Regioselective and Chemodivergent Synthesis of Azulenolactones and Azulenolactams from Rhodium(III)-Catalyzed Reactions of Azulenecarboxamides with Sulfoxonium Ylides

Article abstract of DOI:10.1002/adsc.202001082

A regioselective and chemodivergent synthetic approach for azulenolactones and azulenolactams as a new scaffold was demonstrated through Rh(III)-catalyzed reaction of N-methoxyazulene-1-carboxamides with sulfoxonium ylides. Sulfoxonium ylides that act as a precursor of secondary carbene was described, leading to the selective formation of azulenolactones and azulenolactams bearing two substituents on a newly introduced double bond. This method demonstrated functionalization of less reactive 2-position of azulene to overcome the natural reactivity. (Figure presented.).

Full text of DOI:10.1002/adsc.202001082

Title: Regioselective and Chemodivergent Synthesis of
Azulenolactones and Azulenolactams from Rhodium(III)-
Catalyzed Reactions of Azulenecarboxamides with Sulfoxonium
Ylides
Authors: Seung Cheol Lee, Jeong-Yu Son, Jin Young Kim, Hyeonsik
Eom, Seong Bin Jang, and Phil Ho Lee
This manuscript has been accepted after peer review and appears as an
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.202001082
Link to VoR: https://doi.org/10.1002/adsc.202001082

Advanced Synthesis & Catalysis
10.1002/adsc.202001082
FULL PAPER
DOI: 10.1002/adsc.202((will be filled in by the editorial staff))
Regioselective and Chemodivergent Synthesis of
Azulenolactones and Azulenolactams from Rhodium(III)-
Catalyzed Reactions of Azulenecarboxamides with Sulfoxonium
Ylides
b,c
b,c
b
b
Seung Cheol Lee, Jeong-Yu Son, Jin Young Kim, Hyeonsik Eom, Seong Bin
b
a,b,
Jang, and Phil Ho Lee *
a
The Korean Academy of Science and Technology, Seongnam 13630, Republic of Korea
Department of Chemistry, Kangwon National University, Chuncheon 24341, Republic of Korea
b
E-mail: phlee@kangwon.ac.kr
S. C. Lee and J.-Y. Son contributed equally to this work.
c
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
Abstract. A regioselective and chemodivergent synthetic bearing two substituents on a newly introduced double
approach for azulenolactones and azulenolactams as a new bond. This method demonstrated functionalization of less
scaffold was demonstrated through Rh(III)-catalyzed reactive 2-position of azulene to overcome the natural
reaction of N-methoxyazulene-1-carboxamides
with reactivity.
sulfoxonium ylides. Sulfoxonium ylides that act as a
precursor of secondary carbene was described, leading to the Keywords: azulene; rhodium; azulenolactone;
selective formation of azulenolactones and azulenolactams
azulenolactam; sulfoxonium ylide
(
Scheme 1a).[6] Although these methods provided
new scaffolds with nonbenzenoid aromatic azulene
moiety, the formation of regioisomeric mixtures
Introduction
Because azulene derivatives have been found in
natural products, pharmacologically active substances,
[1]
and functional materials, the establishment of a new
synthetic approach is required. To date, C−H
activation has received considerable attention in the
development of new synthetic methods for valuable
compounds that could not be synthesized by
conventional methods.[
2,3]
In particular, transition
metal-catalyzed cyclization reactions of aromatic
compounds with a large number of coupling partners
have been reported.[ Despite great progress, this
promising C−H activation is mainly applied to
benzenoid aromatic compounds. Therefore, C–H
3]
activation using nonbenzenoid aromatic compounds
is challenging.[
4,5a]
Moreover, because azulene has a
dipole moment of 1.08 D as a result of an electron-
poor seven-membered ring and an electron-rich five-
membered ring, 2-position of azulene is less reactive
than 1,3-position, and then introduction of
substituents into 2-position has been an irresistible
synthetic challenge.[ In this regard, we have
developed a Rh(III)-catalyzed cyclization via the
C−H activation of azulene carboxylic acids with
alkynes, leading to the formation of azulenolactones
5]
Scheme 1. Cyclization Reactions Using Sulfoxonium
Ylides and Synthetic Approaches for Azulenolactones and
Azulenolactams.
1
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Advanced Synthesis & Catalysis
10.1002/adsc.202001082
Table 1. Reaction optimization.[a]
cannot be avoided when unsymmetrical internal
alkynes are employed. Also, it cannot be applied to
terminal alkynes. Thus, the establishment of a
regioselective
and
chemodivergent
synthetic
approach for azulenolactone and azulenolactam to
overcome these shortcomings is in high demand.
Recently, the Aïssa and Li groups reported Rh(III)-
catalyzed carbenoid insertion reactions into
benzenoid aromatic C−H functionalization with
sulfoxonium ylides,[ and various synthetic methods
Yield [%][b]
Entry Additive (equiv)
Solvent
3
a
4a
1[c]
2[c]
CsOAc (0.3)
DCE
DCE
45
65
39
7]
CsOAc (0.3)/
PivOH (2.0)
CsOAc (0.3)/
PivOH (2.0)
KOAc (0.3)/
PivOH (2.0)
KOAc (0.3)/
PivOH (2.0)
KOAc (0.3)/
PivOH (2.0)
20
14
14
17
5
have also been described by other groups (Scheme
8]
1
b).[ In addition, Li and coworkers have developed
3[d]
4[d]
5[d]
6[d]
DCE
DCE
70
78
Rh(III)-catalyzed chemodivergent reactions between
benzamides and sulfoxonium ylides, regioselectively
producing isocoumarins and isoquinolones (Scheme
9]
1
c).[ However, sulfoxinium ylides to act as
t-AmOH
toluene
73
precursor of primary carbene have been investigated
in the main to date. Thus, the reported methods could
largely be used for the synthesis of cyclic compounds
92 (92)[e]
with one substituent in a newly introduced double
7[c]
Zn(OTf)
(1.0)
toluene
toluene
toluene
0
0
56
bond.[10] Therefore, it is necessary to expand synthetic
2
utility of a sulfoxonium ylide that acts as a precursor
of secondary carbene to selectively introduce two
8[c]
CsOAc (1.0)
KOAc (1.0)
33
21
substituents into
a
newly introduced double
To continue our recent studies on the
functionalization of nonbenzenoid aromatic
we envisioned that the reaction of N-
9[c]
36 (22)[f]
bond.[
7a,11]
CsOAc (1.0)/
KOAc (1.0)
CsOAc (1.0)/
KOAc (1.0)
CsOAc (1.0)/
KOAc (1.0)
CsOAc (1.0)/
KOAc (1.0)
CsOAc (1.0)/
KOAc (1.0)
10[c]
toluene
MeCN
toluene
MeCN
MeCN
26
8
70
azulenes,[
6,12]
11[c]
60
methoxyazulene-1-carboxamides with sulfoxonium
ylides would selectively provide azulenolactones and
1
2[d]
34
5
30 (16)[f]
66 (28)[g]
91 (90)[e]
azulenolactams. Herein, we demonstrated
a
regioselective and chemodivergent synthetic method
for azulenolactones and azulenolactams with mono-
and di-substituents on a newly introduced double
bond via tandem Rh(III)-catalyzed alkylation and
cyclization reaction of N-methoxyazulene-1-
carboxamides with sulfoxonium ylides (Scheme 1d
and 1e). Therefore, challenging functionalization of
less reactive 2-position of azulene to overcome the
natural reactivity was achieved.
13[d]
14[d,h]
5
1
1
5[d]
6[d]
CsOAc (2.0)
KOAc (2.0)
MeCN
MeCN
5
50 (20)[g]
17 (30)[g]
19
[
a]
1
a (0.10 mmol, 1.0 equiv) reacted with 2a (1.5 equiv) in
the presence of a catalyst and additive in solvent (0.5
mL) at 100 °C for 12 h under N
2
.
[
[
[
[
[
b]
c]
d]
e]
f]
NMR yields using CH
2
Br
(4.0 mol %).
Cp Rh(MeCN) ](SbF
Isolated yield.
2
as an internal standard.
Results and Discussion
*
[
[
2 2
Cp RhCl ]
*
First, we investigated Rh-catalyzed reaction of N-
3
6 2
) (4.0 mol %).
methoxyazulene-1-carboxamide
(1a)
with
N-methoxy-3-hydroxy-3-phenyl-3,4-dihydroazu-
lenolactam (5).
phenylsulfoxonium ylide (2a) to selectively obtain
azulenolactone (3a) and azulenolactam (4a) (Table 1).
[
[
g]
h]
Recovered yield of 1a.
When 1a (0.1 mmol, 1.0 equiv) reacted with 2a (1.5
*
1
6 h.
equiv) in the presence of [Cp RhCl
2
]
2
(4.0 mol %) and
CsOAc (0.3 equiv) in DCE, reaction took place
through C−H activation followed by cyclization,
leading to the formation of the desired compounds 3a
and 4a in 45 and 39% yields, respectively (entry 1).
