A Mild Rhodium Catalyzed Direct Synthesis of Quinolones from Pyridones: Application in the Detection of Nitroaromatics

Article abstract of DOI:10.1021/acs.joc.7b01932

A rhodium catalyzed direct regioselective oxidative annulation by double C-H activation is described to synthesize highly substituted quinolones from pyridones. The reaction proceeds at mild conditions with broad scope and wide functional group tolerance. These novel quinolones were explored to recognize nitroaromatic compounds.

Full text of DOI:10.1021/acs.joc.7b01932

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Article
A Mild Rhodium Catalyzed Direct Synthesis of Quinolones
from Pyridones: Application in the Detection of Nitroaromatics
Aniruddha Biswas, Dipanjan Giri, Debapratim Das, Anurima De, Sanjib Kumar Patra, and Rajarshi Samanta
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.7b01932 • Publication Date (Web): 13 Sep 2017
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A Mild Rhodium Catalyzed Direct Synthesis of
Quinolones from Pyridones: Application in the
Detection of Nitroaromatics
Aniruddha Biswas, Dipanjan Giri, Debapratim Das, Anurima De, Sanjib K. Patra* and Rajarshi Samanta *
Department of Chemistry, Indian Institute of Technology Kharagpur, Kharagpur 721302, India.
Supporting Information Placeholder
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ABSTRACT: A rhodium catalyzed direct regioselective oxidative annulation by double CꢀH activation is described
to synthesize highly substituted quinolones from pyridones. The reaction proceeds at mild conditions with broad scope
and wide functional group tolerance. These novel quinolones were explored to recognize nitroaromatic compounds.
INTRODUCTION:
Recently, polyaromatic and heteroaromatic compounds as organic πꢀconjugated materials have attracted significant
1
attention due to their wide application in detection of explosive nitroaromatic compounds (NACs). To prepare those
heteroaromatic compounds classical methods using difunctionalized starting materials were well recognized in the
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literature . Alternative approaches using monofunctionalized arenes were also extensively studied by mainly Satoh
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and Miura group. Arguably, the most effective and direct method to synthesize benzoꢀfused heteroaromatics is the
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transition metal catalyzed dehydrogenative annulation of heteroarenes with internal alkynes (scheme 1). For instance,
Wu first reported the transition metal catalyzed oxidative annulation of arenes without any assistance from chelation
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group . Recently, this strategy was efficiently extended by Cramer group and successively by Tsui and Joo group.
Since the pioneering development of Rh(III) catalyzed directed oxidative annulations of phenylazoles with alkynes by
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a,b
8c
Satoh and Miura group (scheme 1a) and of 2ꢀphenyl pyridines with alkynes by You group (Scheme 1b), many
transition metal catalyzed elegant methods were emerged to construct polyarenes via oxidative annulation strategy
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,10
using heteroatom containing directing groups.
Moreover, Chatani group recently developed cost effective Ni
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catalyzed oxidative annulaion using benzamide directing group. However, in contrast to these tremendous
development made with functionalized arenes, there are very limited reports on transition metal catalyzed direct
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2
annulations on electron deficient nitrogen containing heterocycles especially at mild conditions. Quinolones are well
admired in organic and medicinal chemistry for their frequent appearance in bioactive molecules and functional
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materials. The conventional synthetic methods to prepare this scaffold do not provide sufficient control over the
more inert carbocycle part. In continuation with our and others works on recent direct pyridone functionalizations at
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its C3 , C4 and C6 positions, we envisaged that a new synthetic strategy starting from pyridone would provide
poly arylated quinolones via oxidative annulation.
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Scheme 1: Conventional method versus our approach
Herein, we report a Rh(III)ꢀcatalyzed directed dehydrogenative annulation of pyridones and alkynes to provide
quinolone derivatives. Moreover, a thorough screening of the obtained molecules was executed to find a potential
nitroaromatics detector.
RESULTS AND DISCUSSION:
The required reaction parameters were initially scrutinized with various Nꢀprotected 2ꢀpyridones and diphenyl
acetylene (2a) in the presence of [(Cp*RhCl
2
)
2
] (2 mol%, Cp*= 1,2,3,4,5ꢀpentamethyl cyclopentadiene), Cu(OAc)
2.0 equiv.), AgOAc (10 mol%) in MeOH at 100 °C. Various protecting groups like methyl (1a), benzyl (1b), acetyl
1c) and pivaloyl (1d) did not afford the desired annulated product (Table 1, entries 1ꢀ4). Gratifyingly, when 2ꢀpyridyl
2
(
(
group (2ꢀPy) was chosen as the protecting group (1e), our desired annulated product was obtained in 82% isolated
yield (Table 1, entry 5). To improve the yield further, several reaction conditions were explored. Screening of other
silver salts (Table 1, entries 6ꢀ11) did not improve the yield further. Satisfyingly, the isolated yield was improved to
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7% (Table 1, entry 12) when the reaction was performed at 40 °C. In general, screening of other solvents (Table 1,
entries 13ꢀ15) did not able to improve the isolated yields further.
To explore the scope and limitations with our most favourable established catalytic system, different substituted
pyridones (scheme 2 and 3) were tested. Substitutions at the C3 position of 2ꢀpyridones with variant electronic and
steric properties provided satisfied yields of the desired products (scheme 2, 3eꢀ3l). Gratifyingly, pyridones with
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electronꢀdonating groups at their C3 position smoothly underwent to give the desired products in good to excellent
yields (scheme 2, 3eꢀ3j).
a
Table 1. Optimization table
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b
Entry PG
Additive
AgOAc
AgOAc
AgOAc
AgOAc
Solvent
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
EtOH
Temp (°C)
100
100
100
100
100
100
100
100
100
100
100
40
Yield(%)
n.d.
n.d.
n.d.
n.d.
82
80
80
trace
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87
80
trace
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Me (1a)
Bn (1b)
Ac (1c)
Piv (1d)
2ꢀPy (1e) AgOAc
2ꢀPy
2ꢀPy
2ꢀPy
2ꢀPy
2ꢀPy
2ꢀPy
2-Py
2ꢀPy
2ꢀPy
2ꢀPy
AgSbF6
Ag
AgNTf
AgPF
AgNO
AgBF4
2
CO
3
2
6
3
11
12
13
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AgOAc
AgOAc
AgOAc
AgOAc
40
40
40
t
AmOH
MeCN
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a
Reaction conditions: 1a (0. 1 mmol), 2a (0.22 mmol), [(Cp*RhCl ) ] (2 mol%), additive (10 mol%), Cu(OAc) (0.2
mmol), 100 °C, 24 h, 0.05 M. Isolated yields. DCE= 1,2 dicholoroethane. n.d. = not detected.
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2
2
b
However, electronꢀwithdrawing groups at that position provided corresponding products in moderate to good yields
(
scheme 2, 3kꢀ3l). To our delight, C4 substituted pyridones provided the desired products in moderate to good yield
(scheme 2, 3mꢀ3n). Interestingly, reaction of isoquinolone derivative afforded the respective annulated product in
acceptable yield (Scheme 2, 3o). Next, we turned our attention to make the protocol more general by the reactions of
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e with different alkynes. Diarylalkynes having electronically varying substituents gave desired annulated products in
moderate to excellent yields (Scheme 2, 4aꢀ4f). Interestingly, 3, 5ꢀdiꢀtrifluromethyl diphenyl acetylene afforded
corresponding annulated product in moderate yield (Scheme 2, 4g). It was noteworthy that sterically more challenging
dinaphthyl acetylene derivative smoothly afforded respected annulated product, albeit in moderate yield (Scheme 2,
4
h). Notably, heterocycle attached acetylene like dithiophenyl acetylene also provided desired annulated product in
good yield (Scheme 2, 4i). We were delighted to see that less reactive dialkyl acetylenes also worked under the
developed conditions with lesser yields of desired products (Scheme 2, 4j-4k). Unfortunately, when we explored our
reaction with unsymmetrical alkynes, there was formation of inseparable mixture of regioisomeric products. As a
demonstration of scalability, pyridone 1e could be transformed into its corresponding final product in gram scale with
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8% yield (Scheme 2, 3e).
Strikingly, the annulation in 4ꢀpyridone scaffold could be controlled in one double bond keeping the window open for
further modifications in nitrogen containing ring (Scheme 3, 3p). Beside the formation of substituted quinolones, the
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method was further extended for the synthesis of acridone derivative (Scheme 3, 3q). Aside from pyridine protecting
group, pyrimidyl protected 4ꢀpyridone would also provide the corresponding annulated product in excellent yield
(
Scheme 3, 3r).
Ar
[Cp*RhCl2]2
(2 mol%)
Ar
Ar
R
R
O
+
Ar
Ar
0
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N
O
MeOH, 40 °C
N
Py
3
1e-1o
2
Ar Py
Ph Py
N
R = Me, 3f, 86%
Ph Py
N
Ph Py
N
Ph
O
= SiMe , 3g, 92%
Ph
Ph
O
Ph
Ph
O
R
3
= OBn, 3h, 77%
Ph
= Ph, 3i, 88%
Ph
= N(SO2Ph)2, 3j, 96%
Ph
Ph
Ph
a
3
e, 92%, (78%)
= CF , 3k, 77%
3m, 68%
3
= CN, 3l, 69%
Ph Py
Ph
Ph
Ph
O
1
Ph
Ph
N
O
Ar = 4-PhMe, 4a, 92%
= 4-PhCl, 4b, 83%
Py
N
Ar1 = 4-PhBr, , 80%
4c
N
= 4-PhF, 4d, 63%
Ph OBn
Py
t
= 4-Ph Bu, 4e, 63%
3n, 87%
O
3
Ar1
Ar1
o, 41%
Ar1
= 4-PhCF3, 4f, 88%
F3C
CF3
CF3
CF3
Py
F3C
F3C
CF3
N
O
N
Py
S
h, 59%b
4
4g, 72%
CF3
O
S
S
N
O
N
O
N
O
Py
Py
Py
S
4j, 41%c
4k, 34%c
4i, 84%
Scheme 2: Substrate scope: Reaction conditions: 1e-1o (0.1 mmol), 2 (0.22 mmol), [(Cp*RhCl ) ] (2 mol%),
2
2
a
b
AgOAc (10 mol%), Cu(OAc)
conditions: 60 ºC. Reaction conditions: solvent ethanol and at 80 ºC.
