic process is shown to take place
first via intermediate formation of an allyl ketone
and then addition of an aniline derivative to the
allyl ketone. The p-TSA is a catalyst for both allyl
ketone and quinoline synthetic steps. The method
allowed us to synthesize a wide range of quinoline
derivatives and introduce different substituents by
employing various simple starting materials. The re-
action allows the synthesis of halogen-containing
products.
The conventional synthetic methods for quinoline
derivatives such as the Skraup,[12] Friedlander,[13] and
Combes reactions[14] were reported as early as the end
of the 19th century. In the past decade, remarkable
new protocols have brought about a new access to
functional quinolines. They involve, for example, the
cyclization of ortho-alkynylanilines,[15] ortho-propar-
AHCTUNGTRENNUNG
gylanilines[16] or ortho-azido-containing derivatives,[17]
multicomponent coupling reactions[18], imine Diels–
Alder reactions[19], the condensation-cyclization from
ortho-haloacetophenones[20] and sequential cyclization
via Baylis–Hillman adduct intermediates.[21] These
recent methods are not always satisfactory due to the
not readily available starting materials or the require-
ment of multiple steps. However, there is still a con-
tinuous interest to discover direct quinoline syntheses
from readily available starting materials under mild
Keywords: alkynes; allyl ketones; anilines; quino-
lines; ruthenium; sequential catalysis
Quinolines and their analogues represent a very im- conditions.
portant class of nitrogen-containing heterocycles, as
Previous work on head-to-head oxidative coupling
the quinoline scaffold is present in both various bio- of alkynes at a Cp*Ru(II) moiety have led to the cat-
logically active compounds and useful functionalized alytic formation of dienes via proton and oxygen nu-
molecular materials. Applications of quinolines in me- cleophile addition at the 1,4-positions of the resulting
dicinal chemistry include their use as antimalarial,[1] biscarbene intermediate [Eq. (1)], by addition of car-
antileishmanial,[2] anti-inflammatory,[3] antiasthmatic,[4] boxylic acids generating dienyl esters,[22] alcohols lead-
antibacterial,[5] antihypertensive,[6] tyrosine kinase in- ing to dienyl ethers[23] and water to generate allylic
hibitory agents,[7] histamine H3 receptor inverse ago- ketones.[24]
nists[8] and for the treatment of estrogen-dependent
diseases.[9] Quinoline-based polymers have been pro- Cu(II)-catalyzed formation of furans [Eq. (2)].[23] This
.
The latter allylic ketones are the precursors of the
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Adv. Synth. Catal. 2010, 352, 1896 – 1903

One-Pot Synthesis of Quinoline Derivatives Directly from Terminal Alkynes
this reaction in the absence of Cu(II) salt, by using
the allylic ketone 4a and p-toluidine 2a with molecu-
lar sieves. The results leading to the formation of 3a
are reported in Table 1.
catalytic transformation of allyl ketones into furans
led us to study the formation of nitrogen-containing
heterocycles from alkynes via their sequential catalyt-
ic transformations.
Table 1. Influence of p-TSA, ruthenium catalyst and temper-
ature on the formation of quinoline 3a from allyl ketone
4a.[a]
Herein, we now wish to report the newÀone-pot se-
+
Entry Catalyst
T
Yield [%]
quential ruthenium Cp*Ru
N
[8C] of 3a[b]
toluenesulfonic acid (p-TSA) catalyzed synthesis of 2-
substituted 3-arylquinolines directly from terminal al-
kynes and aniline derivatives [Eq. (3)].
1
2
3
4
5
p-TSA (30 mol%)
p-TSA (30 mol%)
120 65
100 83
90 31
p-TSA (30 mol%)
Cp*Ru
(MeCN)3 PF6À (8 mol%)
100
–
+
p-TSA (30 mol%) and Cp*Ru-
100 81
+
À
AHCTUNGRTENGUN(N MeCN)3 PF6 (8 mol%)
[a]
Reaction performed in a closed Schlenk tube: the mix-
ture of 1 mmol of 4a, 0.6 mmol of p-toluidine 2a with
molecular sieves in 2 mL of dioxane was stirred at 90–
1208C for 6 h.
[b]
GC yields based on 4a.
When the reaction mixture was stirred at 1208C,
1008C, 908C for 5 h in the presence of 30 mol% of p-
TSA catalyst alone in dioxane, the quinoline 3a was
formed in 65%, 83%, 31% GC yields, respectively.
The reaction of an allyl ketone 4a with p-toluidine Thus, a temperature of 1008C was more suitable for
in the presence of molecular sieves to generate the this transformation (Table 1, entries 1, 2 and 3). The
+
À
imine and of Cu2+ salt with air to afford the 2,5-disub- utilization of 8 mol% of Cp*Ru
ACHTNUGTRENUNG(MeCN)3 PF6 cata-
stituted pyrrole, an analogue of furan, was studied lyst alone in the absence of acid at 1008C for 5 h did
first. In that case, a mixture of the corresponding not produce the desired product (Table 1, entry 4).