Fortunately, the addition of pivalic acid (2.0 equiv)
result was obtained from the reaction of 1a (0.1 mmol,
.0 equiv) with 2a (1.2 equiv) in the presence of
1
*
[
Cp Rh(MeCN)
3
][(SbF ) ] (4.0 mol %), KOAc (0.3
6
2
equiv), and PivOH (2.0 equiv) in toluene at 100 °C
for 12 h under a nitrogen atmosphere, providing
azulenolactone (3a) in 92% yield (entry 6). Next,
increased the selectivity of 3a and 4a to 3.25:1 (entry
*
2
). In addition, when [Cp Rh(MeCN)
3
](SbF
6
) (4.0
2
mol %) was used as a catalyst in the presence of
KOAc and pivalic acid, azulenolactone (3a) was
selectively obtained in 78% yield (entry 4). Among
the solvents tested in this study, toluene gave the best
results, although DCE and tert-amyl alcohol were
also effective to some extent (entries 4-6). The best
optimization of the formation of azulenolactam (4a)
*
was attempted with [Cp RhCl
2
]
2
(4.0 mol %) as a
, CsOAc,
catalyst. Among the additives [Zn(OTf)
2
KOAc, and CsOAc/KOAc] screened in toluene,
CsOAc/KOAc (1.0 equiv, each) gave the best results,
producing 3a and 4a in 26 and 70% yields,
2
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Advanced Synthesis & Catalysis
10.1002/adsc.202001082
respectively (entries 7-10). The use of acetonitrile
regioselective annulation of 1a by variation at the α-
position of the sulfoxonium ylides 2. The reaction
efficiency was not influenced by the electronic
properties of the aryl ring of α,β-diaryl sulfoxonium
ylides. Electron-donating methyl and methoxy groups
on the phenyl ring of sulfoxonium ylides
substantially increased the selectivity (3a:4a = 1:7.5)
despite a slight decrease in yield (entry 11). Although
*
[
Cp Rh(MeCN)
3
](SbF
6
) (4.0 mol %) was used in the
2
presence of CsOAc and KOAc (1.0 equiv, each) in
toluene or acetonitrile, inferior results were obtained
(
entries 12 and 13). Based on the fact that 1a was
regioselectively
yielded
the
corresponding
recovered in 28% (entry 13), optimum reaction
conditions for azulenolactam (4a) were obtained
when the reaction time was extended to 16 h,
providing 4a in 90% yield (entry 14). The use of
CsOAc or KOAc (2.0 equiv, each) gave inferior
results (entries 15 and 16). However, N-
methoxyazulene-2-carboxamide was not effective.
With the optimum reaction conditions in hand, we
examined the substrate scope of azulenecarboxamides
disubsititued azulenolactones (3u and 3x) in 75 and
83%, respectively. α,β-Diphenyl sulfoxonium ylide
possessing a 4-chloro group was
Table 2. Scope of Azulenes and Sulfoxonium Ylides for
[
a]
the Synthesis of Azulenolactones.
(
1) and sulfoxonium ylides (2) (Table 2). The
reaction efficiency was not influenced by the
electronic properties of the azulenes and sulfoxonium
ylides. Electron-donating methyl and tert-butyl
groups on the phenyl ring of sulfoxonium ylides
afforded the corresponding compounds (3b-3e).
Substrate bearing a strongly electron-donating 4-
methoxy group on the phenyl ring underwent C−H
activation followed by cyclization, producing 3f in
9
0% yield. Because 4-(N,N-dimethylamino)phenyl-
substituted sulfoxonium ylide has a slightly low
reactivity, the reaction conditions were modified, and
the desired product 3g was produced in 90% yield
with 3.0 equivalents of sulfoxonium ylide. In addition,
halogenated aryl sulfoxonium ylides bearing fluoro,
chloro, and bromo groups were well tolerated in the
reaction conditions to afford the corresponding
azulenolactones (3h-3k). The azulenolactone 3l was
produced in 82% yield despite the presence of a
strong electron-withdrawing trifluoromethyl group.
Also, a sulfoxonium ylide containing a thiophenyl
group underwent cyclization reaction, providing 3m
in 81% yield. Although the sulfoxonium ylides
bearing an ethyl and n-butyl group provided
unexpectedly the corresponding lactams (4l and 4m)
in quantitative yield instead of lactones under
condition A, the sulfoxonium ylide bearing a tert-
butyl group provided the desired lactone (3n) in 84%
yield. When sulfoxonium ylides obtained from (E)-
but-2-enoyl chloride and cinnamoyl chloride were
used, the desired lactones (3o and 3p) were produced
in 17 and 36%, respectively, together with lactam
compounds (4n and 4o) in major under condition A.
Gratifyingly, Rh-catalyzed cyclization reaction using
6
-methyl and 6-phenyl-substituted azulenes produced
the corresponding azelenolactones 3q and 3r in 80
and 85% yields, respectively. Additionally, azulene-
1-carboxamide bearing a 3-chloro group was
[a]
Condition A: 1a (0.2 mmol, 1.0 equiv), 2 (1.5 equiv),
applicable in the present transformation. Stimulated
by these results, regioselective synthesis of 3,4-
disubstituted azulenolactones was attempted with α,β-
disubstituted sulfoxonium ylides. For example, when
α,β-diphenyl sulfoxonium ylide was treated with 1a,
*
[
Cp Rh(MeCN)
3 6 2
](SbF ) (4.0 mol %), KOAc (0.3 equiv),
and PivOH (2.0 equiv) in toluene (1.0 mL) at 100 °C for
5
1
2 h. R = Me.
[b]
[c]
[d]
[e]
[f]
1
.0 mmol scale of 1a.
Sulfoxonium ylide (3.0 equiv).
the
corresponding
diphenyl-substituted
Isolated yields of 4n and 4o.
azulenolactone 3t was obtained in 78% yield. Next,
we investigated the scope of Rh-catalyzed
*
[
Cp Rh(MeCN)
3
](SbF
6
)
2
(8.0 mol %).
5
R = Et.
3
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Advanced Synthesis & Catalysis
10.1002/adsc.202001082
smoothly cyclized to produce 3v in 70% yield.
Gratifyingly, sulfoxonium ylide with phenyl and
methyl groups was subjected to a Rh-catalyzed
cyclization reaction, regioselectively producing the
desired aznulenolactone (3w) in 81% yield. To
demonstrate the applicability of the present method to
larger scale processes, a 1.0 mmol scale reaction of
converted to the desired azulenolactams (4b-4f) in
good yields. When sulfoxonium ylides bearing
electron-withdrawing fluoro, chloro, bromo, and
trifluoromethyl groups were used, the corresponding
azulenolactams (4g-4j) were selectively obtained in
good yields varying from 75 to 88%. Notably, ylide
with a 2-thiophenyl group was successfully applied to
the current method, producing 4k in 74% yield. The
cyclization was highly selective and useful, as proven
by the quantitative reaction using ethyl- and n-butyl-
sulfoxonium ylides (4l and 4m). In the case of
sulfoxonium ylides obtained from (E)-but-2-enoyl
chloride and cinnamoyl chloride, the desired lactams
(4n and 4o) were produced in 78 and 98% yields,
respectively, under condition B. However, the
sulfoxonium ylide bearing a tert-butyl group did not
react with N-methoxyazulene-1-carboxamide (1a)
under condition B. In addition, substrates having 6-
methyl, 3-methyl, and 3-chloro groups on the azulene
ring worked well with phenyl sulfoxonium ylide,
providing azulenolactams 4p-4r in good yields. Since
the Pd-catalyzed reaction of N-methoxyazulene-1-
carboxamides (1a) with unsymmetrical alkynes
provided regioisomeric products, a regioselective
synthetic method is extremely needed. Thus, we
investigated the Rh-catalyzed regioselective reaction
of 1a with sulfoxonium ylide 2 having substituents at
the α-position. When sulfoxonium ylide bearing
electron-donating methyl and methoxy groups on
each phenyl ring was treated with 1a, the desired
1
a (0.20 g) was attempted with 2a (1.5 equiv), thus
affording the desired azulenolactone 3a in 88% yield
0.24 g).
We next attempted the selective synthesis of
azulenolactams from the reaction of N-
methoxyazulene-1-carboxamides (1) with
(
sulfoxonium ylides (2) under the optimum condition
B (Table 3). Electronic variation of the substituents
did not largely influence the reaction efficiency. The
sulfoxonium ylides bearing electron-donating methyl,
tert-butyl, and methoxy groups were smoothly
Table 3. Scope of Azulenes and Sulfoxonium Ylides for
the Synthesis of Azulenolactams.[a]
diaryl-substituted
azulenolactam
4s
was
regioselectively obtained in 60% yield. Gratifyingly,
sulfoxoniumylides having not only aryl groups but
also alkyl groups were subjected to Rh-catalyzed
reactions,
regioselectively
providing
the
corresponding azulenolactams (4t and 4u)in 71% and
82% yields, respectively.
A catalytic C−H activation in toluene:D O (5:1)
2
and MeCN:D
significant D/H exchange at 2- and 8-position of
product 1a-[D ] (Scheme 2a and 2b). These results
2
O (5:1) was conducted, affording a
2
suggest that the C−H activation step is reversible.
H/D exchange in the substrates did not occur in the
absence of
a
catalyst, indicating that the
regioselective and chemodivergent synthesis of
azulenolactones and azulenolactams took place
through Rh(III)-catalyzed C−H activation reactions of
azulenecarboxamides with sulfoxonium ylides. Also,
H/D scrambling at the 8-position of N-
methoxyazuleneamide was observed, indicating that
8-position of nonbenzenoid aromatic compounds can
be used as a reactive site for C−H activation reaction.
Next, we performed kinetic isotope effect (KIE)
studies to obtain insight into the reaction mechanism
[
a]
Condition B: 1a (0.2 mmol, 1.0 equiv), 2 (1.5 equiv),
*
[
Cp Rh(MeCN)
3 6 2
](SbF ) (4.0 mol %), CsOAc (1.0
(
Scheme 2c and 2d). The KIE was observed (K
H
/K
D
=
equiv), and KOAc (1.0 equiv) in MeCN (1.0 mL) at
1.62, 1.60) by independent reactions using 1a or 1a-
5
1
00 °C for 16 h. R = Me.
[
[
[
[
b]
c]
d]
e]
[D ] as the substrate under condition A and B,
3
1
.0 mmol scale of 1a.