2
(2 equiv.), 40 °C, 24ꢀ36 h. reaction performed at 1 gm scale. Reaction
c
1
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Finally, the 2ꢀpyridyl directing group was removed via twoꢀstep quaternization−hydride reduction process at room
temperature to furnish tetraphenyl quinolone derivative 5 in very good yield (Scheme 4a). To check the electronic
effects of pyridone substrates during the transformation, 1k and 1h were chosen to react with 2a under standard
reaction conditions. Formation of 3k and 3h were found in 1.8:1 ratio (Scheme 4b). This result suggests that the
electronꢀwithdrawing group at the C3 position of pyridone is kinetically more favoured for the developed protocol.
Further, the electronic effects of alkyne substrates were studied through substrates 2a and 2f (Scheme 4c). The
product ratio of 4a and 4f was found to be 2.1:1, indicating that electronꢀdonating groups at alkyne substituents were
kinetically more favoured. Moreover, a kinetic isotope effect (k /k = 1.75) was observed from two parallel reactions
H
D
of 1e and 6ꢀ[D ]ꢀ1e with 2a (for details, see the experimental section).
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Scheme 3: Substrate scope: Reaction conditions: 1pꢀ1r (0.1 mmol), diphenylacetylene (0.22 mmol),
[(Cp*RhCl ) ] (2 mol%), AgOAc (10 mol%), Cu(OAc) (2 equiv.), 40 °C, 24ꢀ36 h. Pym= 2ꢀpyrimidyl.
2 2 2
Scheme 4: Protecting group removal and control experiments
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Based on the previous literature precedents , a plausible mechanism for the dehydrogenative annulation of pyridones
is illustrated in scheme 5. Initially, with the help of Cu(OAc) and AgOAc a cationic Rh(III) species is generated.
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Next the pyridine directed CꢀH cleavage appears to occur at the C6 position of 2ꢀpyridone to generate rhodacycle
intermediate A presumably via acetate assisted concerted metalationꢀdeprotonation (CMD) pathway. Further, alkyne
2a coordinates at rhodium centre to give intermediate B and subsequent migration of the rhodiumꢀcarbon bond across
the alkyne results in the formation of a seven membered rhodacycle intermediate C. Apparently this intermediate
triggers a second intramolecular CꢀH activation leading to a more stable five membered rhodacycle E via intermediate
D. Accordingly, the five membered rhodacycle E undergoes second alkyne insertion and subsequent migration affords
the desired annulated product 3e with Rh(I) species via reductive elimination. Furthermore, the active Rh(III) species
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is regenerated from Rh(I) species by Cu(II) mediated oxidation. In general, the initial formation of the intermediate A
guided the obtained regioselectivity in the final product.
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Scheme 5: Plausible Mechanism
Among the synthesized quinolones, 4h and 4i having substituted naphthalene and thiophene units at the fused ring
system exhibit intense emission at λem of 438 and 466 nm respectively, while phenyl substituted quinolones (3h, 3i,
ꢀ
5
3
m, 3o and 3q) are moderately blue emissive in solution as studied in chloroform in 1 × 10 M concentration at
ambient temperature. The photoluminiscent quantum yields (Φ) of the synthesized emissive quinolones are in the
range of 10ꢀ18% (quinine sulphate in 0.5 M H SO as reference). The relevant photophysical data of all the emissive
2
4
molecules are summarized (Table S2, see supporting information). In the recent years, large scale use of explosives by
terrorist groups has prompted the scientific community to develop novel and synthetically ease small molecule based
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chemosensors for easy, rapid and selective detection of explosives. Nitroaromatic (NAC) compounds such as
trinitrotoluene and picric acid are essential energetic materials and are heavily used as component in landmines and
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explosive materials. Being rigid πꢀconjugated polyaromatic compounds, naphthalene and thiophene substituted
quinolones (4hꢀ4i) can undergo favourable supramolecular πꢀπ interaction with nitroaromatic ring resulting in
fluorescence quenching through electron transfer from quinolones to electron deficient NACs. Thus, the ability of the
synthesized emissive molecules to act as small molecule fluorescent probes for the detection of NACs was
investigated in solution phase (Figure 1). Interestingly, 4h having significant quantum yield (18%) shows good
sensitivity towards the electron deficient nitroaromatic compounds such as nitrobenzene, nitrotoluene, 2,6ꢀ
dinitrotoluene, 2,4ꢀdinitrobenzene, 2,4ꢀdinitrophenol and most importantly picric acid (PA). The relative emission
quenching ability of 4h towards various electron deficient nitroaromatics has been summarized as bar diagram (Figure
S6, see supporting information), showing remarkable visual fluorescence quenching upon the addition of picric acid
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which can be visualized by naked eye (Figure S11, see supporting information). The quenching behaviour of the
o o
probeꢀNAC supramolecular complex was analyzed by the SternꢀVolmer (SV) equation, I /I=1+ KSV[Q], where I and I
are the fluorescence intensities in the absence and presence of the quencher [Q] (KSV is the SternꢀVolmer rate
constant). The linear response in SternꢀVolmer plot for 4h, upon incremental addition of PA (Figure S10, see
supporting information), suggest static quenching mechanism. The highest quenching response was observed for PA
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−1
ꢀ7
with the Ksv value of 1.36 × 10
M
with excellent detection limit in the range of 2.2 × 10 M (52 ppm)
demonstrating 4h as a selective and efficient sensor for explosive picric acid.
ꢀ
5
Figure 1: (Left)
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Quenching of emission of the probe (4h in 1 × 10 M CHCl )
when treated with different nitroaromatics (NB: Nitrobenzene; NT: Nitrotoluene; NBA: Nitrobenzoic acid; HNB: pꢀHydroxy
nitrobenzene; DNP: 2,4ꢀDinitrophenol; DNT: 2,6ꢀDinitrotoluene; PA: Picric acid). (Right) Visual appearance of 4h before
and after addition of PA under 365 nm light.
In summary, we have demonstrated a Rh(III) catalyzed simple, efficient, site selective, dehydrogenative annulation
method for the preparation of polyꢀarylated quinolones directly from pyridones. The pyridyl directing group can
smoothly be removed after operation. The reaction proceeded at mild condition with broad scope and wide functional
group tolerance. The developed protocol would ensure an access towards novel πꢀconjugated organic molecules for
the detection of nitroaromatics. Highly blueꢀgreen light emitting nature of this class of functionalized quinolones can
also be explored as active materials in OLED application. To obtain more potent nitroaromatics detector, modification
of final polyarylated quinolones is under progress.
EXPERIMENTAL SECTION:
General information: Unless otherwise noted, all commercially available compounds were used as provided without
further purification. Solvents for chromatography were technical grade. Analytical thin layer chromatography (TLC)
was performed on Merck preꢀcoated silica gel 60 F254. Visualization on TLC was achieved by the use of UV light (254
nm). Solvents mixtures were understood as volume/ volume. Column chromatography was undertaken on silica gel
(
230ꢀ400 mesh). Chemical shifts were quoted in parts per million (ppm) referenced to the appropriate solvent peak or
0.0 ppm for tetramethylsilane. The following abbreviations were used to describe peak splitting patterns when
appropriate: br = broad, s = singlet, d = doublet, t = triplet, q = quartet, dd = doublet of doublet, td = triplet of doublet,
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ddd = doublet of doublet of doublet, m = multiplet. Coupling constants, J, were reported in hertz unit (Hz). The
spectra were fully decoupled by broad band proton decoupling. Chemical shifts were reported in ppm referenced to
3
the centre of a triplet at 77.16 ppm of chloroformꢀd (CDCl ). In case of Infrared (IR) spectra frequencies are given in
ꢀ
1
reciprocal centimetres (cm ), only selected absorbance peaks are reported and KBr is used as the matrix. Materials
were obtained from commercial suppliers or prepared according to standard procedures unless otherwise noted.
Substrates which are not commercially available were synthesised according to the reported procedures.
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General procedure for the synthesis of substituted 1-(2- Pyridyl)-2-pyridones:
Substituted 2ꢀhydroxypyridine (1 mmol), copper(I) iodide (10 mol %), and potassium carbonate (1 mmol) were added
to DMSO (2 mL), and then 2ꢀbromopyridine (2 mmol) was added. The mixture was stirred at 150 °C for 12 h under
nitrogen atmosphere. The resulting mixture was allowed to cool to room temperature and then quenched with water.
Organic layer was extracted with ethyl acetate, concentration under reduced pressure, and purified with silica gel
column chromatography using hexane/ethyl acetate (1:1ꢀ 100% EA, v/v) to afforded 2Hꢀ[1,2′ꢀbipyridin]ꢀ2ꢀ one in
5
0−90% yield.
Preparation of acetylenes:
A 100 mL round bottom flask with a magnetic stir bar was charged with copper iodide (0.1 equiv.), palladium acetate
0.05 equiv.), and triphenylphosphine (0.1 equiv.) in acetonitrile. The solution was degassed with nitrogen for 20 min.
28
(
Then, triethylamine (3 equiv.), aryl iodides (1 equiv.), and calcium carbide (3 equiv.) were added. The mixture was
stirred at room temperature overnight under nitrogen atmosphere. The reaction mixture was then filtrated through a
short plug of silica gel and washed with hexane. The filtrate was evaporated under vacuum to give the desired
compound. Then products were further purified by silica gel column chromatography.
General procedure for Rhodium (III) catalysed synthesis of polyarylated quinolones from pyridones:
A 10 mL screw cap vial was charged with 1ꢀ(2ꢀ Pyridyl)ꢀ2ꢀpyridone (0.1 mmol) dissolved in 2 mL of dry MeOH.
Diphenylacetylene (0.22 mmol), [Cp*RhCl ] (2 mol%), AgOAc (10 mol%), Cu(OAc) (2 equiv.) were added to the
2
2
2
reaction mixture at the room temperature. Reaction mixture was allowed to stir for 24ꢀ36 h at 40 ꢀ 100 °C. After the
completion of the reaction, solvent was removed under reduced pressure and purified by flash column
chromatography using hexane/ EtOAc (4:1ꢀ 1:1, v/v) mixture as the eluant.
