Categories: Synthesis of N-Heterocycles >
Synthesis of quinolines and related compounds
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Recent Literature
Heteroaromatic tosylates and phosphates are suitable electrophiles in
iron-catalyzed cross-coupling reactions with alkyl Grignard reagents. These
reactions are performed at low temperature allowing good functional group
tolerance with full conversion within minutes.
T. M. Gøgsig, A. T. Lindhardt, T. Skrydstrup, Org. Lett., 2009,
11, 4886-4888.
A series of 2,4-disubstituted quinolines were easily prepared through a
one-pot reaction of structurally diverse 2-aminoaryl ketones with various
arylacetylenes in the presence of K5CoW12O40 •
3 H2O as a reusable and environmentally benign catalyst under
microwave irradiation and solvent-free conditions.
I. Mohammadpoor-Baltork, S. Tangestaninejad, M. Moghadam, V. Mirkhani, S.
Anvar, A. Mirjafari, Synlett, 2010,
3104-3112.
An eco-friendly method allows the synthesis of 2,4-disubstituted quinolines via
Meyer-Schuster rearrangement of 2-aminoaryl ketones and phenylacetylenes in the
presence of a catalytic amount of zinc trifluoromethanesulfonate in the ionic
liquid [hmim]PF6. The ionic liquid can be recycled.
R. Sarma, D. Prajapati, Synlett, 2008,
3001-3005.
An iron-promoted tandem reaction of anilines with styrene oxides via C-C
cleavage and C-H activation utilizes inexpensive FeCl3 as promoter
and is suitable for forming various 3-arylquinolines from simple and readily
available starting materials.
Y. Zhang, M. Wang, P. Li, L. Wang, Org. Lett., 2012,
14, 2206-2209.
An efficient single-step approach toward the synthesis of 2-alkylquinolines is
mediated by a Lewis acid through [3 + 3] annulation reaction between
3-ethoxycyclobutanones and aromatic amines. Various multisubstituted
2-alkylquinoline derivatives were prepared regioselectively at room temperature.
G. Shan, X. Sun, Q. Xia, Y. Rao, Org. Lett., 2011,
13, 5770-5773.
An environmentally friendly and highly efficient procedure gives
2,4-disubstituted quinoline derivatives by a simple alkynylation-cyclization
reaction of 2-aminoaryl ketones with phenylacetylenes in the presence of
indium(III) trifluoromethanesulfonate In(OTf)3 under microwave
irradiation and solvent-free conditions. The catalyst can be reused.
K. C. Lekhok, D. Prajapati, R. C. Boruah, Synlett, 2008,
655-658.
A cooperative catalytic system, consisting of CuI and pyrrolidine enables an
efficient synthesis of 2-substituted quinolines. A combination of both catalysts
is necessary; the use of either catalyst alone does not give the product.
N. T. Patil, V. S. Raut, J. Org. Chem., 2010,
75, 6961-6964.
A three-component reaction of nitroarenes, aldehydes, and phenylacetylene in the
presence of indium in dilute hydrochloric acid produces quinoline derivatives
under reflux. The conversion involves reduction of the nitroarenes to anilines
followed by coupling of the anilines, aldehydes, and phenylacetylene, followed
by cyclization of the resulting species and dehydrogenation of the cyclic
intermediates.
B. Das, P. Jangili, J. Kashanna, R. A. Kumar, Synthesis, 2011,
3267-3270.
A straightforward and efficient Yb(OTf)3 catalyzed three-component
reaction of aldehydes, alkynes, and amines under microwave irradiation in an
ionic liquid provides 2,4-disubstituted quinolines in excellent yield under mild
reaction condition. The catalyst can be recycled up to four times.
A. Kumar, V. K. Rao, Synlett, 2011,
2157-2162.
A Fe(acac)3/TBAOH-catalyzed three-component
coupling-cycloisomerization reaction of aldehydes, terminal alkynes, and amines
provides a diverse range of heterocyclic compounds such as aminoindolizines and
quinoline derivatives in good yields.