*
respectively (see the Supporting Information for
details). Also, the KIE was obtained (K /K = 1.54,
[
Cp Rh(MeCN)
3
](SbF
6
)
2
(8.0 mol %).
5
R = Et.
Sulfoxonium ylide (2.0 equiv).
H
D
1.57) via parallel reactions. Then, the KIE was
4
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Advanced Synthesis & Catalysis
10.1002/adsc.202001082
Scheme 3. A Proposed Mechanism.
with A to generate rhodium alkyl species B, and the
subsequent α-elimination of DMSO from B affords
Rh-carbene intermediate C. Then, it would undergo
migratory insertion of the Rh–C bond to give six-
membered rhodacycle D, and protonolysis would
afford acylmethylated intermediate E. Next, two
pathways are possible. In pathway a, PivOH activates
the amide group toward a nucleophilic attack by the
enol oxygen, leading to the formation of
Scheme 2. Deuterium-Labeling Experiments.
azulenolactones 3 with the elimination of NH OMe.
2
measured (K
H
/K
D
= 2.13) from intermolecular
] due to H/D
In contrast, in pathway b, the intramolecular
nucleophilic addition followed by dehydration
produces azulenolactam 4.
competition reaction using 1a and 1a-[D
3
scrambling. These results suggested that the cleavage
of C−H bond at the 2-position of N-
methoxyazuleneamide is not involved in the rate-
determining step.
Conclusion
When
N-methoxy-3-hydroxy-3-phenyl-3,4-
dihydroazulenolactam (5) was treated with KOAc
o
In conclusion, we have developed a regioselective
and chemodivergent reaction of N-methoxyazulene-
and PivOH in toluene at 100 C for 12 h,
azulenolactone (3a) was obtained in quantitative
yield with the release of methoxyamine, indicating
that ring-opening followed by ring-closing reaction
occurred smoothly under the equilibrium conditions
1
-carboxamides with sulfoxonium ylides, leading to
the selective formation of azulenolactones and
azulenolactams from the same starting materials.
Sulfoxonium ylides that act as a precursor of
secondary carbene was investigated, providing
azulenolactones and azulenolactams bearing two
substituents on a newly introduced double bond. The
present method demonstrated functionalization of less
reactive 2-position of azulene to overcome the natural
reactivity.
(
eq 1). Additionally, when 5 was treated with KOAc
o
and CsOAc in acetonitrile at 100 C for 12 h,
azulenolactam (4a) was produced in quantitative
yield through dehydration (eq 2).
Experimental Section
Commercial available reagents were used without
purification. All reaction mixtures were stirred
magnetically and were monitored by thin-layer
chromatography using silica gel pre-coated glass plates,
which were visualized with UV light and then, developed
using either iodine or a solution of anisaldehyde. For
reactions that require heating, oil bath was used as the
source of heating. Flash column chromatography was
A proposed mechanism for the Rh-catalyzed
reaction is illustrated in Scheme 3. Rhodacyclic
intermediate A is generated through C–H activation
from N-methoxyazulene-1-carboxamide (1) with a
Rh(III) catalyst. Sulfoxonium ylide 2 is coordinated
1
carried out using silica gel (230-400 mesh). H NMR (400
13
1
19
MHz), C{ H} NMR (100 MHz), and F NMR (377
MHz) spectra were recorded on NMR spectrometer.
Deuterated chloroform, dimethyl sulfoxide, and acetone
5
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Advanced Synthesis & Catalysis
10.1002/adsc.202001082
were used as the solvents, and chemical shift values (δ) are
To a stirred solution of potassium tert-butoxide (3.0 g,
reported in parts per million relative to the residual signals
27.2 mmol) in THF (30 mL) was added
1
o
of these solvent [δ 7.26 for H (chloroform-d), δ 2.50 for
trimethylsulfoxonium iodide (5.0 g, 20.6 mmol) at 25 C.
1
13
1
H (DMSO-d
6
), δ 77.2 for C{ H} (chloroform-d), δ 39.5
The resulting mixture is refluxed for 2 h. Then, reaction
mixture was cooled to 0 °C, followed by addition of acyl
chlorides (7.0 mmol) in THF (5 mL). The reaction was
1
3
1
6
for C{ H} (DMSO-d )]. Infrared spectra were recorded
on FT-IR spectrometer as either a thin film pressed
between two sodium chloride plates or as a solid
suspended in a potassium bromide disk. High resolution
mass spectra (HRMS) were obtained by electron impact
o
allowed to 25 C and stirred for 3 h. Next, the solvent was
evaporated and water (15 mL) and ethyl acetate (20 mL)
were added to the resulting slurry. The layers were
separated and the aqueous layer was washed with ethyl
acetate (2 x 30 mL) and the organic layers were combined.
(
EI) ionization technique (magnetic sector - electric sector
double focusing mass analyzer) from the KBSI (Korea
Basic Science Institute Daegu Center). Melting points were
determined in open capillary tube.
4
The organic phase was dried over MgSO and evaporated
under reduced pressure. The crude product was purified by
recrystalization using EtOAc and hexane to afford the
corresponding sulfoxonium ylide.
1
. General Procedure for the Starting Material
(
a) Synthetic Procedure for Azulene-1-carboxylic
[2b,13]
Acid
(e) Synthetic Procedure for α-Aryl-β-keto Sulfoxonium
[
15,16]
Phosphoryl trichloride (1.1 mL, 12 mmol) was added to
anhydrous DMF (5.0 mL) very slowly at 0 °C and the
mixture was stirred for 30 min. After 30 min, a solution of
azulene (1.28 g, 10 mmol) in DMF was added to reaction
Ylides
To an oven dried 25 mL round bottom flask containing a
magnetic stirrer, β-ketosulfoxonium ylide (1.0 equiv, 1.0
mmol), activated molecular sieves 4 Å powder (200 mg),
CsF (4.0 equiv, 607.6 mg, 4.0 mmol), and dry acetonitrile
(8.0 mL) were added. Under vigorous stirring, the
appropriate precursor of aryne (1.5 equiv, 1.5 mmol) was
added in three portions at intervals of 1 h at 65 ºC. After 3
h, the organic solvent was removed into rotary evaporator
and the crude product purified by column chromatography,
employing the basic silica gel (MeOH : DCM = 1 : 50) to
afford the corresponding α-aryl-β-keto sulfoxonium ylides.
o
mixture slowly at 25 C. The reaction mixture was stirred
o
at 25 C for 2 h. The mixture was quenched by addition of
1
0 % aqueous NaOH (20 mL). Then, the mixture was
extracted with ethyl acetate (3 x 30 mL) and the combined
organic phase was washed with brine. After drying over
4
MgSO , the solvent was removed under reduced pressure
to afford the azulene-1-carboxaldehyde as an oil (1.48 g,
9
0
5%). To a solution of azulene-1-carboxaldehyde (0.109 g,
.70 mmol) and Na CO in acetone/H O 5:1 (13.5 mL)
(0.283 g, 1.79 mmol) in H
2
3
2
o
were added KMnO
4
2
O at 25 C
[11,15]
(
f) Procedure for the Triethylsulfoxonium chloride
o
for 5 min. The mixture was stirred for 4 h at 25 C. The
suspension was then treated with 5% aq. HCl and acetone
was removed by evaporation. Then, the mixture was
extracted with ethyl acetate (3 x 15 mL). After drying over
Diethyl sulfide (2.0 g, 22.7 mmol, 1.0 equiv) was added
to a flame-dried schlenk tube, followed by iodoethane (3.9
g, 25.0 mmol, 1.1 equiv) and iodine (2.9 g, 11.4 mmol, 0.5
equiv) under nitrogen condition. The tube was sealed and
the mixture was stirred at 70 °C overnight. Then, the
MgSO
red-violet crystals).
4
, the desired product was obtained (91.6 mg, 76%,
o
mixture was transferred at 25 C to a conical flask with
water
(70
mL),
DCM
(46
mL)
and
(
b)
Synthetic
Procedure
for
Azulene-1-N-
tributylbenzylammonium chloride (7.1 g, 22.7 mmol, 1.0
equiv). The mixture was protected from light and stirred
[
14]
methoxyamide
o
1
) To a solution of the azulene-1-carboxaldehyde (10.0
overnight at 25 C. The two layers were separated and the
mmol, 1.0 equiv) in dry DCM (50 mL) at 0°C under a
nitrogen atmosphere was dropwise added oxalyl chloride
aqueous layer was washed with 5 times with DCM (30
mL). The aqueous layer was evaporated to give
triethylsulfonium chloride as hygroscopic white solid.
(
1.0 mL, 12.0 mmol, 1.2 equiv) followed by a catalytic
amount of dry DMF (10 drops). The reaction was stirred at
o
2
5 C for 2 h. The solvent was then removed under reduce
Triethylsulfonium chloride was dissolved with water
112 mL) in a round bottom flask, the resulting solution
pressure.