Control experiments:
1
1
. Experiment with electronically variable 1-(2- Pyridyl)-2-pyridones:
k (0.1 mmol) and 1h (0.1 mmol) were dissolved in 2 mL of dry MeOH. Diphenylacetylene (0.22 mmol),
[Cp*RhCl ] (4 mol%), AgOAc (20 mol%), Cu(OAc) (0.4 mmol) were added to the reaction mixture at the room
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temperature. Reaction mixture was allowed to stir for 8 h at 40 °C. After the completion of the reaction time, solvent
was removed under reduced pressure. Product (3k) 31% and (3h) 17% were purified by flash column chromatography
using hexane/ EtOAc (2:1ꢀ1:1, v/v) mixture as the eluant. The product ratio was calculated based on the isolated
yields.
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60
2
. Experiment with electronically variable diphenylacetylene:
Ditolylacetylene (0.1 mmol) and 2f (0.1 mmol) were dissolved in 2 mL of dry MeOH. Then 1e (0.2 mmol),
[Cp*RhCl ] (4 mol%), AgOAc (20 mol%), Cu(OAc) (0.4 mmol) were added to the reaction mixture at the room
2
2
temperature. Reaction mixture was allowed to stir for 8 h at 40 °C. After the completion of the reaction time, solvent
was removed under reduced pressure. Product (4a) 43% and (4f) 20% were purified by flash column chromatography
using hexane/ EtOAc mixture (2:1 to 1:1, v/v) as the eluant. And the product ratio was calculated based on isolated
yields.
3. Large scale experiment:
1ꢀ(2ꢀPyridyl)ꢀ2ꢀpyridone (1 gm, 5.8 mmol), 1e was taken in a 25 mL sealed tube with teflon cap and dissolved in 10
mL of dry MeOH. Diphenylacetylene (2.58 gm, 14.5 mmol), [Cp*RhCl
equiv.) were added to the reaction mixture at the room temperature. Reaction mixture was allowed to stir for 36 h at
0 °C. After the completion of the reaction time, solvent was removed under reduced pressure. Product 3e was
2 2
] (1 mol%), AgOAc (10 mol%), Cu(OAc) (2
4
purified by flash column chromatography using hexane/ EtOAc (3:1, v/v) mixture as the eluant with 78% isolated
yield.
2
9
4
. Directing group removal:
,6,7,8ꢀtetraphenylꢀ1ꢀ(pyridinꢀ2ꢀyl)quinolinꢀ2(1H)ꢀone (3e) (350 mg, 0.66 mmol) was dissolved in 5 mL of dry
Cl in a 25 mL roundꢀbottom flask, filled with nitrogen. It was cooled to 0 °C in an ice bath. Then MeOTf (110
L, 1.0 mmol) was added to it and allowed to warm to room temperature with stirring for 24 h. Volatile materials
were evaporated off in vacuum. The residue was dissolved in 5 mL of dry CH OH and cooled to 0 °C. Then NaBH4
5
CH
2
2
ꢁ
3
(
100 mg, 2.7 mmol) was added in three portions over 10 minutes, and the flask was filled with nitrogen again. The
reaction mixture was allowed to warm to room temperature and stirred 8 h. The reaction mixture was quenched with
HCl (2 N) and extracted with ethyl acetate. Organic layer was dried over anhydrous Na SO , filtered, and concentrated
2
4
under reduced pressure. The product (5) was purified by flash chromatography acetone/ hexane (1:3, v/v) mixture as
eluant in 72% yield.
5. KIE Experiment 1: Following the general procedure of synthesis of polyarylated quinolones, two parallel
reactions were carried out with 1ꢀ(2ꢀPyridyl)ꢀ2ꢀpyridone (1e) and 6‐ D ‐ 1ꢀ(2ꢀPyridyl)ꢀ2ꢀpyridone (6-[D ]-1e) in 0.1
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mmol scale. Both the reactions were stopped after 3 h and product 3e was isolated separately by flash silica gel
column chromatography. The reactions were repeated two times. Based on the isolated yields, KIE values were
calculated as 1.78, and 1.73. So the average k
Analytical Data:
H D
/k was 1.75.
0
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,6,7,8-Tetraphenyl-1-(pyridin-2-yl)quinolin-2(1H)-one (3e): White amorphous solid, Yield (48.5 mg, 92%) : H
3
NMR (400 MHz, CDCl ) δ 8.27 (dd, J = 4.9, 1.9 Hz, 1H), 7.62 (d, J = 9.9 Hz, 1H), 7.33 (dd, J = 14.4, 7.4 Hz, 2H),
7.24 – 7.07 (m, 3H), 7.07 – 6.92 (m, 3H), 6.87 (dd, J = 7.5, 4.9 Hz, 2H), 6.83 – 6.70 (m, 8H), 6.65 (d, J = 7.4 Hz, 2H),
1
3
6
1
1
3
.60 (d, J = 9.9 Hz, 1H), 6.42 (q, J = 7.8 Hz, 2H), 6.04 (d, J = 7.7 Hz, 1H). C NMR (150 MHz, CDCl ) δ 163.9,
53.6, 148.3, 145.0, 139.9, 139.7, 139.6, 139.5, 139.2, 139.1, 138.2, 137.2, 136.3, 132.1, 131.5, 131.3, 131.0, 130.9,
30.7, 130.4, 127.9, 127.8, 127.5, 127.2, 126.8, 126.7, 126.7, 126.6, 126.4, 125.7, 125.6, 125.6, 122.2, 121.3, 120.9;
~
1
‐
+
ν
FTꢀIR:
= (KBr, cm ): 3054, 2924, 1669, 1601, 1549, 1492, 1407, 1278; HRMS (ESIꢀTOF) Calculated for [M+H] :
38 27 2
C H N O: Exact Mass: 527.2118; found: 527:2125
3-Methyl-5,6,7,8-tetraphenyl-1-(pyridin-2-yl)quinolin-2(1H)-one (3f): White amorphous solid, Yield (46.5 mg,
1
8
3
–
6%): H NMR (400 MHz, CDCl
3
) δ 8.27 (dd, J = 4.8, 1.9 Hz, 1H), 7.48 (s, 1H), 7.41 – 7.29 (m, 2H), 7.24 – 7.09 (m,
H), 7.01 (dd, J = 13.9, 7.0 Hz, 3H), 6.86 (dt, J = 9.4, 4.8 Hz, 2H), 6.82 – 6.71 (m, 8H), 6.65 (d, J = 6.9 Hz, 2H), 6.50
13
3
6.36 (m, 2H), 6.05 (d, J = 7.7 Hz, 1H), 2.14 (s, 3H). C NMR (150 MHz, CDCl ) δ 164.5, 153.9, 148.2, 143.7,
139.8, 139.6, 139.2, 138.7, 138.5, 138.2, 137.0, 136.3, 136.1, 132.1, 131.5, 131.3, 131.1, 130.9, 130.8, 130.5, 130.3,
129.6, 127.9, 127.8, 127.7, 127.4, 126.9, 126.7, 126.6, 126.5, 126.5, 126.3, 125.6, 125.5, 125.4, 122.1, 120.9, 17.5;
~
1
‐
+
ν
FTꢀIR:
= (KBr, cm ): 3056, 2920, 1654, 1589, 1551, 1492, 1411, 1269; HRMS (ESIꢀTOF) Calculated for [M+H] :
C
39
H
29
N
2
O: Exact Mass: 541.2274; found: 541.2277
5,6,7,8-Tetraphenyl-1-(pyridin-2-yl)-3-(trimethylsilyl)quinolin-2(1H)-one (3g): White amorphous solid, Yield (55
1
mg, 92%) : H NMR (400 MHz, CDCl
3
) δ 8.26 (d, J = 4.7 Hz, 1H), 7.74 (s, 1H), 7.40 – 7.28 (m, 2H), 7.21 – 7.14 (m,
3H), 7.04 – 6.94 (m, 3H), 6.92 – 6.69 (m, 10H), 6.65 (d, J = 7.7 Hz, 2H), 6.42 (q, J = 8.0 Hz, 2H), 6.05 (d, J = 7.7 Hz,
1
3
1
1
3
H), 0.15 (s, 9H). C NMR (100 MHz, CDCl ) δ 166.0, 154.0, 148.4, 146.7, 144.9, 139.8, 139.7, 139.6, 139.5, 139.1,
38.2, 136.8, 136.2, 133.5, 132.2, 131.5, 131.3, 131.0, 130.9, 130.8, 130.5, 130.3, 127.9, 127.7, 127.6, 127.4, 127.1,
~
1
ν
‐
126.8, 126.7, 126.6, 126.5, 126.3, 125.6, 125.5, 125.5, 122.0, 120.9, ꢀ1.6; FTꢀIR:
= (KBr, cm ): 3052, 2952, 1644,
+
1
592, 1494, 1406, 1365, 1261; HRMS (ESIꢀTOF) Calculated for [M+H] : C41
H
35
N
2
OSi: Exact Mass: 599.2513;
found: 599.2512
3-(Benzyloxy)-5,6,7,8-tetraphenyl-1-(pyridin-2-yl)quinolin-2(1H)-one (3h): White amorphous solid, Yield (48.7
1
mg, 77%): H NMR (400 MHz, CDCl
3
) δ 8.26 (d, J = 4.3 Hz, 1H), 7.27 (q, J = 3.0 Hz, 4H), 7.23 – 7.15 (m, 6H), 7.01
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6.96 (m, 2H), 6.93 – 6.81 (m, 5H), 6.79 – 6.70 (m, 7H), 6.63 (q, J = 7.4 Hz, 2H), 6.47 – 6.31 (m, 2H), 6.02 (d, J =
1
3
3
.7 Hz, 1H), 5.00 (s, 2H). C NMR (150 MHz, CDCl ) δ 159.9, 153.5, 148.2, 146.2, 142.1, 139.9, 139.6, 139.2,
38.7, 138.1, 137.2, 136.3, 135.9, 134.6, 132.1, 131.2, 130.8, 130.8, 130.6, 130.3, 128.7, 128.1, 128.0, 127.9, 127.8,
~
ν
127.7, 127.4, 126.9, 126.8, 126.6, 126.6, 126.5, 126.3, 125.6, 125.5, 125.4, 122.3, 120.8, 114.1, 70.7. FTꢀIR:
=
10
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12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
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33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
‐
1
+
(
KBr, cm ): 3066, 2928, 1659, 1659, 1560, 1509, 1459, 1365, 1268; HRMS (ESIꢀTOF) Calculated for [M+H] :
C H N O : Exact Mass: 633.2537; found: 633.2536
4
5
33
2
2
1
3,5,6,7,8-Pentaphenyl-1-(pyridin-2-yl)quinolin-2(1H)-one (3i): White amorphous solid, Yield (53 mg, 88%): H
NMR (400 MHz, CDCl
3
) δ 8.30 (d, J = 5.1 Hz, 1H), 7.81 (s, 1H), 7.60 (d, J = 7.5 Hz, 2H), 7.44 – 7.27 (m, 5H), 7.22 –
13
6.97 (m, 6H), 6.92 – 6.61 (m, 12H), 6.44 (d, J = 8.3 Hz, 2H), 6.08 (d, J = 7.9 Hz, 1H). C NMR (100 MHz, CDCl
3
) δ
163.2, 153.9, 148.2, 144.7, 139.8, 139.6, 139.5, 139.0, 138.7, 138.2, 137.3, 137.2, 136.3, 136.1, 132.1, 131.6, 131.4,
131.3, 131.2, 131.0, 130.9, 130.8, 130.4, 130.3, 129.1, 128.1, 128.07, 127.9, 127.8, 127.5, 127.1, 126.8, 126.7, 126.6,
~
ν
‐1
126.5, 126.4, 125.7, 125.6, 125.5, 122.2, 121.1; FTꢀIR:
= (KBr, cm ): 3056, 2924, 1658, 1552, 1494, 1414, 1328,
+
1
274; HRMS (ESIꢀTOF) Calculated for [M+H] : C44
H
31
N
2
O: Exact Mass: 603.2431; found: 603.2437
N-(2-oxo-1,5,6,7,8-Pentaphenyl-1,2-dihydroquinolin-3-yl)-N-(phenylsulfonyl)benzenesulfonamide (3j): White
1
amorphous solid, Yield (78.5 mg, 96%): H NMR (400 MHz, CDCl ) δ 8.26 (dd, J = 4.8, 1.8 Hz, 1H), 8.07 (d, J = 7.9
3
Hz, 2H), 7.89 (d, J = 7.7 Hz, 2H), 7.60 – 7.55 (m, 2H), 7.45 (t, J = 7.8 Hz, 3H), 7.37 – 7.22 (m, 4H), 7.21 – 6.96 (m,
5H), 6.96 – 6.83 (m, 3H), 6.83 – 6.71 (m, 8H), 6.69 – 6.62 (m, 2H), 6.41 (q, J = 7.7 Hz, 2H), 6.01 (d, J = 7.6 Hz, 1H).