+
À
furan, pyrrole 3a’ and quinoline 3a was formed, each The combination of 8 mol% Cp*RuACTHNUTGRNEG(UN MeCN)3 PF6
of them in a small amount. However, when the same and 30 mol% para-toluenesulfonic acid (p-TSA) cata-
reaction was performed in the presence of molecular lysts resulted in similar result as with the use of
sieves (MS) but without Cu2+ salt, the pyrrole was no 30 mol% para-toluenesulfonic acid (p-TSA) catalyst
longer formed and the 2-benzyl-3-phenylquinoline alone at 1008C for 5 h (Table 3, entries 2 and 5). This
product 3a and acetophenone were obtained [Eq. observation proved that the real catalyst for the trans-
(4)].
formation of allyl ketones into quinoline was para-tol-
We then evaluatedÀthe influence of p-TSA acid and uenesulfonic acid itself and not the ruthenium cata-
+
Cp*Ru
N
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Min Zhang et al.
COMMUNICATIONS
After having found the best conditions for the for- worthy that the initially introduced p-TSA (15 mol%
mation of 3a without any negative influence of with respect to alkyne and 30 mol% with respect to
+
À
Cp*Ru
sis of quinolines directly from alkynes by sequential tion of both allyl ketone and then quinoline.
catalytic reactions, via the formation of in situ gener- The scope of this reaction was then investigated. A
ACHTUNGTRENNUNG(MeCN)3 PF6 , we have attempted the synthe- the in situ formed allyl ketone) promotes the forma-
ated allyl ketones. Thus, after the co-catalyzed forma- series of commercially available terminal arylacety-
tion of allyl ketone 4a from terminal alkyne 1a lenes 1 and the aromatic primary amines 2 were em-
(1 mmol) and water in the presence of Cp*Ru- ployed to evaluate the substrate scope (Table 2).
+
À
ACHTUNGTRENNUNG(NCMe)3 PF6 (4 mol%) and p-TSA (15 mol%), ani- 1 mmol of arylacetylene 1 was used to give the allyl
line derivative 2a (0.3 mmol) and molecular sieves ketone, after completion of the reaction after 0.5 h,
were added and the catalytic mixture was heated at the aromatic primary amine 2 (0.3 mmol) was then
1008C for 6 h. The quinoline 3a was isolated in 39% added with molecular sieves and the mixture was
yield with respect to the alkyne, and 78% yield with heated at 1008C for 5–24 h. All the reactions proceed-
respect to the aniline, as the formation of methyl aryl ed smoothly in a closed Schlenk tube and provided
ketone was also observed (Table 2, entry 1). It is note- the 2,3-disubstituted and 2,3,6-trisubstituted quinoline
Table 2. Sequential ruthenium and acid co-catalyzed synthesis of substituted quinolines directly from terminal alkynes.[a]
Entry
1
1
2
Time [h][b]
Quinoline 3
Yield [%]
78,[b] 39[c]
1a
1a
1a
1a
2a
6
3a
3b
3c
3d
2
3
4
2b
2c
2d
5
84[b]
72[b]
54[b]
10
24
5
1b
1b
2a
2c
6
3e
3f
78[b]
6
10
62[b]
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One-Pot Synthesis of Quinoline Derivatives Directly from Terminal Alkynes
Table 2. (Continued)
Entry
1
2
Time [h][b]
Quinoline 3
Yield [%]
72[b]
7
1c
1d
1e
1e
1e
2a
6
3g
3h
3i
8
2a
2b
2c
2e
5
82[b]
86[b]
86[b]
60[b]
9
5
10
5
3j
11
10
3k
[a]
Reaction performed in a closed Schlenk tube: the mixture of 1 mmol of 1 and 1 mmol of H2O with 0.04 mmol of RuCp*-
ACHTUNGTRENNUNG(NCMe)3 PF6 catalyst (4 mol% based on alkyne and 13 mol% on aniline) and 0.15 mmol p-TSA.H2O (15 mol% based
+
À
on alkyne and 50 mol% on aniline) in 2 mL of dioxane was stirred at room temperature for 0.5 h, then molecular sieves
and 0.3 mmol aniline derivatives were added, the resulting mixture was stirred at 1008C for 5–24 h.
Isolated yields based on anilines.
[b]
[c]
Isolated yields based on alkynes.
derivatives (Table 2, entries 1–11). We observed that
the electronic influence of substituents on the arylace-
tylenes 1 did not affect too much the formation of
quinolines. However, the influence of substituents on
the aromatic primary amines 2 is quite effective for
the transformation. The aromatic amines bearing
electron-donating substituents such as CH3, OCH3
groups favored the reaction (Table 2, entries 1, 2, 5, 7,
8 and 9), for example, the p-toluidine 2a and anisidine
2b needed relatively shorter reaction times and pro-
vided relatively higher yields, while the use of 4-
chloroACHTUNGTRENNUNGbenzenamine 2d and 4-bromobenzenamine 2e
afforded relatively lower yields of 3d and 3k (Table 2,
entries 4 and 11). As the products tolerate aryl halides
(Table 2, entries 4, 7, 8 and 11), the method has the
potential to provide access for further functionaliza-
tion via classical cross-coupling reactions.