(
was cooled to 0 °C and NaOH (5.4 g, 0.13 mol, 6 equiv)
was added. The mixture was stirred at 0 °C until
homogeneous. mCPBA (22.2 g, 90.0 mmol, 4 equiv (77%
grade)) was added in portions and the mixture was stirred
at 50 °C for 30 minutes. Then the pH was adjusted to pH =
1 with 6 M HCl (20 mL) at 0 °C. The precipitate was
filtered off and washed with water. The corresponding
filtrate was concentrated to 60 mL and washed with DCM
(20 mL). The pH of the aqueous layer was adjusted to pH
2
) After methoxyamine hydrochloride (1.7 g, 20.0 mmol,
2
.0 equiv) and triethylamine (3.5 mL, 25.0 mmol, 2.5
equiv) in DCM (80 mL) was stirred for 10 min, the
resulting solution was cooled to 0°C followed by a
dropwise addition of the unpurified azulene-1-carbonyl
chloride dissolved in a DCM (20 mL). The reaction was
o
stirred at 25 C for 1 h. Afterwards, the reaction was
4
quenched with aqueous NH Cl solution and extracted with
dichloromethane (3 x 30 mL). The organic phase was dried
2 3
= 5-6 with saturated Na CO and evaporated to dryness.
over MgSO
4
and evaporated under reduced pressure. The
The resulting solid was dispersed in warm iPrOH (40 mL)
and the mixture was filtered. All volatiles were removed
and the crude product was recrystallized from iPrOH to
give triethylsulfoxonium chloride as white solid.
pure products were purified by column chromatography on
silica gel (ether : DCM : hexane = 1 : 4 : 1) to afford N-
methoxyazuleneamide (1.4g, 74%). Violet solid.
(
c)
Synthetic
Procedure
for
3-Chloro-N-
2. General Procedure for Rh-Catalyzed Tandem
Annulation Reaction of N-Methoxyazuleneamides with
Sulfoxonium Ylides
methoxyazulene-1-carboxamide
NCS (133.5 mg, 1.0 mmol) was added to a stirred
solution of azulene-1-N-methoxyamide (201.2 mg, 1.0
(a) Synthesis of azulenolactone
mmol) in CH
2
Cl
2
(5 mL) at 0 °C. After being stirred for 10
To an oven-dried test tube charged with N-
min, the cooling bath was removed, and the reaction
methoxyazuleneamide
1
(40.1 mg, 0.2 mmol),
o
*
mixture was stirred at 25 C for 30 min. Next, the reaction
3 2
[Cp Rh(MeCN) ] (6.7 mg, 0.008 mmol, 4.0 mol %),
mixture was evaporated to a small volume (~ 2 mL), and
the residue was diluted with hexane (15 mL). As a result, a
precipitate of succinimide formed was filtered off. The
volatiles were evaporated, and the residue was purified by
column chromatography (hexane) to afford the 3-chloro-N-
methoxyazulene-1-carboxamide as a blue solid (233.3 mg,
KOAc (5.9 mg, 0.06 mmol), PivOH (40.8 mg, 0.4 mmol),
sulfoxonium ylide 2 (58.9 mg, 0.3 mmol), and toluene (1.0
mL). The reaction mixture was stirred at 100 °C for 12 h
under a nitrogen atmosphere. Then, the solvent was
evaporated under reduced pressure and the residue was
purified by column chromatography on silica gel using
dichloromethane : hexane = 4:1.
9
9%).
(
d) Synthetic Procedure for Sulfoxonium Ylides[11,15]
(b) Synthesis of azulenolactam
6
This article is protected by copyright. All rights reserved.

Advanced Synthesis & Catalysis
10.1002/adsc.202001082
To an oven-dried test tube charged with N-
3-(4-Methoxyphenyl)-1H-azuleno[1,2-c]pyran-1-one
methoxyazuleneamide
1
(40.1 mg, 0.2 mmol),
(3f) : Yield : 54.3 mg (90%); R = 0.3 (dichloromethane :
f
*
o 1
[
Cp Rh(MeCN)
3
]
2
(6.7 mg, 0.008 mmol, 4.0 mol %),
hexane = 4:1); Red solid; Melting point : 190-192 C; H
KOAc (19.6 mg, 0.2 mmol), CsOAc (38.4 mg, 0.2 mmol),
sulfoxonium ylide 2 (58.9 mg, 0.3 mmol) and MeCN (1.0
mL). The reaction mixture was stirred at 100 °C for 16 h
under a nitrogen condition. Then, the solvent was
evaporated under reduced pressure and the residue was
purified by column chromatography on silica gel using
acetone : hexane = 1 : 7.
3
NMR (400 MHz, CDCl )  9.45 (d, J = 9.2 Hz, 1H), 8.34
(d, J = 10.2 Hz, 1H), 7.94 (d, J = 9.0 Hz, 2H), 7.70 (tt, J =
2.7 Hz, 1H), 7.61 (t, J = 9.7 Hz, 1H), 7.50-7.45 (m, 1H),
7.19 (s, 1H), 7.17 (s, 1H), 6.99 (d, H = 9.0 Hz, 2H), 3.88 (s,
1
3
1
3H); C{ H} NMR (100 MHz, CDCl )  161.4, 160.2,
3
157.9, 149.9, 146.5, 141.9, 137.4, 136.6, 135.5, 130.0,
128.8, 127.6, 125.4, 114.4, 112.1, 107.4, 98.0, 55.6; IR
-
1
(
film): 3076, 1715, 1604, 1258, 1177, 913, 631 cm ;
+
14 3
HRMS (EI) m/z: [M] Calcd for C20H O 302.0943;
3
3
5
. Characterization data
Found 302.0945.
-Phenyl-1H-azuleno[1,2-c]pyran-1-one (3a) : Yield :
0.1 mg (92%); R = 0.3 (dichloromethane : hexane = 4:1);
f
o 1
Red solid; Melting point : 192-194 C; H NMR (400 MHz, 3-(4-(Dimethylamino)phenyl)-1H-azuleno[1,2-c]pyran-
CDCl
3
)  9.51 (d, J = 9.2 Hz, 1H), 8.4 (d, J = 10.2 Hz, 1H), 1-one (3g) : Yield : 56. 7 mg (90%); R
f
= 0.3
8
.01 (d, J = 7.0 Hz, 1H), 7.76 (t, J = 9.7 Hz, 1H), 7.65 (t, J (dichloromethane : hexane = 4:1); Red solid; Melting
o
1
=
9.7 Hz, 1H), 7.54-7.43 (m, 4H), 7.31 (s, 1H), 7.25 (s,
point : 250-252 C; H NMR (400 MHz, CDCl )  9.04 (d,
3
1
3
1
1
1
1
1
H); C{ H} NMR (100 MHz, CDCl
3
)  160.0, 157.5,
J = 9.0 Hz, 1H), 8.29 (d, J = 10.2 Hz, 1H), 7.90 (d, J = 9.0
Hz, 2H), 7.64 (t, J = 9.5 Hz, 1H), 7.58 (t, J = 9.6 Hz, 1H),
7.43 (t, J = 9.6, Hz, 1H), 7.15 (s, 1H), 7.11 (s, 1H), 6.75 (d,
49.3, 146.3, 141.6 137.8, 136.9, 135.9, 132.7, 130.2,
29.9, 128.9, 128.8, 125.9, 112.2, 107.6; IR (film): 3059,
-
1
+
13
1
711, 1607, 1017, 914, 686 cm ; HRMS (EI) m/z: [M]
J = 9.0 Hz, 2H), 3.05 (s, 6H); C{ H} NMR (100 MHz,
Calcd for C19
H
12
O
2
272.0837; Found 272.0838.
CDCl
3
)  160.4, 159.2, 152.0, 150.7, 146.7, 142.3, 136.6,
35.9, 134.7, 130.0, 128.6, 127.5, 120.5, 112.1, 111.9,
07.3, 96.3, 40.3; IR (film): 3056, 1703, 1598, 1373, 1197,
1
1
9
3
-(o-Tolyl)-1H-azuleno[1,2-c]pyran-1-one (3b) : Yield :
2.6 mg (92%); R = 0.3 (dichloromethane : hexane = 4:1);
-
1
+
45, 635 cm ; HRMS (EI) m/z: [M] Calcd for C21H17NO
2
5
f
o
1
315.1259; Found 315.1256.
Red solid; Melting point : 175-177 C; H NMR (400 MHz,
CDCl
3
)  9.54 (d, J = 9.3 Hz, 1H), 8.42 (d, J = 10.2 Hz,
1
H), 7.78 (t, J = 9.8 Hz, 1H), 7.67 (t, J = 9.8 Hz, 1H), 7.60
3-(2-Fluorophenyl)-1H-azuleno[1,2-c]pyran-1-one (3h) :
Yield : 47.0 mg (81%); R = 0.3 (dichloromethane : hexane
= 4:1); Red solid; Melting point : 202-204 C; H NMR
(
d, J = 4.5 Hz, 1H), 7.53 (t, J = 9.7 Hz, 1H), 7.38-7.27 (m,
f
1
3
1
o
1
4
H), 7.25 (s, 1H), 2.26 (s, 3H); C{ H} NMR (100 MHz,
)  160.5, 159.8, 149.4, 146.3, 141.6, 138.0, 137.03,
37.02, 136.2, 133.7, 131.2, 130.0, 129.9, 129.5, 128.9,
26.1, 112.1, 107.5, 103.6, 21.1; IR (film) : 3062, 1712,
CDCl
3
3
(400 MHz, CDCl )  9.51 (d, J = 9.2 Hz, 1H), 8.41 (d, J =
1
1
1
10.2 Hz, 1H), 8.15 (td, J = 3.5 Hz, 1H), 7.77 (t, J = 9.8 Hz,
1H), 7.65 (t, J = 9.8 Hz, 1H), 7.54-7.49 (m, 2H), 7.43-7.38
-
1
+
13
1
612, 1012, 915, 640 cm ; HRMS (EI) m/z: [M] Calcd
286.0994; Found 286.0992.