1
3
3
C NMR (100 MHz, CDCl ) δ 160.8, 153.1, 148.0, 146.9, 143.8, 140.8, 139.7, 139.2, 139.1, 138.5, 137.8, 137.1,
1
1
36.6, 133.9, 133.9, 132.1, 131.3, 131.2, 130.8, 130.7, 130.2, 129.2, 129.1, 129.1, 128.9, 128.8, 127.9, 128.0, 127.51,
27.4, 126.9, 126.8, 126.84, 126.78, 126.74, 126.59, 126.56, 126.54, 126.52, 126.48, 125.9, 125.8, 125.7, 124.6,
~
ν
‐1
122.5, 119.7. FTꢀIR:
= (KBr, cm ): 3055, 2956, 1678, 1552, 1496, 1446, 1380, 1170; HRMS (ESIꢀTOF)
+
37 2 5 2
Calculated for [M+H] : C51H N O S
: Exact Mass: 821.2138; found: 821.2142.
5,6,7,8-Tetraphenyl-1-(pyridin-2-yl)-3-(trifluoromethyl)quinolin-2(1H)-one (3k): White amorphous solid, Yield
1
(
45.7 mg, 77%): H NMR (400 MHz, CDCl ) δ 8.26 (d, J = 5.0 Hz, 1H), 8.04 (s, 1H), 7.33 (d, J = 4.3 Hz, 2H), 7.25 –
3
7.11 (m, 3H), 7.05 – 6.97 (m, 3H), 6.91 – 6.85 (m, 2H), 6.82 – 6.71 (m, 8H), 6.70 – 6.61 (m, 2H), 6.49 – 6.34 (m, 2H),
1
3
6
.00 (d, J = 7.8 Hz, 1H). C NMR (150 MHz, CDCl ) δ 171.2, 159.5, 152.7, 148.3, 147.5, 141.3, 140.3, 139.7 (q, J =
3
5.4 Hz), 139.0, 138.9, 138.3, 138.0, 137.1, 136.4, 131.9, 131.3, 131.1, 131.0, 130.9, 130.8, 130.6, 130.6, 130.1, 128.1,
128.0, 127.9, 127.7, 127.6, 127.0, 126.8, 126.8, 126.6, 126.5, 126.0, 125.9, 125.8, 122.6, 122.3 (q, J = 273.2 Hz),
~
1
9
1
‐
ν
1
1
18.8 ; F NMR (376 MHz, CDCl
3
) δ ꢀ65.64 .FTꢀIR:
= (KBr, cm ): 3058, 2927, 1683, 1557, 1508, 1416, 1376,
+
293; HRMS (ESIꢀTOF) Calculated for [M+Na] : C39
H
25
F
3
N
2
NaO:Exact Mass: 617.1811; found:617.1817.
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-oxo-5,6,7,8-Tetraphenyl-1-(pyridin-2-yl)-1,2-dihydroquinoline-3-carbonitrile (3l): Bright yellow amorphous
1
solid, Yield (38 mg, 69%): H NMR (400 MHz, CDCl
3
) δ 8.27 (d, J = 4.6 Hz, 1H), 8.14 (s, 1H), 7.35 (dt, J = 12.5, 7.6
Hz, 2H), 7.23 (dt, J = 22.0, 6.3 Hz, 3H), 7.00 (d, J = 11.9 Hz, 3H), 6.95 – 6.90 (m, 1H), 6.88 (d, J = 7.3 Hz, 1H), 6.86
6.65 (m, 9H), 6.63 (d, J = 7.7 Hz, 1H), 6.43 (t, J = 7.7 Hz, 1H), 6.38 (d, J = 7.7 Hz, 1H), 5.99 (d, J = 7.8 Hz, 1H).
–
1
3
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
3
C NMR (100 MHz, CDCl ) δ 160.1, 152.5, 148.7, 148.4, 141.2, 140.5, 138.7, 138.6, 138.4, 138.0, 136.7, 136.7,
131.9, 131.4, 131.0, 130.7, 130.5, 130.0, 128.2, 128.2, 127.9, 127.7, 127.6, 127.1, 126.9, 126.9, 126.7, 126.6, 126.2,
~
1
ν
‐
1
1
4
26.1, 126.0, 122.8, 119.6, 115.2, 106.7; FTꢀIR:
= (KBr, cm ): 3058, 2927, 2232, 1672, 1598, 1548, 1410, 1322,
+
232; HRMS (ESIꢀTOF) Calculated for [M+H] : C39
H
26
N
3
O; Exact Mass: 552.2070; found: 552.2077
-Methyl-5,6,7,8-tetraphenyl-1-(pyridin-2-yl)quinolin-2(1H)-one (3m): White amorphous solid, Yield (36.6 mg,
1
68%): H NMR (400 MHz, CDCl
3
) δ 8.35 – 8.20 (m, 1H), 7.36 (d, J = 7.6 Hz, 1H), 7.23 (t, J = 7.4 Hz, 1H), 7.17 –
7.11 (m, 2H), 7.08 – 6.94 (m, 4H), 6.91 – 6.55 (m, 12H), 6.51 (s, 1H), 6.38 (q, J = 7.7 Hz, 2H), 5.90 (d, J = 7.8 Hz,
13
1
1
3
H), 1.74 (s, 3H). C NMR (150 MHz, CDCl ) δ 163.0, 153.8, 150.4, 148.0, 143.8, 141.3, 140.3, 139.7, 139.7, 139.5,
39.1, 138.2, 136.13 , 132.0, 131.6, 131.3, 131.0, 130.6, 130.3, 127.8, 127.5, 127.4, 127.2, 127.1, 126.8, 126.6, 126.5,
~
1
ν
‐
1
1
26.4, 125.6, 125.4, 125.3, 123.5, 122.2, 121.8, 25.1; FTꢀIR:
= (KBr, cm ): 3054, 2925, 1672, 1586, 1537, 1491,
+
443, 1394, 1262; HRMS (ESIꢀTOF) Calculated for [M+H] : C H N O: Exact Mass: 541.2274: found: 541.2273
3
9
29
2
4-(Benzyloxy)-5,6,7,8-tetraphenyl-1-(pyridin-2-yl)quinolin-2(1H)-one (3n): White amorphous solid, Yield (55 mg,
1
87%): H NMR (400 MHz, CDCl
3
) δ 8.25 (d, J = 5.1 Hz, 1H), 7.25 – 7.11 (m, 5H), 7.04 (q, J = 7.4 Hz, 2H), 6.98 –
6
1
1
.87 (m, 3H), 6.87 – 6.62 (m, 14H), 6.54 (d, J = 7.1 Hz, 1H), 6.45 – 6.25 (m, 2H), 6.03 (s, 1H), 5.91 (d, J = 7.7 Hz,
13
3
H), 4.73 (d, J = 4.2 Hz, 2H). C NMR (100 MHz, CDCl ) δ 164.9, 153.9, 147.9, 144.9, 141.8, 141.0, 140.3, 139.8,
39.6, 139.5, 138.6, 138.1, 136.1, 134.4, 132.8, 132.0, 131.4, 131.2, 131.1, 130.9, 130.6, 130.2, 129.4, 129.3, 128.4,
~
ν
‐1
1
28.2, 128.1, 128.1, 126.5, 126.4, 126.3, 125.7, 125.6, 125.4, 125.2, 121.8, 117.0, 71.1; FTꢀIR:
= (KBr, cm ):
+
3056, 2928, 1660, 1544, 1496, 1428, 1364, 1222; HRMS (ESIꢀTOF) Calculated for [M+H] : C H N O : Exact
45
33
2
2
Mass: 633.2537; found: 633.2352.