Figure 1. The X-ray structure of quinoline 3g.
The reaction of 2-naphylamine 2f with phenylacety-
lene led only to one regioisomer 3l isolated in 45%
The nature of the 2,3-disubstituted quinolines 3, yield with respect to the alkyne, corresponding at the
with the benzyl group linked to carbon 2, was estab- expected selective reactivity of the a-carbon [Eq.
lished by NMR experiments, and then confirmed by (5)].
the X-ray crystal diffraction of derivative 3g.
The substrate scope of aniline derivative 2g was
then investigated to evaluate the regioselectivity of
(Figure 1).[25]
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Min Zhang et al.
COMMUNICATIONS
the reaction which can lead to two possible regioisom-
ers 5 and 5’’. The results showed that only one regio-
isomer 5 was formed, the 2,3,6,7-tetrasubstituted quin-
oline derivatives 5a–5e (Table 3, entries 1–5).
It is to be noted that the quinoline yield never
exceed 50% with respect to the alkyne and, besides
the formation of the quinoline 3, that the formation
of the aryl ketone, arising from water addition to the
arylacetylene, is always observed. This indicates that
all the alkyne is not incorporated into the quinoline
and that the allyl ketone is fragmented [Eq. (4)].
Thus the mechanism of the quinoline formation is
Table 3. Regioselective synthesis of quinolines directly from terminal alkynes.[a]
Entry
1
1
Time [h]
6
Quinoline 5
Yield [%]
1a
1b
5a
5b
80%,[b] 40[c]
2
5
68[b]
3
4
1f
1c
5
5
5c
62[b]
5d
74[b]
5
1e
5
5e
78[b]
[a]
Reaction perfÀormed in closed Schlenk tube: The mixture of 1 mmol of 1 and 1 mmol of H2O with 0.04 mmol of RuCp*-
+
N
lecular sieves and 0.3 mmol 3,4-dimethylbenzenamine was added, the resulting mixture was stirred at 1008C for 5–6 h.
Isolated yields based on anilines.
Isolated yields based on alkynes.
[b]
[c]
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Adv. Synth. Catal. 2010, 352, 1896 – 1903

One-Pot Synthesis of Quinoline Derivatives Directly from Terminal Alkynes
Scheme 1. Proposed mechanism for quinoline derivative formation directly from terminal alkynes.
likely to take place as shown in Scheme 1. The allyl
ketone 4 is first generated starting from arylacetylene
and water with the cooperative action of Cp*Ru-
+
À
ACHTUNGTRENNUNG
(MeCN)3 PF6 and p-TSA catalysts.[23,24] The conden-
sation and aza-Michael addition of the aniline deriva-
tive with the allyl ketone 4 result in the formation of
ketimine A. The p-TSA-catalyzed retro-Mannich type
fragmentation is expected to produce the ketimine B
(giving the methyl aryl ketone D on hydrolysis) and
the imine C. The more reactive imine C should under-
go a self-aldol condensation and o-carbon nucleophil-
ic addition to the imine moiety to generate tetrahy- water and p-TSA, only one molecule of alkyne is
droquinoline intermediate E, and the quinoline is fi- transformed into quinoline. This sequential ruthenium
nally formed by aniline elimination and aromatiza- and p-TSA-catalyzed formation of quinoline from ter-
tion.
minal alkynes is a new method to produce quinolines
To support this mechanism the 1-para-tolylbut-3- via allyl ketone intermediates, but does not constitute
en-1-one 7 which contains differently substituted car- an atom-economic reaction as the loss of one alkyne
bons 1 and 4, was reacted with p-toluidine in the pres- skeleton is observed.
ence of p-TSA. The 2,6-dimethylquinoline 8 and 1-p-
In conclusion, we have established a convenient
tolylethanone were produced and this formation is one-pot synthesis of 2,3-disubstituted, 2,3,6-trisubsti-
consistent with a retro-Mannich fragmentation [Eq. tuted, and 2,3,6,7-tetrasubstituted quinoline analogues
(6)].[26,27]
simply from terminal alkynes via sequential a ruthe-
This experiment and mechanism explain that, in the nium(II) and p-TSA co-catalyzed processes. The reac-
formation of quinoline 3 from terminal alkyne 1, tion is shown to take place via intermediate formation
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Min Zhang et al.
COMMUNICATIONS
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Typical Procedure
In a Schlenk tube equipped wiÀth a magnetic stirring bar, the
+
catalyst RuCp*
N
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down to room temperature, the resulting mixture was direct-
ly filtered through a pad of silica, washed with 20 mL of a
mixture of ethyl acetate and petroleum ether (1:20), the
combined solvents were evaporated to afford the crude
product. This was purified by flash column chromatography
on silica, eluting with petroleum ether: ethyl acetate (20: 1)
to give 4-benzyl-6-methyl-2-phenylquinoline 3a as a light
yellow oil; yield: 60.3 mg (78%).
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Acknowledgements
The authors are grateful to the “Fundamental Research
Funds for the Central Universities” (No. JUSRP10905), to
the China Scholarship Council” for a grant to Min Zhang,
and to “Institut Universitaire de France” (PHD).
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