(m, 1H), 7.31-7.27 (m, 1H), 7.22-7.17 (m, 1H); C{ H}
for C20
H
14
O
2
NMR (100 MHz, CDCl
3
)  160.4 (d, J = 253.3 Hz), 160.0,
52.1, 152.0, 149.3, 146.3, 141.6, 138.2, 137.3, 136.4,
31.4 (d, J = 9.2 Hz), 130.0, 129.4, 128.9, 124.7 (d, J = 3.5
1
1
3
-(m-Tolyl)-1H-azuleno[1,2-c]pyran-1-one (3c) : Yield :
1.5 mg (90%); R = 0.3 (dichloromethane : hexane = 4:1);
Hz), 121.1, 121.0, 116.6 (d, J = 23.2 Hz), 112.7, 108.1,
5
f
19
o
1
3
104.9, 104.7; F NMR (376 MHz, CDCl )  -111.5; IR
-1
Red solid; Melting point : 200-202 C; H NMR (400 MHz,
CDCl
(
film): 3064, 1731, 1604, 1215, 1018, 944, 629 cm ;
+
3
)  9.50 (d, J = 9.2 Hz, 1H), 8.39 (d, J = 10.2 Hz,
2
HRMS (EI) m/z: [M] Calcd for C19H11FO 290.0743;
1
H), 7.85 (s, 1H), 7.79 (d, J = 7.9 Hz, 1H), 7.75 (t, J = 10.5
Found 290.0743.
Hz, 1H), 7.64 (t, J = 9.8 Hz, 1H), 7.50 (t, J = 9.7 Hz, 1H),
7
7
.37 (t, J = 7.7 Hz, 1H), 7.29 (s, 1H), 7.26 (d, J = 7.5, 1H),
13 1
.24 (s, 1H), 2.45 (s, 3H); C{ H} NMR (100 MHz,
3-(3-Chlorophenyl)-1H-azuleno[1,2-c]pyran-1-one (3i) :
Yield : 51.4 mg (84%); R = 0.3 (dichloromethane : hexane
= 4:1); Red solid; Melting point : 219-221 C; H NMR
1
3
1
CDCl
3
)
C{ H} NMR (100 MHz, CDCl
3
)  160.2, 157.8,
f
o
1
1
1
2
49.5, 146.4, 141.7, 138.7, 137.8, 136.9, 135.9, 132.7,
31.1, 130.0, 128.8, 128.8, 126.6, 123.1, 112.2, 107.7, 99.4,
3
(400 MHz, CDCl )  9.52 (d, J = 9.3 Hz, 1H), 8.42 (d, J =
-
1
1.6; IR (film): 3027, 1710, 1611, 1023, 934, 794 cm ;
10.1 Hz, 1H), 7.99 (s, 1H), 7.89-7.86 (m, 1H), 7.79 (t, J =
9.8 Hz, 1H), 7.67 (t, J = 9.8 Hz, 1H), 7.53 (t, J = 9.7, Hz,
+
HRMS (EI) m/z: [M] Calcd for C20
H
14
O
2
286.0994;
13
1
Found 286.0995.
1H), 7.42-7.41 (m, 1H), 7.30 (s, 1H), 7.26 (s, 1H); C{ H}
NMR (100 MHz, CDCl
3
)  159.8, 156.0, 148.9, 146.5,
41.7, 138.3, 137.3, 136.5, 135.2, 134.6, 130.22, 130.18,
30.17, 129.1, 126.1, 124.0, 112.4, 107.8, 100.3; IR (film):
1
1
3
-(p-Tolyl)-1H-azuleno[1,2-c]pyran-1-one (3d) : Yield :
3.2 mg (93%); R = 0.3 (dichloromethane : hexane = 4:1);
5
f
-
1
o
1
3089, 1710, 1609, 1030, 950, 787, 671 cm ; HRMS (EI)
Red solid; Melting point : 202-204 C; H NMR (400 MHz,
+
m/z: [M] Calcd for C19
06.0450.
H
11ClO
2
306.0448; Found
CDCl
H), 7.90 (d, J = 8.2 Hz, 2H), 7.72 (t, J = 9.7 Hz, 1H), 7.62
t, J = 9.7 Hz, 1H), 7.48 (t, J = 9.7 Hz, 1H), 7.28 (d, J = 8.1
3
)  9.47 (d, J = 9.2 Hz, 1H), 8.36 (d, J = 10.2 Hz,
3
1
(
13
1
Hz, 2H), 7.24 (s, 1H), 7.21 (s, 1H), 2.45 (s, 3H); C{ H}
3-(4-Chlorophenyl)-1H-azuleno[1,2-c]pyran-1-one (3j) :
Yield : 50.8 mg (83%); R = 0.3 (dichloromethane : hexane
= 4:1); Red solid; Melting point : 230-232 C; H NMR
NMR (100 MHz, CDCl
3
)  160.2, 158.0, 149.7, 146.4,
41.8, 140.7, 137.7, 136.8, 135.8, 130.1, 130.0, 129.7,
28.8, 126.0, 112.2, 107.7, 98.8, 21.6; IR (film): 3027,
+
f
o
1
1
1
1
(400 MHz, CDCl )  9.48 (d, J = 9.3 Hz, 1H), 8.38 (d, J =
3
-
1
710, 1611, 1023, 934, 608 cm ; HRMS (EI) m/z: [M]
286.0994; Found 286.0996.
10.2 Hz, 1H), 7.91 (d, J = 8.5, 1H), 7.76 (t, J = 9.7 Hz, 1H),
7.64 (t, J = 9.8 Hz, 1H), 7.51 (t, J = 9.7 Hz, 1H), 7.43 (d, J
Calcd for C20
H
14
O
2
1
3
1
=
8.6, Hz, 1H), 7.25 (s, 1H), 7.22 (s, 1H); C{ H} NMR
(
100 MHz, CDCl
3
)  159.9, 156.4, 149.0, 146.4, 141.7,
3
-(4-(tert-Butyl)phenyl)-1H-azuleno[1,2-c]pyran-1-one
3e) : Yield : 59.1 mg (90%); R = 0.3 (dichloromethane :
hexane = 4:1); Red solid; Melting point : 207-209 C; H
1
38.1, 137.1, 136.3, 136.3, 131.3, 130.1, 129.2, 129.0,
(
f
o
1
127.2, 112.3, 107.7, 99.7; IR (film): 3091, 1710, 1611,
-
1
+
1
091, 913, 828, 673 cm ; HRMS (EI) m/z: [M] Calcd for
306.0448; Found 306.0451.
NMR (400 MHz, CDCl
3
)  9.48 (d, J = 9.2 Hz, 1H), 8.37
19 2
C H11ClO
(
d, J = 10.2 Hz, 1H), 7.94 (d, J = 8.5Hz, 2H), 7.73 (t, J =
9
7
.7 Hz, 1H), 7.63 (t, J = 9.7 Hz, 1H), 7.51-7.47 (m, 3H),
13 1
.27 (s, 1H), 7.23 (s, 1H), 1.37 (s, 9H); C{ H} NMR (100
)  160.2, 157.9, 153.8, 149.7, 146.4, 141.8,
37.7, 136.8, 135.8, 130.0, 130.0, 128.8, 125.9, 125.8,
12.2, 107.7, 98.9, 35.0, 31.3; IR (film): 3069, 1709, 1608,
3-(4-Bromophenyl)-1H-azuleno[1,2-c]pyran-1-one
(3k) : Yield : 54.8 mg (78%); R = 0.3 (dichloromethane :
hexane = 4:1); Red solid; Melting point : 239-241 C; H
MHz, CDCl
3
f
o
1
1
1
1
NMR (400 MHz, CDCl )  9.50 (d, J = 9.3 Hz, 1H), 8.40
3
-
1
+
021, 915, 640 cm ; HRMS (EI) m/z: [M] Calcd for
328.1463; Found 328.1460.
(d, J = 10.2 Hz, 1H), 7.85 (d, J = 8.6 Hz, 2H), 7.78 (t, J =
9.8 Hz, 1H), 7.66 (t, J = 9.8 Hz, 1H), 7.60 (d, J = 8.6 Hz,
C
23
H
20
O
2
2
H), 7.52 (t, J = 9.8, Hz, 1H), 7.28 (s, 1H), 7.24 (s, 1H);
7
This article is protected by copyright. All rights reserved.

Advanced Synthesis & Catalysis
10.1002/adsc.202001082
1
3
1
C{ H} NMR (100 MHz, CDCl
3
)  159.9, 156.5, 149.0,
10.6 Hz, 1H), 8.01-7.98 (m, 2H), 7.54 (d, J = 9.9 Hz, 1H),
1
1
1
46.5, 141.7, 138.2, 137.2, 136.3, 132.2, 131.8, 130.2,
29.1, 127.4, 124.7, 112.3, 107.7, 99.7; IR (film): 3054,
7.50-7.41 (m, 4H), 7.28 (s, 1H), 7.17 (s, 1H), 2.73 (s, 3H);
1
3
1
C{ H} NMR (100 MHz, CDCl )  160.3, 157.1, 150.4,
3
-
1
708, 1610, 1025, 948, 671, 607 cm ; HRMS (EI) m/z:
148.3, 145.2, 140.1, 136.1, 135.5, 133.0, 131.2, 130.7,
130.1, 128.9, 126.0, 112.0, 107.9, 99.5, 28.3; IR (film):
3031, 1705, 1613, 1016, 915, 663 cm ; HRMS (EI) m/z:
+
+
79
81
[
M] Calcd for C19
H
11Br O
2
349.9942, C19
H11Br O
2
-
1
3
51.9922; Found 349.9945, 351.9940.
[
14 2
M] Calcd for C20H O 286.0994; Found 286.0994.
