2-(5-Arylterphenyl-4-yl)quinolines from 2-methylquinoline and 1-(het)aryl-3-phenylprop-2-yn-1-ones in just a one step: A miracle of molecular interplay

Article abstract of DOI:10.1016/j.mencom.2018.05.012

2-Methylquinoline reacts with 1-(het)aryl-3-phenylprop-2-yn-1-ones under mild transition metal-free conditions (55–60 °C, 20 mol% KOH, H2O, MeCN) to afford 2-{5’-(het)aryl[1,1’: 3’,1”]terphenyl-4’-yl}quinolines in up to 35% yield. The reaction likely proceeds via the intermediate 1,3-dipole followed by the double nucleophilic vinylation of the methyl group with two molecules of ynone and subsequent elimination of (het)arenecarboxylic acid.

Full text of DOI:10.1016/j.mencom.2018.05.012

Mendeleev
Communications
Mendeleev Commun., 2018, 28, 267–269
2-(5-Arylterphenyl-4-yl)quinolines from 2-methylquinoline
and 1-(het)aryl-3-phenylprop-2-yn-1-ones in just a one step:
a miracle of molecular interplay
Boris A. Trofimov,* Kseniya V. Belyaeva, Lina P. Nikitina,
Andrei V. Afonin and Alexander V. Vashchenko
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences,
6
64033 Irkutsk, Russian Federation. Fax: +7 3952 419 346; e-mail: boris_trofimov@irioch.irk.ru
DOI: 10.1016/j.mencom.2018.05.012
2
1
2
-Methylquinoline reacts with 1-(het)aryl-3-phenylprop-2-yn-
-ones under mild transition metal-free conditions (55–60 °C,
Ph
Ph 20 mol% KOH
0 mol% KOH, H O, MeCN) to afford 2-{5'-(het)aryl-
2
H2O, MeCN
+
2
N
[
1,1':3',1'']terphenyl-4'-yl}quinolines in up to 35% yield.
N
Me
55–60 °C,
The reaction likely proceeds via the intermediate 1,3-dipole
followed by the double nucleophilic vinylation of the methyl
group with two molecules of ynone and subsequent elimination
of (het)arenecarboxylic acid.
Ar
up to 35%
Ph
4
8–96 h
Ar
O
Ar = Ph, 4-O2NC6H4, 2-furyl
Activation of nitrogen aromatic heterocycles by the zwitterion
formation with electron-deficient acetylenes is now dynamically
developed. This concept permitted a number of synthetically
important functionalizations and reactions of azines and azoles to
be implemented. Just to mention a few: annulation of cyano
version of ynone 2 remains 47% (yields of product 3a are 12%
based on acetylene taken and 25% based on acetylene consumed).
Quinolines 3 were purified by chromatography. As by-products,
the corresponding acids 4a–c were isolated (see Scheme 1).
The structures of quinolines 3a,b were established by single
1
2
‡
propargylic alcohols with pyridine nucleus, functionalization
crystal X-ray analysis (Figure 1).
3
and ring-opening of pyridines under the action of electron-
As follows from the X-ray diffraction data, molecules 3a,b are
essentially non-planar. The dihedral angle between the quinoline
cycle plane and the C(6)–C(9)C(20)C(21) phenyl ring plane
2
4,5
6–13
deficient acetylenes, C -vinylation and functionalization
imidazoles.
of
Here we disclose one more example of nitrogen heterocycle
activation under the action of electron-deficient acetylenes that
results in formation of the unexpected molecular structure.