1,2,3,4-Tetraphenyl-5-(pyridin-2-yl)phenanthridin-6(5H)-one (3o): White amorphous solid, Yield (23.6 mg, 41%):
1
H NMR (400 MHz, CDCl
3
H), 6.91 – 6.61 (m, 12H), 6.48 – 6.31 (m, 2H), 5.90 (m, 1H). C NMR (100 MHz, CDCl ) δ 163.44 , 154.5, 147.9,
3
) δ 8.44 (d, J = 7.9 Hz, 1H), 8.28 (d, J = 5.2 Hz, 1H), 7.42 – 7.29 (m, 2H), 7.21 – 6.96 (m,
1
3
9
142.9, 141.8, 139.9, 139.8, 139.6, 138.2, 138.2, 138.1, 136.1, 135.2, 131.7, 131.5, 131.5, 129.1, 128.6, 128.0, 127.7,
~
1
ν
‐
127.4, 126.9, 126.8, 126.6, 126.5, 125.6, 125.4, 125.3, 121.7, 120.4; FTꢀIR:
= (KBr, cm ): 3056, 2928, 1668,
+
1
600, 1496, 1440, 1384, 1286; HRMS (ESIꢀTOF) Calculated for [M+H] : C42
29 2
H N O: Exact Mass: 577.2274; found:
5
77.2280
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5
,6,7,8-Tetraphenyl-1-(pyridin-2-yl)quinolin-4(1H)-one (3p): White amorphous solid, Yield (37.8 mg, 72%) H
NMR (600 MHz, CDCl ) δ 8.18 (dd, J = 4.9, 1.9 Hz, 1H), 7.63 (d, J = 7.7 Hz, 1H), 7.37 (td, J = 7.7, 1.9 Hz, 1H), 7.15
7.00 (m, 5H), 6.92 (dd, J = 7.4, 4.9 Hz, 1H), 6.84 (d, J = 8.0 Hz, 1H), 6.82 – 6.68 (m, 12H), 6.64 – 6.54 (m, 3H),
3
–
6
13
3
.18 (d, J = 7.7 Hz, 1H). C NMR (100 MHz, CDCl ) δ 178.9, 157.0, 148.9, 144.5, 143.6, 141.6, 141.1, 141.0, 140.2,
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
139.2, 139.1, 138.9, 138.5, 132.3, 132.1, 131.3, 130.5, 130.3, 129.5, 127.2, 126.9, 126.6, 126.5, 126.2, 125.8, 125.6,
~
1
ν
‐
125.5, 122.3, 121.4, 114.5, 113.4, 112.0. FTꢀIR:
= (KBr, cm ): 3054, 2924, 1666, 1601, 1549, 1492, 1407, 1278;
+
HRMS (ESIꢀTOF) Calculated for [M+H] : C H N O: Exact Mass: 527.2118; found: 527.2130
38 27
2
1
1
,2,3,4-Tetraphenyl-10-(pyridin-2-yl)acridin-9(10H)-one (3q): White amorphous solid, Yield (37.4 mg, 65%): H
NMR (400 MHz, CDCl ) δ 8.34 (d, J = 8.1 Hz, 1H), 8.25 (d, J = 4.7 Hz, 1H), 7.40 (t, J = 7.9 Hz, 1H), 7.33 (t, J = 7.8
Hz, 1H), 7.16 (d, J = 4.8 Hz, 5H), 7.10 (t, J = 8.0 Hz, 2H), 7.03 – 6.94 (m, 1H), 6.86 (t, J = 7.4 Hz, 1H), 6.82 – 6.76
3
1
3
(m, 6H), 6.75 – 6.67 (m, 5H), 6.60 – 6.55 (m, 2H), 6.52 (d, J = 7.5 Hz, 2H). C NMR (100 MHz, CDCl
3
) δ 179.1,
1
1
63.5, 156.2, 149.3, 147.5, 144.0, 143.4, 142.2, 141.6, 139.9, 139.6, 139.4, 138.3, 137.4, 137.1, 133.2, 132.2, 131.5,
31.4, 130.5, 129.4, 127.9, 127.4, 127.1, 126.5, 126.4, 125.7, 125.6, 125.5, 125.4, 124.0, 122.4, 122.4, 122.2, 116.8 ;
~
1
ν
‐
FTꢀIR:
= (KBr, cm ): 3056, 2929, 1655, 1603, 1543, 1509, 1457, 1421, 1268; HRMS (ESIꢀTOF) Calculated for
+
[
M+H] : C H N O: Exact Mass: 577.2274; found: 577.2269.
42 29 2
1
5,6,7,8-Tetraphenyl-1-(pyrimidin-2-yl)quinolin-4(1H)-one (3r): White amorphous solid, Yield (47 mg, 89%): H
NMR (400 MHz, CDCl ) δ 8.36 (d, J = 4.8 Hz, 2H), 8.10 (d, J = 7.9 Hz, 1H), 7.15 – 7.05 (m, 5H), 6.88 – 6.73 (m,
3
1
3
1
3
2H), 6.71 – 6.69 (m, 2H), 6.65 – 6.56 (m, 2H), 6.20 (d, J = 8.0 Hz, 1H). C NMR (150 MHz, CDCl ) δ 179.3, 161.5,
1
59.0, 145.9, 142.5, 141.4, 141.2, 140.6, 139.7, 139.4, 139.3, 138.3, 132.7, 132.5, 131.3, 130.7, 129.5, 127.1, 126.9,
~
ν
‐1
1
26.7, 126.6, 126.4, 126.0, 125.8, 125.7, 125.5, 118.1, 113.2; FTꢀIR:
= (KBr, cm ): 3055, 2924, 1638, 1562, 1498,
+
1
441, 1406, 1294; HRMS (ESIꢀTOF) Calculated for [M+H] : C37
H
26
N
3
O: Exact Mass: 528.2070; found: 528.2064.
1
1-(Pyridin-2-yl)-5,6,7,8-tetrap-tolylquinolin-2(1H)-one (4a): White amorphous solid, Yield (53.5 mg, 92%) : H
NMR (600 MHz, CDCl ) δ 8.24 (d, J = 4.2 Hz, 1H), 7.60 (d, J = 9.9 Hz, 1H), 7.22 – 7.14 (m, 2H), 7.10 (d, J = 7.8 Hz,
3
1
8
2
H), 6.94 (d, J = 7.8 Hz, 1H), 6.90 – 6.83 (m, 3H), 6.80 – 6.76 (m, 3H), 6.67 (s, 2H), 6.64 – 6.50 (m, 4H), 6.47 (d, J =
.0 Hz, 1H), 6.28 (d, J = 7.8 Hz, 1H), 6.21 (d, J = 7.8 Hz, 1H), 5.88 (d, J = 7.9 Hz, 1H), 2.28 (s, 3H), 2.10 (s, 3H),
1
3
3
.05 (s, 3H), 2.01 (s, 3H). C NMR (100 MHz, CDCl ) δ 164.03 , 153.9, 148.1, 145.3, 140.1, 139.9, 139.6, 139.4,
137.4, 136.8, 136.6, 136.5, 136.3, 135.9, 135.5, 135.0, 134.7, 134.7, 132.0, 131.4, 131.1, 130.8, 130.6, 130.3, 128.8,
~
1
ν
‐
128.6, 128.4, 128.3, 127.8, 127.5, 127.2, 127.2, 127.1, 121.9, 121.0, 120.9, 21.4, 21.2, 21.1; FTꢀIR:
= (KBr, cm ):
+
3
055, 2924, 1658, 1562, 1498, 1441, 1406, 1294; HRMS (ESIꢀTOF) Calculated for [M+H] : C42
H
35
N
2
O: Exact Mass:
583.2744; found: 583.2746.
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2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
5
8
7
,6,7,8-Tetrakis(4-chlorophenyl)-1-(pyridin-2-yl)quinolin-2(1H)-one (4b): White amorphous solid, Yield (55 mg,
1
3%): H NMR (400 MHz, CDCl
3
) δ 8.20 (d, J = 5.0 Hz, 1H), 7.47 (d, J = 9.9 Hz, 1H), 7.37 – 7.22 (m, 2H), 7.19 –
.11 (m, 2H), 6.98 – 6.73 (m, 8H), 6.68 (d, J = 7.5 Hz, 1H), 6.63 (d, J = 7.8 Hz, 1H), 6.56 (d, J = 9.9 Hz, 2H), 6.48 (d,
13
J = 8.3 Hz, 1H), 6.40 (d, J = 8.2 Hz, 1H), 6.25 (d, J = 8.4 Hz, 1H), 5.88 (d, J = 8.4 Hz, 1H). C NMR (100 MHz,
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
CDCl
3
) δ 163.5, 153.4, 148.4, 143.5, 139.7, 139.1, 138.9, 137.4, 137.2, 137.0, 136.6, 136.1, 135.9, 133.8, 133.1,
1
1
32.5, 132.3, 132.3, 132.2, 132.0, 131.8, 131.5, 129.9, 128.6, 128.5, 128.0, 127.8, 127.7, 127.4, 127.3, 127.2, 122.6,
~
1
‐
ν
22.2, 121.2; FTꢀIR:
= (KBr, cm ): 3061, 2924, 1672, 1593, 1564, 1477, 1430, 1396, 1279; HRMS (ESIꢀTOF)
+
35
Calculated for [M+H] : C38
H
23 Cl
4
N
2
O: Exact Mass: 663.0559; found:663.0552
5,6,7,8-Tetrakis(4-bromophenyl)-1-(pyridin-2-yl)quinolin-2(1H)-one (4c): White amorphous solid, Yield (67 mg,
1
80%): H NMR (600 MHz, CDCl
3
) δ 8.26 (dd, J = 4.9, 1.9 Hz, 1H), 7.51 (d, J = 9.9 Hz, 1H), 7.48 (d, J = 8.1 Hz, 1H),
6.59 – 6.54 (m, 1H), 7.34 (dt, J = 7.8, 3.8 Hz, 2H), 7.17 (d, J = 8.0 Hz, 2H), 7.07 (d, J = 8.2 Hz, 1H), 7.03 – 6.92 (m,
3
1
1
H), 6.93 – 6.77 (m, 4H), 6.65 – 6.61 (m, 3H), 6.57 (d, J = 7.4 Hz, 1H), 6.48 (d, J = 8.3 Hz, 1H), 6.26 (d, J = 7.7 Hz,
13
H), 5.87 (d, J = 7.7 Hz, 1H). C NMR (150 MHz, CDCl
3
) δ 163.5, 153.3, 148.4, 143.2, 139.6, 139.1, 138.8, 137.7,
37.6, 137.3, 136.7, 136.4, 135.7, 133.4, 132.8, 132.5, 132.5, 132.3, 132.2, 132.1, 131.8, 131.5, 131.4, 131.0, 130.6,
~
1
‐
ν
130.6, 130.4, 130.2, 130.1, 129.8, 127.8, 122.6, 122.2, 121.1, 120.6, 120.6; FTꢀIR:
= (KBr, cm ): 3056, 2924,
+
79
1662, 1595, 1494, 1432, 1372, 1280; HRMS (ESIꢀTOF) Calculated for [M+H] : C38
838.8538; found: 838.8537.