3
1
-(4-(Trifluoromethyl)phenyl)-1H-azuleno[1,2-c]pyran-
-one (3l) : Yield : 55.8 mg (82%); R = 0.3
f
3,8-Diphenyl-1H-azuleno[1,2-c]pyran-1-one
Yield : 59.2 mg (85%); R = 0.3 (dichloromethane : hexane
= 4:1); Red solid; Melting point : 241-243 C; H NMR
(3r)
:
(
dichloromethane : hexane = 4:1); Red solid; Melting
f
o
1
o
1
point : 240-242 C; H NMR (400 MHz, CDCl )  9.54 (d,
3
J = 9.2 Hz, 1H), 8.43 (d, J = 10.2 Hz, 1H), 8.10 (d, J = 8.1
Hz, 2H), 7.81 (t, J = 9.7 Hz, 1H), 7.73 (d, J = 8.3 Hz, 2H),
3
(400 MHz, CDCl )  9.52 (d, J = 10.0 Hz, 1H), 8.43 (d, J =
10.8 Hz, 1H), 8.02 (d, J = 7.3 Hz, 2H), 7.85 (d, J = 9.9 Hz,
1H), 7.75 (d, J = 10.8 Hz, 1H), 7.67 (t, J = 7.4 Hz, 2H),
7
1
1
1
3
.68 (t, J = 10.3 Hz, 1H), 7.55 (t, J = 9.7, Hz, 1H), 7.37 (s,
13 1
13
1
H), 7.28 (s, 1H); C{ H} NMR (100 MHz, CDCl
3
) 
7.54-7.43 (m, 6H), 7.32 (s, 1H), 7.25 (s, 1H); C{ H}
59.7, 155.8, 148.6, 146.5, 141.7, 138.6, 137.5, 136.7,
3
NMR (100 MHz, CDCl )  160.2, 157.6, 151.8, 149.2,
36.1, 131.7 (q, J = 31.7 Hz), 130.2, 129.2, 124.0 (q, J =
145.1, 144.3, 140.5, 136.3, 135.4, 132.9, 130.3, 130.0,
129.9, 129.2, 129.0,128.8, 128.7, 126.0, 112.4, 108.1, 99.7;
19
.6 Hz), 124.0 (q, J = 169.0 Hz), 112.5, 107.9, 101.0;
F
-
1
NMR (376 MHz, CDCl
615, 1169, 1118, 955, 669 cm ; HRMS (EI) m/z: [M]
Calcd for C20 O 340.0711; Found 340.0713.
3
)  -62.8; IR (film): 3090, 1714,
IR (film): 3047, 1712, 1609, 1016, 913, 631 cm ; HRMS
+
-
1
+
1
16 2
(EI) m/z: [M] Calcd for C25H O 348.1150; Found
H
11
F
3
348.1147.
3
-(Thiophen-2-yl)-1H-azuleno[1,2-c]pyran-1-one (3m) :
5-Chloro-3-phenyl-1H-azuleno[1,2-c]pyran-1-one (3s) :
Yield : 52.6 mg (86%); R = 0.3 (dichloromethane : hexane
= 4:1); Green solid; Melting point : 247-249 C; H NMR
Yield : 45.0 mg (81%); R = 0.3 (dichloromethane : hexane
f
f
o
1
o
1
=
4:1); Red solid; Melting point : 220-222 C; H NMR
)  9.45 (d, J = 9.3 Hz, 1H), 8.36 (d, J =
0.2 Hz, 1H), 7.75-7.70 (m, 2H), 7.63 (t, J = 9.7, 1H), 7.49
(
400 MHz, CDCl
3
3
(400 MHz, CDCl )  9.47 (d, J = 8.8 Hz, 1H), 8.46 (d, J =
1
10.2 Hz, 1H), 8.06-8.04 (m, 2H), 7.80 (t, J = 9.8 Hz, 1H),
7.66 (t, J = 9.8 Hz, 1H), 7.59 (t, J = 9.8 Hz, 1H), 7.53-7.46
(
t, J = 9.7 Hz, 1H), 7.44 (dd, J = 2.0 Hz, 1H), 7.18 (s, 1H),
1
3
1
13
1
7
.13 (dd, J = 2.9 Hz, 1H), 7.11 (s, 1H); C{ H} NMR (100
)  159.5, 153.4, 149.2, 146.6, 142.0, 137.8,
36.9, 136.8, 135.8, 130.2, 129.1, 128.4, 128.2, 127.0,
12.1, 107.4, 98.7; IR (film): 3073, 1799, 1710, 1603,
3
(m, 3H), 7.36 (s, 1H); C{ H} NMR (100 MHz, CDCl ) 
MHz, CDCl
3
159.3, 158.8, 146.0, 140.1, 139.9, 138.8, 136.4, 134.0,
132.5, 130.8, 130.5, 129.3, 129.1, 126.2, 111.3, 105.6,
1
1
1
-
96.7; IR (film): 3061, 1737, 1611, 1014, 913, 761, 601 cm
-
1
+
1
+
115, 946, 666 cm ; HRMS (EI) m/z: [M] Calcd for
S 278.0402; Found 278.0405.
2
; HRMS (EI) m/z: [M] Calcd for C19H11ClO 306.0448;
C
17
H
10
O
2
Found 306.0445.
3
-(tert-Butyl)-1H-azuleno[1,2-c]pyran-1-one
Yield : 42.3 mg (84%); R = 0.3 (acetone: hexane = 1:7);
Red solid; Melting point : 87-89 C; H NMR (400 MHz,
CDCl )  9.47 (d, J = 9.3 Hz, 1H), 8.37 (d, J = 10.2 Hz,
H), 7.73 (t, J = 9.8 Hz, 1H), 7.62 (t, J = 9.8 Hz, 1H), 7.48
t, J = 9.7 Hz, 1H), 7.14 (s, 1H), 6.68 (s, 1H), 1.40 (s, 9H);
(3n)
:
3,4-Diphenyl-1H-azuleno[1,2-c]pyran-1-one
Yield : 54.3 mg (78%); R = 0.3 (dichloromethane : hexane
= 4:1); Red solid; Melting point : 207-209 C; H NMR
(3t)
:
f
f
o
1
o
1
3
3
(400 MHz, CDCl )  9.61 (d, J = 9.3 Hz, 1H), 8.33 (d, J =
1
10.1 Hz, 1H), 7.78 (t, J = 9.8 Hz, 1H), 7.68 (t, J = 9.7 Hz,
(
1H), 7.48-7.45 (m, 3H), 7.44-7.37 (m, 5H), 7.30-7.21 (m,
1
3
1
13
1
C{ H} NMR (100 MHz, CDCl
3
)  170.1, 160.8, 150.1,
3
2H), 7.00 (s, 1H); C{ H} NMR (100 MHz, CDCl ) 
1
1
9
2
46.2, 141.6, 137.5, 136.6, 135.7, 129.8, 128.6, 111.8,
07.4, 97.4, 36.4, 28.4; IR (film): 3070, 1708, 1616, 1094,
160.1, 154.6, 151.3, 145.9, 141.9, 138.2, 137.3, 136.7,
135.6, 133.4, 130.6, 130.1, 129.9, 129.3, 129.1, 128.9,
128.0, 127.9, 116.0, 112.5, 107.5; IR (film): 3059, 1700,
-
1
+
16 2
40, 693 cm ; HRMS (EI) m/z: [M] Calcd for C17H O
-
1
+
52.1150; Found 252.1147.
1586, 1147, 963, 634 cm ; HRMS (EI) m/z: [M] Calcd
16 2
for C25H O 348.1150; Found 348.1151.
(
(
E)-3-(prop-1-en-1-yl)-1H-azuleno[1,2-c]pyran-1-one
3o) : Yield : 8.0 mg (17%); R = 0.3 (dichloromethane :
f
4-(3-Methoxyphenyl)-3-phenyl-1H-azuleno[1,2-
f
c]pyran-1-one (3u) : Yield : 62.8 mg (83%); R = 0.3
o
1
hexane = 4:1); Red solid; Melting point : 102-104 C; H
NMR (400 MHz, CDCl
3
)  9.45 (d, J = 9.2 Hz, 1H), 8.35
(dichloromethane : hexane = 4:1); Red solid; Melting
o 1
(
d, J = 10.2 Hz, 1H), 7.72 (t, J = 9.8 Hz, 1H), 7.62 (t, J =
3
point : 188-190 C; H NMR (400 MHz, CDCl )  9.61 (d,
9
6
.8 Hz, 1H), 7.48 (t, J = 9.7 Hz, 1H), 7.15 (s, 1H), 6.87-
.78 (m, 1H), 6.59 (s, 1H), 6.19 (dd, J = 5.7 Hz, 1H), 1.96
J = 9.2 Hz, 1H), 8.34 (d, J = 10.2 Hz, 1H), 7.79 (t, J = 9.8
Hz, 1H), 7.68 (t, J = 9.7 Hz, 1H), 7.52-7.48 (m, 3H), 7.36-
1
3
1
13
1
(
dd, J = 2.7 Hz, 3H); C{ H} NMR (100 MHz, CDCl
3
) 
7.23 (m, 4H), 7.05 (s, 1H), 6.98-6.94 (m, 3H); C{ H}
1
1
60.2, 156.6, 149.7, 146.5, 141.9, 137.6 136.7 135.7 133.4
30.1 128.9 124.4 112.0 101.4 77.5 77.2 76.9, 18.7; IR
3
NMR (100 MHz, CDCl )  160.1, 160.0, 154.6, 151.2,
145.9, 141.9, 138.2, 137.4, 136.9, 136.7, 133.4, 130.1,
130.1, 129.8, 129.3, 128.8, 128.1, 123.1, 116.1, 115.9,
113.6, 112.6, 107.5, 55.4; IR (film): 3061, 1705, 1586,
-
1
(
film): 3060, 1681, 1556, 1211, 1148, 928, 641 cm ;
+
12 2
HRMS (EI) m/z: [M] Calcd for C16H O 236.2700;
-
1
+
Found 236.2701.