S. S. Patil, S. V. Patil, V. D. Bobade, Synlett, 2011,
2379-2383.
A modified Larock method enables a one-pot synthesis of substituted quinolines
via a Heck reaction of 2-bromoanilines and allylic alcohols followed by
dehydrogenation with diisopropyl azodicarboxylate (DIAD).
M. T. Stone, Org. Lett., 2011,
13, 2326-2329.
A novel copper-catalyzed [5 + 1] annulation of 2-ethynylanilines with an N,O-acetal
gives quinoline derivatives with an ester substituent on the 2-position. A
combination of CuBr2 and trifluoroacetic acid (TFA) promotes a [5 +
1] annulation of 2-ethynylaniline with ethyl glyoxylatein the presence of
piperidine.
N. Sakai, K. Tamura, K. Shimamura, R. Ikeda, T. Konakahara, Org. Lett., 2012,
14, 836-839.
Highly substituted 3-iodoquinolines bearing different alkyl and aryl moieties
can be synthesized in good yields by a regioselective 6-endo-dig iodocyclization
of 2-tosylaminophenylprop-1-yn-3-ols with molecular iodine under mild conditions.
The resulting 3-iodoquinolines can be further functionalized by various coupling
reactions.
S. Ali, H.-T. Zhu, X.-F. Xia, K.-G. Ji, Y.-F. Yang, X.-R. Song, Y.-M. Liang, Org. Lett., 2011,
13, 2598-2601.
Upon photoirradiation of o-alkynylaryl isocyanides in the presence of
iodine, an intramolecular cyclization affords the corresponding
2,4-diiodoquinolines in good yields. 2,4-Diiodoquinolines can be employed in
regioselective transition metal-catalyzed cross-coupling reactions.
T. Mitamura, A. Ogawa, X. Pan, J. Org. Chem., 2011,
76, 1163-1166.
A Pd-catalyzed Wacker-type oxidative cyclization under air allows the
construction of 2-methylquinolines in good yields under mild conditions.
Z. Zhang, J. Tang, Z. Wang, Org. Lett., 2008,
10, 173-175.
A direct reaction between 2-aminobenzylic alcohol derivatives and either ketones
or alcohols in the presence of a base and benzophenone as hydride scavenger
allows the synthesis of polysubstituted quinolines without any transition-metal
catalyst.
R. Martínez, D. J. Ramón, M. Yus, J. Org. Chem., 2008,
73, 9778-9780.
An efficient and convenient nickel-catalyzed cyclization of 2-iodoanilines
with alkynyl aryl ketones gives 2,4-disubstituted quinolines. Naturally
occurring quinoline derivatives have been prepared in good yields. The
mechanism is discussed.
R. P. Korivi, C.-H. Cheng, J. Org. Chem., 2006, 71, 7079-7082.
A direct convergent two-component synthesis of quinolines from α,β-unsaturated
ketones and o-aminophenylboronic acid derivatives is regiocomplementary
to the traditional Skraup-Doebner-Von Miller synthesis and proceeds under basic
rather than strongly acidic conditions.
J. Horn, S. P. Marsden, A. Nelson, D. House, G. G. Weingarten, Org. Lett.,
2008,
10, 4117-4120.
An efficient reductive cyclization of o-nitrocinnamoyl compounds was
achieved by employing Hantzsch 1,4-dihydropyridine diethyl ester as a biomimetic
reducing agent in the presence of catalytic palladium on carbon. This approach
was successfully applied to the synthesis of substituted quinolines.
R.-G. Xing, Y.-N. Li, Q. Liu, Y.-F. Han, X. Wei, J. Li, B. Zhou, Synthesis, 2011,
2066-2072.
Reduction of secondary and tertiary o-nitrophenyl propargyl alcohols followed
by acid-catalyzed Meyer-Schuster rearrangement gave 2-substituted and
2,4-disubstituted quinolines, respectively in good yields.
M. J. Sandelier, P. DeShong, Org. Lett., 2007,
9, 3209-3212.