H
23 Br
4
N
2
O: Exact Mass:
5
6
6
,6,7,8-Tetrakis(4-fluorophenyl)-1-(pyridin-2-yl)quinolin-2(1H)-one (4d): White amorphous solid, Yield (37.6 mg,
1
3%): H NMR (400 MHz, CDCl
3
) δ 8.28 (d, J = 5.0 Hz, 1H), 7.56 (d, J = 9.9 Hz, 1H), 7.36 – 7.20 (m, 2H), 7.09 –
.81 (m, 6H), 6.62 (tdd, J = 31.4, 12.2, 5.9 Hz, 8H), 6.48 – 6.39 (m, 1H), 6.39 – 6.30 (m, 1H), 6.23 – 6.11 (m, 1H),
1
3
6.00 (t, J = 6.9 Hz, 1H). C NMR (101 MHz,CDCl
245), 160.7 (d, J = 245 Hz), 153.4, 148.3, 144.1, 139.5, 139.2, 139.0, 136.4, 135.1 (d, J = 3.1 Hz), 134.9 (d, J = 3.3
Hz), 134.6 (d, J = 3.4 Hz), 133.6 (d, J = 3.2 Hz), 133.5 (d, J = 7.3 Hz), 132.7 (d, J = 7.5 Hz), 132.4 (d, J = 7.9 Hz),
32.3, 132.2, 132.1, 131.9 (d, J = 8.3 Hz), 131.6 (d, J = 8.2 Hz), 130.0, 127.6, 122.4, 121.8, 121.1, 115.2 (d, J = 8.8
3
) δ 163.46 , 161.7 (d, J =247Hz), 160.9 (d, J = 245Hz), 160.8 (d, J
=
1
19
Hz), 115.0 (d, J = 9.2 Hz), 114.8, 114.5, 114.2, 114.0, 113.9, 113.9, 113.8, 113.7, 113.7; F NMR (376 MHz,
~
1
ν
‐
Chloroformꢀd) δ ꢀ114.17 , ꢀ115.52 , ꢀ115.82 , ꢀ115.89 . FTꢀIR:
= (KBr, cm ): 3048, 2928, 1655, 1626, 1543, 1457,
+
1413, 1286, 1232; HRMS (ESIꢀTOF) Calculated for [M+H] : C38
H
23
F
4
N
2
O: Exact Mass: 599.1741; found:599.1744.
5,6,7,8-Tetrakis(4-tert-butylphenyl)-1-(pyridin-2-yl)quinolin-2(1H)-one (4e): White amorphous solid, Yield (47.2
1
mg, 63%): H NMR (400 MHz, CDCl
3
) δ 8.24 (d, J = 4.6 Hz, 1H), 7.75 (d, J = 9.8 Hz, 1H), 7.35 – 7.20 (m, 2H), 7.20
–
7.03 (m, 2H), 6.97 – 6.71 (m, 8H), 6.67 – 6.47 (m, 5H), 6.47 – 6.34 (m, 1H), 6.30 – 6.20 (m, 1H), 6.07 – 5.75 (m,
1
3
3
1H), 1.25 (s, 9H), 1.13 (s, 9H), 1.06 (s, 9H), 1.01 (s, 9H). C NMR (100 MHz, CDCl ) δ 164.1, 153.8, 149.7, 148.3,
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48.2, 147.9, 145.6, 140.3, 139.8, 139.0, 137.6, 136.8, 136.7, 136.2, 136.0, 135.4, 132.1, 131.3, 130.9, 130.8, 130.7,
30.6, 130.4, 130.1, 128.1, 124.6, 124.4, 124.3, 123.3, 123.0, 122.8, 122.0, 120.8, 120.7, 34.6, 34.2, 34.2, 34.1, 31.4,
1
~
1
ν
‐
3
1.3, 31.2, 31.2; FTꢀIR:
= (KBr, cm ): 3070, 2930, 1666, 1604, 1512, 1418, 1362, 1228, 1156; HRMS (ESIꢀTOF)
+
Calculated for [M+H] : C54
H
59
N
2
O: Exact Mass: 751.4622; found: 751.4624.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1
-(Pyridin-2-yl)-5,6,7,8-tetrakis(4-(trifluoromethyl)phenyl)quinolin-2(1H)-one (4f): White amorphous solid,
1
Yield (70 mg, 88%): H NMR (600 MHz, CDCl ) δ 8.27 (dd, J = 5.0, 1.8 Hz, 1H), 7.60 (d, J = 8.0 Hz, 1H), 7.52 (d, J
3
=
9.9 Hz, 1H), 7.48 (d, J = 7.9 Hz, 1H), 7.43 (d, J = 8.4 Hz, 1H), 7.27 (d, J = 8.1 Hz, 1H), 7.22 (td, J = 7.7, 1.9 Hz,
1
6
H), 7.17 (t, J = 7.6 Hz, 2H), 6.93 (d, J = 7.7Hz, 1H), 6.88 (d, J = 7.7 Hz, 1H), 6.78 (m, 7H), 6.64 (d, J = 9.8 Hz, 2H),
13
.37 (d, J = 7.7 Hz, 1H), 6.19 (d, J = 8.1 Hz, 1H). C NMR (150 MHz,CDCl
3
) δ 163.5, 153.3, 148.5, 144.9, 142.9,
141.9, 139.1, 138.7, 138.6, 138.5, 137.3, 136.6, 131.74 (q, J = 5.3 Hz), 131.61 (q, J = 264 Hz), 131.63 (q, J = 265
Hz), 131.60 (q, J = 265Hz), 131.2 (q, J = 4.9 Hz), 131.0, 130.8 (q, J = 5.9 Hz), 130.2, 129.8, 129.4, 128.2, 127.9,
127.2, 127.1, 126.9, 126.8, 126.2, 126.2, 124.9, 124.9, 124.8, 124.4, 124.2, 124.1, 123.6 (q, J = 7.2 Hz), 122.6, 122.1,
~
1
9
1
‐
ν
1
1
5
20.7; F NMR (376 MHz, CDCl ) δ ꢀ62.76, ꢀ62.87, ꢀ62.99; FTꢀIR:
= (KBr, cm ): 3056, 2932, 1667, 1608, 1512,
3
+
418, 1288, 1248; HRMS (ESIꢀTOF) Calculated for [M+H] : C H F N O: Exact Mass: 799.1613; found: 799.1611.
4
2
23 12
2
,6,7,8-Tetrakis(3,5-bis(trifluoromethyl)phenyl)-1-(pyridin-2-yl)quinolin-2(1H)-one (4g): yellow oil, Yield (77
1
mg, 72%): H NMR (600 MHz, CDCl
3
) δ 8.30 (dd, J = 5.1, 1.9 Hz, 1H), 7.82 (s, 1H), 7.79 (d, J = 10.0 Hz, 1H), 7.59
– 7.49 (m, 2H), 7.46 (s, 2H), 7.39 (s, 1H), 7.36 (s, 1H), 7.34 – 7.26 (m, 3H), 7.11 (d, J = 6.2 Hz, 1H), 7.01 – 6.92 (m,
1
3
2
H), 6.84 (t, J = 10.6 Hz, 2H), 6.59 (s, 1H). C NMR (150 MHz, CDCl
3
) δ 162.5, 152.2, 149.2, 141.7, 139.8, 139.6,
1
39.6, 139.4, 138.6, 138.2, 137.5, 137.2, 134.2, 132.7, 132.5, 132.2 (q, J = 4.2 Hz), 131.9, 131.7, 131.6 (d, J = 8.3
Hz), 131.5 (d, J = 4.3 Hz), 131.4 (q, J = 4.4 Hz), 131.2 (q, J = 4.5 Hz), 131.1, 131.0 (q, J = 6.5 Hz), 130.7 (q, J = 3.6
Hz), 130.5, 130.5, 130.4, 130.4, 130.4, 130.4, 130.1, 130.0, 129.95, 129.93 (q, J = 4.9 Hz), 128.8, 127.4, 124.8, 124.6,
124.1, 123.8, 123.6 (q, J = 4.5 Hz), 123.3 (q, J = 6.6 Hz), 122.4, 122.37, 122.34 , 121.82, 121.81 , 121.4, 121.0 (q, J =
19
3.9 Hz), 120.84, 120.82, 120.61 , 120.6; F NMR (376 MHz, CDCl
3
) δ ꢀ62.99 , ꢀ63.09 , ꢀ63.29 , ꢀ63.38 , ꢀ63.50 , ꢀ
~
1
ν
‐
6
3.89 , ꢀ63.94 . FTꢀIR:
= (KBr, cm ): 3057, 2923, 1671, 1590, 1544, 1489, 1431, 1378, 1275; HRMS (ESIꢀTOF)
+
Calculated for [M+H] : C46
H
19
F
24
N
2
O: Exact Mass: 1071.1109; found: 1071.1115.