Namely, 2-methylquinoline 1 and two molecules of 1-(het)aryl-
2
0 mol% KOH,
H2O, MeCN
O
R
+
2 Ph
5
5–60 °C
N
Me
3
2
-phenylprop-2-yn-1-ones 2a–c are surprisingly assembled to
-{5'-(het)aryl[1,1':3',1'']terphenyl-4'-yl}quinolines 3a–c in 7–35%
1
2a–c
5
4
4
a
O
unoptimized yields (Scheme 1). The reaction proceeds at 55–60°C
6
7
3
2
Ph
3'
+
R
in the presence of 20 mol% of KOH, 5 equiv. of H O in MeCN
2
1
4'
†
8a
2'
1'
OH
a–c
for 48–96 h and does not require any transition metal catalysts.
N
8
4
5
'
The process was controlled by IR spectroscopy and stopped
6'
–
1
R
Ph
after disappearance of the absorption bands at 2198–2220 cm
the stretching vibrations of the triple bond in ynones 2).
Oddly, the best result for product 3a has been obtained at the
reactant molar ratio 1:1, while with two molar excess of ynone
3
3
3
a 96 h, 35%
b 48 h, 10%
c 72 h, 7%
a R = Ph
b R = 4-O NC H
c R = 2-furyl
(
2
6
4
2
a relative to quinoline 1, the process slows down and the con-
Scheme 1
from C -Ph), 7.40 (m, 1H, H-6), 7.36 (m, 1H, p-H from C -Ph), 7.16
†
5'
1'
2
-(5'-Phenyl[1,1':3',1'']terphenyl-4'-yl)quinoline 3a. A solution of
-methylquinoline 1 (0.143 g, 1.0 mmol) in MeCN (0.5 ml) and KOH
0.012 g, 20 mol%) were subsequently added to the solution of ynone 2a
0.206 g, 1.0 mmol) in MeCN (0.5 ml) and H O (0.090 g, 5.0 mmol). The
Ph
3'
5'
2
(
(
(m, 2H, o-H from C -Ph; 2H, o-H from C -Ph), 7.06 (m, 2H, m-H
Ph Ph Ph
3
'
1'
5'
from C -Ph; 2H, m-H from C -Ph; 2H, m-H from C -Ph), 7.01 (d,
Ph Ph
3
13
2
1H, H-3, J
H3,H4
8.6 Hz). C NMR (100.62 MHz, CDCl ) d: 150.3 (C ),
3
2
8a
3'
5'
3'
5'
mixture was stirred at 55–60°C for 96 h. The solvent was removed, the
subsequent column chromatography afforded quinoline 3a (0.075 g, 35%)
as a white powder, mp 247–249°C (EtOH). Starting 2-methylquinoline 1
147.7 (C ), 142.7 (C , C ), 141.5 (i-C from C -Ph; i-C from C -Ph),
4'
1'
1'
4
141.4 (C ), 140.6 (C ), 137.7 (i-C from C -Ph), 134.8 (C ), 129.8 (m-C
3'
5'
8
7
from C -Ph; m-C from C -Ph), 129.3 (C ), 129.2 (C ), 129.0 (m-C from
1'
1'
3'
5'
(0.045 g, conversion was 100% as it was taken in a two molar excess, the
C -Ph), 128.6 (o-C from C -Ph), 127.9 (o-C from C -Ph; o-C from C -Ph),
5
3
1'
3'
overflow quantity was returned) and ynone 2a (0.012 g, conversion was 94%)
127.8 (C ), 124.8 (C ), 127.4 (p-C from C -Ph; p-C from C -Ph; p-C
–1
1
5'
2'
6'
6
4a
were recovered. IR (microlayer, n/cm ): 1599, 1618 (C=C). H NMR
400.13 MHz, CDCl ) d: 7.74 (m, 1H, H-8), 7.72 (s, 1H, H-2'; m, 1H,
from C -Ph), 126.6 (C , C ), 126.3 (C ), 126.1 (C ). Found (%): C, 91.02;
(
H, 5.17; N, 3.27. Calc. for C H N (%): C, 91.42; H, 5.32; N, 3.23.
3
33 23
3'
3
H-6'; 2H, o-HPh from C -Ph), 7.70 (d, 1H, H-4, J
3
4
8.6 Hz), 7.62 (m,
For the syntheses and characteristics of compounds 3b,c, see Online
Supplementary Materials.
H ,H
3'
1
H, H-5), 7.53 (m, 1H, H-7), 7.44 (m, 1H, p-HPh from C -Ph; 1H, p-H
Ph
©
2018 Mendeleev Communications. Published by ELSEVIER B.V.
–
267 –
on behalf of the N. D. Zelinsky Institute of Organic Chemistry of the
Russian Academy of Sciences.