1290, 1243, 923, 634 cm ; HRMS (EI) m/z: [M] Calcd
18 3
for C26H O 378.1256; Found 378.1253.
(
E)-3-styryl-1H-azuleno[1,2-c]pyran-1-one (3p) : Yield :
1.5 mg (36%); R = 0.3 (dichloromethane : hexane = 4:1);
Red solid; Melting point : 203-205 C; H NMR (400 MHz, Yield : 54.3 mg (75%); R
2
f
4-Phenyl-3-(p-tolyl)-1H-azuleno[1,2-c]pyran-1-one (3v):
= 0.3 (dichloromethane : hexane
o
1
f
o
1
CDCl
3
)  9.47 (d, J = 9.2 Hz, 1H), 8.36 (d, J = 10.1 Hz,
= 4:1); Red solid; Melting point : 244-246 C; H NMR
1
H), 7.73 (t, J = 9.8 Hz, 1H), 7.65-7.55 (m, 4H), 7.49 (t, J
3
(400 MHz, CDCl )  9.61 (d, J = 9.2 Hz, 1H), 8.31 (d, J =
=
9.7 Hz, 1H), 7.39 (t, J = 7.4 Hz, 2H), 7.33 (t, J = 7.4 Hz,
10.2 Hz, 1H), 7.76 (td, J = 3.9 Hz, 1H), 7.67 (t, J = 9.7 Hz,
1H), 7.48 (t, J = 9.8 Hz, 1H), 7.45-7.36 (m, 7H), 7.04 (d, J
1
H), 7.18 (s, 1H), 6.84 (s, 1H), 6.79 (d, J = 5.5 Hz, 1H);
13
1
13
1
C{ H} NMR (100 MHz, CDCl
3
)  160.0, 156.6, 149.2,
= 8.0 Hz, 2H), 6.98 (s, 1H), 2.31 (s, 3H); C{ H} NMR
1
1
46.5, 142.0, 137.9, 137.0, 136.2, 136.0, 134.2, 130.2,
29.1, 129.0, 129.0, 127.5, 120.5, 112.3, 108.0, 103.9; IR
film): 3058, 1706, 1621, 1032, 926, 634 cm ; HRMS (EI)
+
3
(100 MHz, CDCl )  160.2, 154.9, 151.5, 145.9, 142.0,
139.5, 138.0, 137.2, 136.5, 135.9, 130.6, 130.5, 130.1,
129.8, 129.1, 128.8, 128.8, 127.9, 115.6, 112.5, 107.5,
-
1
(
-1
m/z: [M] Calcd for C21
H
14
O
2
298.0994; Found 298.0995.
21.5; IR (film): 3060, 1714, 1605, 1202, 913, 644 cm ;
+
HRMS (EI) m/z: [M] Calcd for C26
H
18
O
2
362.1307;
Found 362.1307.
8
-Methyl-3-phenyl-1H-azuleno[1,2-c]pyran-1-one (3q) :
Yield : 45.8 mg (80%); R = 0.3 (dichloromethane : hexane
4:1); Red solid; Melting point : 238-240 C; H NMR
400 MHz, CDCl )  9.35 (d, J = 9.8 Hz, 1H), 8.26 (d, J =
f
o
1
=
(
3-(4-Chlorophenyl)-4-phenyl-1H-azuleno[1,2-c]pyran-
1-one (3w) : Yield : 53.5 mg (70%); R
3
f
= 0.3
8
This article is protected by copyright. All rights reserved.

Advanced Synthesis & Catalysis
10.1002/adsc.202001082
(
dichloromethane : hexane = 4:1); Red solid; Melting
3-(4-(tert-Butyl)phenyl)-2-methoxyazuleno[1,2-
o
1
point : 195-197 C; H NMR (400 MHz, CDCl
3
)  9.61 (d,
f
c]pyridin-1(2H)-one (4e) : Yield : 62.2 mg (87%); R =
J = 9.3 Hz, 1H), 8.34 (d, J = 10.1 Hz, 1H), 7.80 (t, J = 9.8
Hz, 1H), 7.69 (t, J = 9.7 Hz, 1H), 7.51 (t, J = 9.8 Hz, 3H),
0.3 (acetone : hexane = 1:7); Brown solid; Melting point :
o 1
189-191 C; H NMR (400 MHz, CDCl )  9.72 (d, J = 8.8
3
7
.46-7.37 (m, 7H), 7.21 (dd, J = 2.9 Hz, 2H), 7.00 (s, 1H);
Hz, 1H), 8.30 (d, J = 10.4 Hz, 1H), 7.65-7.60 (m, 3H), 7.55
(t, J = 9.7 Hz, 1H), 7.49 (d, J = 8.3 Hz, 2H), 7.35 (t, J = 9.6
Hz, 1H), 7.21 (s, 1H), 6.75 (s, 1H), 3.77 (s, 3H), 1.39 (s,
13
1
C{ H} NMR (100 MHz, CDCl )  159.8, 153.3, 151.0,
3
1
1
1
6
3
46.0, 141.9, 138.5, 137.5, 136.9, 135.4, 135.3, 131.9,
31.1, 130.5, 130.2, 129.3, 129.0, 128.4, 128.2, 116.4,
12.6, 107.5; IR (film): 3058, 1714, 1607, 1091, 914, 832,
13
1
3H); C{ H} NMR (100 MHz, CDCl )  157.8, 152.6,
3
147.2, 146.0, 144.7, 141.3, 136.6, 136.3, 135.3, 130.6,
129.2, 129.0, 127.2, 125.3, 114.4, 112.1, 102.8, 63.9, 34.9,
31.4; IR (film): 3054, 1654, 1530, 1198, 1102, 932, 623
-
1
+
63 cm ; HRMS (EI) m/z: [M] Calcd for C25H15ClO
2
82.0761; Found 382.0761.
-
1
+
cm ; HRMS (EI) m/z: [M] Calcd for C24H23NO
2
3
57.1729; Found 357.1728.
4
-Methyl-3-phenyl-1H-azuleno[1,2-c]pyran-1-one (3x) :
= 0.3 (dichloromethane : hexane
Yield : 46.3 mg (81%); R
f
o
1
=
4:1); Red solid; Melting point : 195-197 C; H NMR
2-Methoxy-3-(4-methoxyphenyl)azuleno[1,2-c]pyridin-
1(2H)-one (4f) : Yield : 56.9 mg (86%); R = 0.3 (acetone :
hexane = 1:7); Brown solid; Melting point : 196-198 C;
(
400 MHz, CDCl
3
)  9.58 (d, J = 9.3 Hz, 1H), 8.45 (d, J =
f
o
1
7
7
0.1 Hz, 1H), 7.79 (t, J = 9.8 Hz, 1H), 7.72-7.70 (m, 2H),
.67 (t, J = 9.7 Hz, 1H), 7.54 (t, J = 10.1 Hz, 1H), 7.51-
1
H NMR (400 MHz, CDCl )  9.71 (d, J = 8.9 Hz, 1H),
3
1
3
1
.42 (m, 3H), 7.29 (s, 1H), 2.47 (s, 3H); C{ H} NMR
8.31 (d, J = 10.4 Hz, 1H), 7.68-7.61 (m, 3H), 7.56 (t, J =
9.6 Hz, 1H), 7.36 (t, J = 9.6 Hz, 1H), 7.22 (s, 1H), 7.03-
6.99 (m, 2H), 6.74 (s, 1H), 3.90 (s, 3H), 3.75 (s, 3H);
(
3
100 MHz, CDCl )  160.5, 154.7, 152.0, 146.0, 141.8,
1
1
1
38.0, 137.2, 136.5, 133.7, 129.9, 129.6, 129.4, 128.8,
28.4, 111.1, 108.9, 107.8, 14.2; IR (film): 3060, 1703,
13
1
C{ H} NMR (100 MHz, CDCl )  160.5, 157.8, 147.2,
3
-
1
+
612, 1211, 917, 605 cm ; HRMS (EI) m/z: [M] Calcd
145.7, 144.7, 141.3, 136.6, 136.2, 135.2, 131.0, 129.0,
127.2 125.8, 114.2, 113.8, 112.1, 102.5, 63.8, 55.5; IR
for C20
H
14
O
2
286.0994; Found 286.0991.
-
1
(
film): 3061, 1650, 1530, 1251, 1180, 1110, 931, 619 cm ;
+
3
HRMS (EI) m/z: [M] Calcd for C21H17NO 331.1208;
2
-Methoxy-3-phenylazuleno[1,2-c]pyridin-1(2H)-one
4a) : Yield : 54.8 mg (91%); R = 0.3 (acetone : hexane =
:7); Brown solid; Melting point : 162-164 C; H NMR
)  9.74 (d, J = 9.0 Hz, 1H), 8.33 (d, J =
0.4 Hz, 1H), 7.73-7.69 (m, 2H), 7.66 (t, J = 9.8, 1H), 7.57
Found 331.1208.
(
f
o
1
1
(
400 MHz, CDCl
3
3-(2-Fluorophenyl)-2-methoxyazuleno[1,2-c]pyridin-
1(2H)-one (4g) : Yield : 52.3 mg (82%); R = 0.3
(acetone : hexane = 1:7); Brown solid; Melting point : 170-
1
f
(
t, J = 9.7, 1H), 7.50-7.48 (m, 3H), 7.38 (t, J = 3.2, 1H),
1
3
1
o
1
7
.24 (s, 1H), 6.77 (s, 1H), 3.76 (s, 3H); C{ H} NMR (100
)  157.8, 147.1, 145.9, 144.7, 141.3, 136.9,
36.4, 135.6, 133.6, 129.6, 129.4, 129.1, 128.3, 127.2,
14.5, 112.2, 103.0, 64.0; IR (film): 3060, 1651, 1530,
3
172 C; H NMR (400 MHz, CDCl )  9.76 (d, J = 9.0 Hz,
MHz, CDCl
3
1H), 8.33 (d, J = 10.4 Hz, 1H), 7.66 (t, J = 9.4 Hz, 1H),
7.59-7.46 (m, 3H), 7.37 (t, J = 9.7 Hz, 1H), 7.29-7.20 (m,
1
1
1
13
1
3H), 6.76 (s, 1H), 3.83 (s, 3H); C{ H} NMR (100 MHz,
-
1
+
196, 1108, 932, 642 cm ; HRMS (EI) m/z: [M] Calcd
301.1103; Found 301.1105.