5
,6,7,8-Tetra(naphthalen-1-yl)-1-(pyridin-2-yl)quinolin-2(1H)-one (4h): Light yellow amorphous solid, Yield
1
(42.1 mg, 59%): H NMR (400 MHz, CDCl
3
) δ 8.38 (d, J = 6.3 Hz, 1H), δ 7.96 (d, J = 8.7 Hz, 1H), 7.84 (m, 2H), 7.78
–
2
1
7.69 (m, 2H), 7.68 – 7.56 (m, 5H), 7.56 – 7.25 (m, 13H), 7.22 – 7.11 (m, 3H), 7.08 – 6.96 (m, 2H), 6.96 – 6.82 (m,
13
H), 6.77 (m, 7.1 Hz, 1H), 6.52 (dd, J = 9.6, 4.4 Hz, 1H), 6.31 (d, J = 7.0 Hz, 1H). C NMR (150 MHz,CDCl
3
) δ
63.6, 152.2, 148.6, 140.6, 139.9, 138.4, 137.7, 136.9, 136.1, 134.6, 133.8, 133.3, 132.5, 130.4, 130.3, 130.1, 129.5,
129.4, 129.3, 128.9, 128.8, 128.6, 128.4, 128.2, 127.7, 127.7, 127.5, 127.5, 127.1, 126.9, 126.8, 126.6, 126.3, 126.1,
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1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
~
ν
1
26.0, 125.9, 125.9, 125.8, 125.5, 125.5, 125.2, 124.9, 124.7, 124.6, 123.2, 122.5, 122.0, 120.5, 120.0: FTꢀIR:
=
1
+
‐
(KBr, cm ): 3046, 2924, 1671, 1592, 1543, 1509, 1459, 1380; HRMS (ESIꢀTOF) Calculated for [M+H] : C54
H
35
N
2
O:
Exact Mass: 727.2744; found: 727.2729
1
-(Pyridin-2-yl)-5,6,7,8-tetra(thiophen-2-yl)quinolin-2(1H)-one (4i): Light yellow amorphous solid, Yield (46.2
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
mg, 84%): H NMR (600 MHz, CDCl
3
) δ 8.31 (dd, J = 5.0, 1.9 Hz, 1H), 7.78 (d, J = 9.9 Hz, 1H), 7.40 (m, 1H), 7.33
(m, 1H), 7.05 – 6.96 (m, 7H), 6.67 (d, J = 9.9 Hz, 1H), 6.65 – 6.61 (m, 1H), 6.56 (t, J = 4.4 Hz, 1H), 6.52 (d, J = 3.5
1
3
Hz, 1H), 6.41 (m, 1H), 6.28 (m, 1H), 5.66 (m, 1H). C NMR (150 MHz, CDCl ) δ 163.4, 153.4, 148.2, 141.4, 140.7,
3
1
1
39.7, 139.5, 139.2, 138.2, 137.9, 136.6, 134.9, 132.9, 130.2, 129.9, 129.4, 128.8, 127.7, 127.4, 126.6, 126.3, 125.9,
~
1
ν
‐
25.7, 125.5, 124.7, 122.7, 122.4, 122.2; FTꢀIR:
= (KBr, cm ): 3072, 2922, 1667, 1589, 1557, 1465, 1931, 1267;
+
HRMS (ESIꢀTOF) Calculated for [M+H] : C30
H
19
N
2
OS
4
:Exact Mass: 551.0375; found: 551.0383.
1
5
,6,7,8-Tetrapropyl-1-(pyridin-2-yl)quinolin-2(1H)-one(4j):Yellow liquid, Yield (41%): H NMR (400 MHz,
3
CDCl ) δ 8.50 (dd, J = 4.9, 1.9 Hz, 1H), 7.96 (d, J = 9.8 Hz, 1H), 7.88 (td, J = 7.7, 2.0 Hz, 1H), 7.70 (d, J = 7.8 Hz,
1
1
1
H), 7.31 (dd, J = 7.4, 4.9 Hz, 1H), 6.59 (d, J = 9.8 Hz, 1H), 2.89 – 2.73 (m, 2H), 2.57 (m, 4H), 1.68 – 1.46 (m, 6H),
13
.46 – 1.37 (m, 2H), 1.09 (m, 8H), 0.99 (t, J = 7.3 Hz, 3H), 0.57 (t, J = 7.2 Hz, 3H); C NMR (125 MHz, CDCl ) δ
3
63.7, 154.5, 149.1, 143.9, 138.6, 138.4, 137.3, 136.0, 135.3, 128.2, 125.3, 122.8, 119.8, 119.6, 33.1, 32.5, 31.7, 30.8,
~ = (KBr, cm‐ 1
2
5.4, 24.83, 24.8, 23.6, 15.1, 14.9, 13.9; FTꢀIR:
ν
): 2958, 2930, 2870, 1666, 1560, 1464, 1312; HRMS
+
(
ESIꢀTOF) Calculated for [M+H] : C26
H
35
N
2
O: 391.2744; found: 391.2746
1
5,6,7,8-Tetraethyl-1-(pyridin-2-yl)quinolin-2(1H)-one(4k): Yellow liquid, Yield (34%): H NMR (400 MHz,
CDCl ) δ 8.52 (m, 1H), 8.01 (d, J = 9.8 Hz, 1H), 7.88 (td, J = 7.8, 1.9 Hz, 1H), 7.75 (d, J = 8.0 Hz, 1H), 7.30 (dd, J =
.4, 4.8 Hz, 1H), 6.61 (d, J = 9.8 Hz, 1H), 2.94 (q, J = 7.6 Hz, 2H), 2.70 (m, 4H), 1.33 – 1.24 (m, 5H), 1.20 (t, J = 7.5
3
7
13
3
Hz, 3H), 1.10 (t, J = 7.5 Hz, 3H), 0.68 (t, J = 7.3 Hz, 3H); C NMR (100 MHz, CDCl ) δ 163.9, 154.7, 149.1, 145.0,
138.7, 138.3, 137.3, 137.2, 136.2, 129.5, 125.5, 122.8, 119.8, 119.7, 23.4, 22.7, 21.9, 21.6, 16.2, 15.8, 15.7, 14.9; FTꢀ
~
ν
‐ 1
+
IR:
= (KBr, cm ): 2968, 2930, 2871, 1664, 1562, 1430, 1298; HRMS (ESIꢀTOF) Calculated for [M+H] :
O: 335.2118; found: 335.2119
,6,7,8-Tetraphenylquinolin-2(1H)-one (5): White amorphous solid, Yield (32.3 mg, 72%): H NMR (600 MHz,
CDCl ) δ 8.57 (s, 1H), 7.62 (d, J = 9.9 Hz, 1H), 7.30 (dd, J = 8.1, 6.6 Hz, 2H), 7.25 (s, 1H), 7.25 – 7.21 (m, 2H), 7.21
d, J = 7.0 Hz, 1H), 7.18 – 7.15 (m, 2H), 7.14 – 7.11 (m, 2H), 6.90 – 6.80 (m, 6H), 6.78 (m, 4H), 6.54 (dd, J = 9.8, 2.0
22 27 2
C H N
1
5
3
(
13
Hz, 1H); C NMR (150 MHz, CDCl
3
) δ 162.3, 143.7, 139.9, 139.7, 139.3, 139.2, 137.8, 136.2, 135.6, 134.6, 131.5,
~
ν
130.9, 130.9, 130.8, 129.2, 128.3, 127.9, 127.4, 127.2, 127.0, 126.9, 126.1, 125.8, 121.5, 118.1; FTꢀIR:
= (KBr,
1
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9
1
+
‐
cm ): 3364, 3056, 1666, 1580, 1496, 1440, 1384, 1294; HRMS (ESIꢀTOF) Calculated for [M+H] : C33
H24NO: Exact
Mass: 450.1852; found: 450.1851
ASSOCIATED CONTENT
Supporting Information
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H, C, F NMR spectra for all new compounds and photophysical studies of quinolone derivatives) This material is
available free of charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*Eꢀmail: rsamanta@chem.iitkgp.ernet.in
*Eꢀmail: skpatra@chem.iitkgp.ernet.in
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
This work was supported by the SERB, India (YSS/2014/000383). Fellowships received from the Council of
Scientific and Industrial Research (CSIR), India (A. B. & D. D.) and IIT Kharagpur (D. G.) are gratefully
acknowledged.
REFERENCES
(
1) (a) Salinas, Y.; Manez, R. M.; Marcos, M. D.; Sancenon, F.; Costero, A. M.; Parra, M.; Gil, S. Chem. Soc. Rev.
2012, 41, 1261. (b) Yang J. –S.; Swager, T. M. J. Am. Chem. Soc. 1998, 120, 11864.
2) (a) Yamaguchi, J.; Yamaguchi, A. D.; Itami, K. Angew. Chem. Int. Ed. 2012, 51, 8960. (b) Kuhl, N.; Hopkinson,
(
M. N.; WencelꢀDelord, J.; Glorius, F. Angew. Chem. Int. Ed. 2012, 51, 10236. (c) Sarkar, S. D.; Liu, W.; Kozhushkov,
S. I.; Ackermann, L. Adv. Synth. Catal. 2014, 356, 1461.
(3) (a) Bras, J. L.; Muzart, J. Synthesis. 2014, 1555. (b) Yasukawa, T.; Satoh, T.; Miura, M.; Nomura, M. J. Am. Chem.
Soc. 2002, 124, 12680. (c) Ueura, K.; Satoh, T.; Miura, M. J. Org. Chem. 2007, 72, 5362. (d) Yamashita, M.; Hirano,
K.; Satoh, T.; Miura, M. Org. Lett. 2009, 11, 2337. (e) Yamashita, M.; Horiguchi, H.; Hirano, K.; Satoh T.; Miura, M.
J. Org. Chem. 2009, 74, 7481. (f) Uto, T.; Shimizu, M.; Ueura, K.; Tsurugi, H.; Satoh, T.; Miura, M. J. Org. Chem.
2008, 73, 298. (g) Fukutani, T.; Hirano, K.; Satoh, T.; Miura, M. J. Org. Chem. 2011, 76, 2867. (h) Ilies, L.;
Matsumoto, A.; Kobayashi, M.; Yoshikai, N.; Nakamura, E. Synlett. 2012, 23, 2381. (i) Adak, L.; Yoshikai, N.;
Tetrahedron. 2012, 68, 5167.
1
7
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The Journal of Organic Chemistry
Page 18 of 20
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
(
4) Recent reviews (a) Segawa, Y.; Maekawa, T.; Itami, K. Angew. Chem. Int. Ed. 2015, 54, 66. (b) Gulías, M.;
Mascareñas, J. L. Angew. Chem. Int. Ed. 2016, 55, 11000. Rhodium catalysed annulation: (c) Yang, Y.; Li, K.; Cheng,
Y.; Wan, D.; Li, M.; You, J. Chem Commun. 2016, 52, 2872. Few recent papers: (d) Zhang, S.ꢀS., Liu, X.ꢀG., Chen, S.ꢀ
Y., Tan, D.ꢀH., Jiang, C.ꢀY., Wu, J.ꢀQ., Li, Q., Wang, H. Adv. Synth. Catal. 2016, 358, 1705. (e) Lao, Y.ꢀX., Zhang, S.ꢀ
S., Liu, X.ꢀG., Jiang, C.ꢀY., Wu, J.ꢀQ., Li, Q., Huang, Z.ꢀS., Wang, H. Adv. Synth. Catal. 2016, 358, 2186. (f) Prakash,
S., Muralirajan,K., Cheng,C.ꢀH. Angew. Chem. Int. Ed. 2016, 55, 1844.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
(
(
5) Wu, Y. –T.; Huang, K. –H.; Shin, C. –C.; Wu, T. –C. Chem. Eur. J. 2008, 14, 6697.