A one-pot dehydrogenative Povarov/oxidation tandem reaction of N-alkyl anilines
with mono- and 1,2-disubstituted aryl and alkyl olefins enables the synthesis of
a various substituted quinolines. The simple protocol uses cheap and benign
iron(III)chloride as the Lewis acid catalyst and a TEMPO oxoammonium salt as a
nontoxic, mild, efficient oxidant.
H. Richter, O. G. Mancheño, Org. Lett., 2011,
13, 6066-6069.
A domino reaction of benzimidoyl chlorides with 1,6-enynes gives quinoline
derivatives via palladium-catalyzed Sonogashira coupling and subsequent
cyclization. The reaction conditions and the scope of the process are examined,
and a plausible mechanism is proposed. The procedure is simple, rapid, and
general, and the substrates are readily available.
G.-L. Gao, Y.-N. Niu, Z.-Y. Yan, H.-L. Wang, G.-W. Wang, A. Shaukat, Y.-M. Liang, J. Org. Chem., 2010,
75, 1305-1308.
The intramolecular cyclization of 1-azido-2-(2-propynyl)benzene proceeds
smoothly in the presence of electrophilic reagents in CH3NO2
at room temperature or in the presence of catalytic amounts of AuCl3/AgNTf2
in THF at 100°C to afford the corresponding quinolines 2 in good to high yields.
Z. Huo, I. D. Gridnev, Y. Yamamoto, J. Org. Chem., 2010,
75, 1266-1270.
4-Aryl and 4-vinyl quinolines were prepared via a sequential procedure involving
regioselective rhodium-catalyzed hydroarylation/hydrovinylation of
β-(2-aminophenyl)-α,β-ynones with arylboronic acids or potassium aryl and vinyl
trifluoroborates, followed by nucleophilic attack of the amino group onto the
carbonyl.
G. Abbiati, A. Arcadi, F. Marinelli, E. Rossi, M. Verdecchia, Synlett, 2006,
3218-3224.
A simple, efficient and convenient copper-catalyzed method allows the synthesis
of quinoline-2-carboxylate derivatives through sequential intermolecular
addition of alkynes onto imines and subsequent intramolecular ring closure by
arylation at room temperature.
H. Huang, H. Jiang, K. Chen, H. Liu, J. Org. Chem., 2009,
74, 5476-5480.
Cu-catalyzed aerobic cyclization of N-(2-alkynylaryl)enamine carboxylates
via intramolecular carbo-oxygenation of alkynes gives highly substituted
quinolines. This strategy was further applied for N-alkynylamidines
leading to imidazole and quinazoline derivatives.
K. K. Toh, S. Sanjaya, S. Sahnoun, S. Y. Chong, S. Chiba, Org. Lett., 2012,
14, 2290-2292.
A single-step conversion of various N-vinyl and N-aryl amides
to the corresponding pyridine and quinoline derivatives involves amide activation with trifluoromethanesulfonic anhydride in the
presence of 2-chloropyridine followed by π-nucleophile addition to the activated
intermediate and annulation. Compatibility of this chemistry with various functional groups is
noteworthy.
M. Movassaghi, M. D. Hill, O. K. Ahmad, J. Am. Chem. Soc.,
2007,
129, 10096-10097.
The direct conversion of amides, including sensitive N-vinyl amides,
to the corresponding trimethylsilyl alkynyl imines followed by a
ruthenium-catalyzed protodesilylation and cycloisomerization gives various
substituted pyridines and quinolines.
M. Movassaghi, M. D. Hill, J. Am. Chem. Soc.,
2006, 128, 4592-4593.
Pyridine N-oxides were converted to 2-aminopyridines in a one-pot fashion
using Ts2O-tBuNH2 followed by in situ deprotection
with TFA. The amination proceeded in high yields, excellent 2-/4-selectivity,
and with good functional group compatibility.
J. Yin, B. Xiang, M. H. Huffman, C. E. Raab, I. W. Davies, J. Org. Chem., 2007,
72, 4554-4557.