Mendeleev Commun., 2018, 28, 267–269
(
a)
C(25)
C(26)
2
OH–
2 of 2
C(24)
C(23)
1
–
H2O
N
R
Me
O
N
CH2
O
C(27)
C(22)
C(21)
Ph
Ph
C(19)
C(10)
C(11)
C(20)
C(9)
C(18)
C(13)
C(15)
C(14)
C(4)
R
C(16)
C(17)
C(5)
N(1)
C(6)
C(7)
A
B
C(1)
C(12)
C(2)
C(3)
C(8)
Ph
O
Ph
R
Ph
R
C(28)
C(29)
C(30)
C(31)
N
R
O
N
O
C(33)
C(32)
Ph
O
R
Ph
R
Ph
O
H
O
R
C
D
(b)
Ph
R
H2O
OH–,
– RCO H,
3
–
N
O
2
Ph
O
–
2
O
Ph
R
R
E
Scheme 2
Figure 1 X-ray structure of (a) 2-(5'-phenyl[1,1':3',1'']terphenyl-4'-yl)-
quinoline 3a and (b) 2-(4-nitro-5'-phenyl[1,1':3',1'']terphenyl-2'-yl)quinoline
3
b. Thermal ellipsoids set at 50% probability.
towards nucleophilic addition to ynone 2 (Scheme 2). Con-
secutive vinylation of one C–H bond by two molecules of ynone 2
leads to intermediate dienic carbanion C. The carbanionic center
is 68.0 and 56.3° for 3a and 3b, respectively. The dihedral angles
between the C(6)–C(9)C(20)C(21) phenyl ring plane and the
C(10)–C(13)C(18)C(19), C(22)–C(27) and C(28)–C(33) phenyl
rings planes are 36.9, 61.9 and 75.6°, respectively, in the molecule
of 3a. The dihedral angles between the C(6)–C(9)C(20)C(21)
phenylring plane and the C(10)–C(13)C(28)C(29), C(14)–C(19)
and C(22)–C(27) phenyl rings planes are 43.3, 50.3 and 57.5°,
respectively, in the molecule of 3b.
of the latter is neutralized by the proton from the CH group to
2
deliver the intermediate D. The CH carbanionic center of the latter
undergoes intramolecular nucleophilic addition to carbonyl group
with the six-member ring closing. After elimination of molecule
of (het)arenecarboxylic acid from intermediate E with simul-
taneous recovery of ynone 2 (reversibly bound with zwitterionic
center), quinoline 3 is finally assembled (see Scheme 2).
The structures of compounds 3b,c were also proved by the
Low to moderate yields of products 3a–c (7–35%) despite
the almost complete conversion of ynones 2a–c (94–100%) and
2-methylquinoline 1a (83–100%) may be related to the oligo-
merization of reactants and side reactions of the reactive inter-
mediates (e.g., further generation of trienes and longer polyenes
like formation of dienic carboanion C). The adverse effect of excess
ynone 2 on the assembly is probably due to a partial trapping
of KOH giving catalytically inactive species (e.g. potassium
benzoate). Lower yields of 3b (10%) and 3c (7%) compared to
1
3
C NMR spectroscopy, the signals being assigned on the basis
14
of the chemical shifts calculations by the GIAO method at the
1
5
B3LYP/6-311G(d,p) level with GAUSSIAN 09 program package
see Table S7, Online Supplementary Materials).
Assumingly, the 1,3-dipole A, reversibly generated from quino-
(
line 1 and ynone 2, activates the methyl substituent as CH-acid
‡
Crystal data for 3a. C H N, 0.77×0.5×0.24 mm, colorless block-
33
23
3
a (35%) could be explained by higher reactivity of the corre-
like crystal, orthorhombic, space group Pbca, 198670 reflections in total,
maximum q angle of 26.5°, 4655 independent reflections (completeness
sponding ynones 2b and 2c vs. 2a towards side oligomerization.
The reaction thus found has obviously a potential for further
development employing other substituted 2-methylquinolines
and ynones, that corresponds to the modern trend to use acetylenes
as universal chemical platform for arriving at the molecular
2
1
00.0%, Rint = 12.06%, R = 2.34%) and 3777 were greater than 2s(F ).
s
The final cell constants are a = 19.4314(12), b = 10.5145(6) and c =
3
=
22.0169(14) Å, Z = 8, V = 4498.3(5) Å . The final anisotropic full-matrix
2
least-squares refinement on F with 308 variables converged at R = 3.74%,
1
for the observed data and wR = 8.85% for all data. GOOF = 1.032, largest
2
16
complexity. The scope and limitations of this synthesis are now
–3
difference peak/hole 0.23/–0.17 eÅ . On the basis of the final model, the
calculated density was 1.280 g cm–3 and F(000) = 1824 e–.
under investigation. It should be mentioned that poly(het)aryl-
benzenes are known to be prospective optoelectronic materials and
Crystal data for 3b. 2(C H N O ), 0.153×0.246×0.690 mm, white
33
22
2
2
–
17–20
21,22
OLEDs.
They are also used in the synthesis of dendrimers,
block-like crystal, triclinic, space group P1, 109115 reflections in total,
maximum q angle of 27.65°, 11331 independent reflectiions (completeness
23,24
and fullerene fragments.
Diverse 2-arylquinolines exhibit good
25
9
8.9%, R = 13.18%, R = 6.98%) and 7766 (68.54%) were greater than
fluorescence properties and serve as precursors for photolabile
int
s
2
26
2s(F ). The final cell constants are a = 12.1392(15), b = 12.6841(15) and
compounds. Therefore, this approach may significantly extend
c = 17.1616(18) Å, Z = 2, a = 110.717(3)°, b = 90.129(4)°, g = 96.142(4)°,
areas of their application, particularly in view of the presence
of media-responsive quinoline moiety (potential sensors) in the
synthesized molecules (see, e.g., ref. 27).
3
V = 2455.1(5) Å . The final anisotropic full-matrix least-squares refinement
2
on F with 308 variables converged at R = 9.99%, for the observed data
1
and wR = 29.66% for all data. GOOF = 1.084, largest difference peak/hole
2
–
3
0
.71/–0.48 eÅ . On the basis of the final model, the calculated density
was 1.295 g cm and F(000) = 1000 e .
–
3
–
This work was supported by the Russian Foundation for Basic
Research (grant no. 18-03-00762_a). The main results were
obtained using the equipment of Baikal Analytical Center of Col-
lective Using SB RAS.
CCDC 1573603 and 1812576 contain the supplementary crystallographic
data for this paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via http://www.ccdc.cam.ac.uk.
–
268 –

Mendeleev Commun., 2018, 28, 267–269
R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant,
Online Supplementary Materials
S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene,
J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts,
R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W.
Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth,
P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, Ö. Farkas,
J. B. Foresman, J. V. Ortiz, J. Cioslowski and D. J. Fox, Gaussian 2009,
Gaussian, Inc., Pittsburg, 2009.
Supplementary data associated with this article can be found
in the online version at doi: 10.1016/j.mencom.2018.05.012.
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