6) Pham, M. V.; Cramer, N. Angew. Chem. Int. Ed. 2014, 53, 3484.
(7) Kim, O. S.; Jang, J. H.; Kim, H. T.; Han, S. J.; Tsui, G. C.; Joo, J. M. Org. Lett. 2017, 19, 1450.
8) (a) Umeda, N.; Tsurugi, H.; Satoh, T.; Miura, M. Angew. Chem. Int. Ed. 2008, 47, 4019. (b) Umeda, N.; Hirano,
K.; Satoh, T.; Shibata, N.; Sato, H.; Miura, M. J. Org. Chem. 2011, 76, 13. (c) Zheng, J.; You, S.ꢀL. Chem. Commun.
014, 50, 8204.
(
2
(9) (a) Miura, M. Chem. Asian J. 2010, 5, 847. (b) Song, G.; Gong, X.; Li, X. J. Org. Chem. 2011, 76, 7583. (c) Shi,
Z.; Tang, C.; Jiao, N. Adv. Synth. Catal. 2012, 354, 2695. (d) Qian, Z.ꢀC.; Zhou, J.; Li, B.; Shi, B. ꢀF. Synlett. 2014,
1
036. (e) Martinez, A. M.; Echaꢀvarren, J.; Alonso, I.; Rodriguez, N.; Gomez Arrayas, R.; Carretero, J. C. Chem. Sci.
2
015, 6, 5802. (f) Wu, J.; Cui, X.; Mi, X.; Li, Y.; Wu, Y. Chem. Commun. 2010, 46, 6771. (g) Wang, L.; Huang, J.;
Peng, S.; Liu, H.; Jiang, X.; Wang, J. Angew. Chem. Int. Ed. 2013, 52, 1768.
10) (a) Fukuzumi, K.; Unoh, Y.; Nishii, Y.; Satoh, T.; Hirano, K.; Miura, M. J. Org. Chem. 2016, 81, 2474. (b) Li, X.;
Yang, X.; Qi, Z. ACS Catal. 2016, 6, 6372. (c) Villar, J. M.; Suárez, J.; Varela, J. A.; Saá, C. Org. Lett. 2017, 19, 1702.
d) Morioka, R.; Nobushige, K.; Satoh, T.; Hirano, K.; Miura, M. Org. Lett. 2015, 17, 3130. (e) Ge, Q.; Hu, Y.; Li, B.;
(
(
Wang, B. Org. Lett. 2016, 18, 2483. (f) Boldt, S.; Parpart, S.; Villinger, A.; Ehlers, P.; Langer, P. Angew. Chem. Int.
Ed. 2017, 56, 4575.
(
(
11) Misal Castro, L. C.; Obata, A.; Aihara, Y.; Chatani, N. Chem. Eur. J. 2016, 22 , 1362.
12) (a) Martínez, Á. M.; Echavarren, J.; Alonso, I.; Rodríguez, N.; Arrayás, R. G.; Carretero, J. C. Chem. Sci. 2015,
6, 5802. (b) Hyster, T. K.; Rovis, T. Chem. Commun. 2011, 47, 11846. (c) Schroder, N.; Lied, F.; Glorius, F. J. Am.
Chem. Soc. 2015, 137, 1448.
(
13) (a) Cui, S. –F.; Addla, D.; Zhou, C. –H. J. Med. Chem. 2016, 59, 4488. (b) Cui, S. –F.; Peng, L. –P.; Zhang, H. –
Z.; Rasheed, S.; Kumar, K. V. Zhou, C. –H. Euro. J. Med. Chem. 2014, 86, 318. (c) Heeb, S.; Fletcher, M. P.; Chhabra,
S. R.; Diggle, S. P.; Williams, P.; Cámara, M. FEMS Microbiol Rev. 2011, 35, 247.
(14) (a) Nakatani, A.; Hirano, K.; Satoh, T.; Miura, M. Chem. Eur. J. 2013, 19, 7691. (b) Nakatani, A.; Hirano, K.;
Satoh, T.; Miura, M. J. Org. Chem. 2014, 79, 1377. (c) Modak, A.; Rana, S.; Maiti, D. J. Org. Chem. 2015, 80, 296.
1
8
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Page 19 of 20
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1
2
3
4
5
6
7
8
9
(
d) Anagnostaki, E. E.; Fotiadou, A. D.; Demertzidou, V.; Zografos, A. L. Chem. Commun. 2014, 50, 6879. (e) Min,
M.; Kim, Y.; Hong, S. Chem. Commun. 2013, 49, 196. (f) Cheng, D.; Gallagher, T. Org. Lett. 2009, 11, 2639. (g) Shi,
Z.; Zhang, B.; Cui, Y.; Jiao, N. Angew. Chem. Int. Ed. 2010, 49, 4036.
(
15) Miura, W.; Hirano, K.; Miura, M. Synthesis. 2017, 49, DOI: 10.1055/sꢀ0036ꢀ1588735.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(16) (a) Nakao, Y.; Idei, H.; Kanyiva, K. S.; Hiyama, T. J. Am. Chem. Soc. 2009, 131, 15996. (b) Tamura, R.; Yamada,
Y.; Nakao, Y.; Hiyama, T. Angew. Chem. 2012, 124, 5777. (c) Donets, P. A.; Cramer, N. Angew. Chem. Int. Ed. 2015,
5
4, 633. (d) Das, D.; Biswas, A.; Karmakar, U.; Chand, S.; Samanta, R. J. Org. Chem. 2016, 81, 842. (e) Peng, P.;
Wang, J.; Jiang, H.; Liu, H. Org. Lett. 2016, 18, 5376. (f) Li, T.; Wang, Z.; Xu, K.; Liu, W.; Zhang, X.; Mao, W.; Guo,
Y.; Ge, X.; Pan, F. Org. Lett. 2016, 18, 1064. (g) Li, Y.; Xie F.; Li, X. J. Org. Chem. 2016, 81, 715. (h) Das, D.;
Poddar, P.; Maity, S.; Samanta, R. J. Org. Chem. 2017, 82, 3612. (i) Li, J.; Yang, Y.; Wang, Z.; Feng, B.; You, J. Org.
Lett. 2017, 19, 3083.
(
17) Smout, V.; Peschiulli, A.; Verbeeck, S.; Mitchell, E. A.; Herrebout, W.; Bultinck, P.; Vande Velde, C. M. L.;
Berthelot, D.; Meerpoel, L.; Maes, B. U. W. J. Org. Chem., 2013, 78, 9803.
18) (a) Germain, M. E.; Knapp, M. J. Chem. Soc. Rev. 2009, 38, 2543. (b) Toal, S. J.; Trogler, W. C. J. Mater. Chem.
006, 16, 2871. For small molecule based NAC chemosensors, see: (c) Shanmugaraju, S.; Mukherjee, P. S. Chem.
(
2
Commun. 2015, 51, 16014 and references cited therein; (d) Chowdhury, A.; Mukherjee, P. S. J. Org. Chem., 2015, 80,
4064. (e) Kumar, S.; Venkatramaiah, N.; Patil, S. J. Phys. Chem. C, 2013, 117, 7236. (f) Venkatramaiah, N.; Firmino,
A. D. G.; Almeida Paz, F. A.; Tome, J. P. C. Chem. Commun. 2014, 50, 9683. (g) Chandrasekaran, Y.; Venkatramaiah,
N.; Patil, S. Chem. Eur. J., 2016, 22, 5288.
(
19) (a) Akhavan, J. The Chemistry of Explosives, RSC, 2004, Cornwall, UK. (b) Czarnik, A. W. Nature, 1998, 394,
417.
(
21) (a) Zhao, J.; Li, P.; Xia, C.; Li, F. RSC Adv. 2015, 5, 32835. (b) Li, G.; Jia, C.; Sun, K.; Lv, Y.; Zhao, F.; Zhoua,
K.; Wu, H. Org. Biomol. Chem. 2015, 13, 3207. (c) Xia, H.; Liu, Y.; Zhao, P.; Gou, S.; Wang, J. Org. Lett. 2016, 18,
1796. (d) Larionov, O. V.; Stephens, D.; Mfuh, A.; Chavez, G. Org. Lett. 2014, 16, 864.
(22) Chauhan, J.; Fletcher, S. Tetrahedron Lett. 2012, 53, 4951.
(
(
(
(
23) Zhu, C.ꢀW.; Yi, M. ꢀL.; Wei, D. ꢀH.; Chen, X.; Wu, Y. ꢀJ.; Cui, X. ꢀL. Org. Lett. 2014, 16, 1840.
24) Liu, M; Shu, M.; Yao, C.; Yin, G.; Wang, D.; Huang, J. Org. Lett. 2016, 18, 824.
25) He, Y.; Huang, J.; Liang, D.; Liu, L.; Zhu, Q. Chem. Commun. 2013, 49, 7352.
26) (a) Ohira, S. Synth. Commun. 1986, 19, 561. (b) Müller, S.; Liepold, B.; Roth, G. J.; Bestmann, H. J. Synlett.
1996, 521.
27) Sughara, M.; Ukita. Chem. Pharm. Bull. 1997, 45, 719.
(
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(
28) Chuentragoola, P.; Vongnamb, K.; Rashatasakhona, P.; Sukwattanasinitta, M.; Wacharasindhu, S. Tetrahedron.
2
011, 67, 8177.
29) Smout, V.; Peschiulli, A.; Verbeeck, S.; Mitchell, E. A.; Herrebout, W.; Bultinck, P.; Vande Velde, C. M. L.;
Berthelot, D.; Meerpoel, L.; Maes, B. U. W.; J. Org. Chem. 2013, 78, 9803.
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