3
CDCl )  160.2 (d, J = 250.2 Hz), 157.6, 146.7, 144.6,
for C20
H
15NO
2
141.1, 140.3, 137.1, 136.7, 135.9, 131.5, 131.4 (d, J = 10.9
Hz), 129.0, 127.2, 124.0 (d, J = 3.6 Hz), 121.9, 121.7,
19
1
15.9 (d, J = 21.6 Hz), 115.0, 112.1, 103.7, 64.3; F NMR
2
-Methoxy-3-(o-tolyl)azuleno[1,2-c]pyridin-1(2H)-one
4b) : Yield : 52.3 mg (83%); R = 0.3 (acetone : hexane =
:7); Brown solid; Melting point : 159-161 C; H NMR
(
376 MHz, CDCl
1424, 1206, 1126, 933, 645 cm ; HRMS (EI) m/z: [M]
Calcd for C20 319.1009; Found 319.1010.
3
)  -111.6; IR (film): 3060, 1652, 1530,
(
f
-1 +
o
1
1
H
14FNO
2
(
3
400 MHz, CDCl )  9.75 (d, J = 9.0 Hz, 1H), 8.35 (d, J =
1
7
1
0.4 Hz, 1H), 7.67 (t, J = 9.7 Hz, 1H), 7.59 (t, J = 9.7, 1H),
.44-7.37 (m, 3H), 7.33-7.28 (m, 2H), 7.24 (s, 1H), 6.66 (s,
3-(3-Chlorophenyl)-2-methoxyazuleno[1,2-c]pyridin-
1(2H)-one (4h) : Yield : 59.0 mg (88%); R = 0.3
(acetone : hexane = 1:7); Brown solid; Melting point : 150-
1
3
1
H), 3.76 (s, 3H), 2.29 (s, 3H); C{ H} NMR (100 MHz,
f
CDCl
3
)  157.7, 147.2, 146.1, 144.7, 141.2, 138.1, 136.9,
36.4, 135.6, 133.6, 130.0, 129.5, 129.4, 129.0, 127.2,
25.5, 114.6, 112.1, 102.4, 64.2, 20.1; IR (film): 3053,
o
1
1
1
1
3
152 C; H NMR (400 MHz, CDCl )  9.75 (d, J = 9.0 Hz,
1H), 8.35 (d, J = 10.4 Hz, 1H), 7.71-7.66 (m, 2H), 7.61-
-
1
653, 1530, 1200, 1111, 932, 681 cm ; HRMS (EI) m/z:
7.56 (m, 2H), 7.48-7.38 (m, 3H), 7.24 (s, 1H), 6.77 (s, 1H),
+
13
1
[
M] Calcd for C21
H
17NO
2
315.1259; Found 315.1259.
3.79 (s, 3H); C{ H} NMR (100 MHz, CDCl
3
)  157.6,
1
1
1
46.7, 144.7, 144.3, 141.2, 137.2, 136.7, 136.0, 135.2,
34.3, 129.6, 129.5, 129.5, 129.1, 127.8, 127.4, 114.6,
12.2, 103.3, 64.1; IR (film): 3063, 1653, 1529, 1200,
2
-Methoxy-3-(m-tolyl)azuleno[1,2-c]pyridin-1(2H)-one
= 0.3 (acetone : hexane =
(
4c) : Yield : 55.5 mg (88%); R
f
-
1
+
o
1
1111, 931, 795, 680 cm ; HRMS (EI) m/z: [M] Calcd for
1
:7); Brown solid; Melting point : 146-148 C; H NMR
20 2
C H14ClNO 335.0713; Found 335.0712.
(
400 MHz, CDCl
3
)  9.73 (d, J = 8.9 Hz, 1H), 8.32 (d, J =
1
7
7
0.4 Hz, 1H), 7.65 (t, J = 9.7 Hz, 1H), 7.56 (t, J = 9.7, 1H),
.51-7.49 (m, 2H), 7.40-7.35 (m, 3H), 7.31-7.29 (m, 2H),
3-(4-Bromophenyl)-2-methoxyazuleno[1,2-c]pyridin-
1(2H)-one (4i) : Yield : 65.4 mg (86%); R = 0.3 (acetone :
hexane = 1:7); Brown solid; Melting point : 181-183 C;
.23 (s, 1H), 6.80 (s, 1H), 3.77 (s, 3H), 2.45 (s, 3H);
f
13
1
o
C{ H} NMR (100 MHz, CDCl
3
)  157.8, 147.1, 146.1,
1
1
1
2
6
3
44.7, 141.3, 138.0, 136.8, 136.4, 135.4, 133.5, 130.2,
H NMR (400 MHz, CDCl
3
)  9.74 (d, J = 8.9 Hz, 1H),
30.1, 129.0, 128.2, 127.2, 126.7, 114.4, 112.1, 102.8, 64.0, 8.35 (d, J = 10.4 Hz, 1H), 7.70-7.56 (m, 6H), 7.40 (t, J =
1.6; IR (film): 3046, 1653, 1601, 1530, 1200, 1109, 917,
9.6 Hz, 2H), 7.24 (s, 1H), 6.76 (s, 1H), 3.76 (s, 3H);
-
1
+
13
1
46 cm ; HRMS (EI) m/z: [M] Calcd for C21
H
17NO
2
3
C{ H} NMR (100 MHz, CDCl )  157.6, 146.8, 144.7,
15.1259; Found 315.1257.
144.6, 141.2, 137.1, 136.6, 135.8, 132.4, 131.6, 131.1,
1
3
29.1, 127.4, 123.9, 114.5, 112.1, 103.0, 64.0; IR (film):
-1
068, 1652, 1530, 1201, 1106, 931, 733, 614 cm ; HRMS
2
-Methoxy-3-(p-tolyl)azuleno[1,2-c]pyridin-1(2H)-one
= 0.3 (acetone : hexane =
+
79
(
EI) m/z: [M] Calcd for C20
H
14Br NO
2
379.0208,
(
4d) : Yield : 55.5 mg (88%); R
f
81
o
1
C
H14Br NO 381.0188; Found 379.0208, 381.0184.
20 2
1
:7); Brown solid; Melting point : 159-161 C; H NMR
(
400 MHz, CDCl
3
)  9.71 (d, J = 8.9 Hz, 1H), 8.31 (d, J =
1
7
3
1
1
1
1
0.4 Hz, 1H), 7.66-7.53 (m, 4H), 7.36 (t, J = 9.6 Hz, 1H),
.29 (d, J = 8.0 Hz, 2H), 7.22 (s, 1H), 6.75 (s, 1H), 3.75 (s,
2-Methoxy-3-(4-(trifluoromethyl)phenyl)azuleno[1,2-
c]pyridin-1(2H)-one (4j) : Yield : 55.4 mg (75%); R = 0.3
(acetone : hexane = 1:7); Brown solid; Melting point : 185-
f
1
3
1
H), 2.45 (s, 3H); C{ H} NMR (100 MHz, CDCl ) 
3
o
1
57.8, 147.2, 146.1, 144.7, 141.3, 139.5, 136.7, 136.3,
35.4, 130.7, 129.5, 129.04, 129.03, 127.2, 114.4, 112.1,
02.7, 63.9, 21.5; IR (film): 3032, 1651, 1600, 1530, 1189,
3
187 C; H NMR (400 MHz, CDCl )  9.76 (d, J = 9.0 Hz,
1H), 8.35 (d, J = 10.2 Hz, 1H), 7.83 (d, J = 7.3 Hz, 2H),
7.75 (d, J = 7.8 Hz, 2H), 7.69 (t, J = 8.6 Hz, 1H), 7.58 (t, J
= 9.2 Hz, 1H), 7.40 (t, J = 9.0 Hz, 1H), 7.25 (s, 1H), 6.78
-
1
+
110, 971, 618cm ; HRMS (EI) m/z: [M] Calcd for
13
1
C
21
H
17NO
2
315.1259; Found 315.1255.
3
(s,1H), 3.76 (s, 3H); C{ H} NMR (100 MHz, CDCl ) 
1
57.6, 146.6, 144.7, 144.1, 141.1, 137.4, 137.0, 136.8,
9
This article is protected by copyright. All rights reserved.

Advanced Synthesis & Catalysis
10.1002/adsc.202001082
o
1
1
36.1, 131.3 (q, J = 32.8 Hz), 129.9, 129.2, 127.5, , 125.3
3
203 C; H NMR (400 MHz, CDCl )  9.58 (d, J = 9.6 Hz,
(
q, J = 3.7 Hz), 124.1 (q, J = 272.3 Hz), 114.6, 112.2,
1H), 8.20 (d, J = 10.8 Hz, 1H), 7.71-7.68 (m, 2H), 7.49-
7.44 (m, 4H), 7.29 (d, J = 10.8 Hz, 1H), 7.16 (s, 1H), 6.74
19
1
3
03.5, 64.1; F NMR (376 MHz, CDCl )  -62.7; IR
-1
13
1
(
film): 3060, 1655, 1530, 1324, 1166, 1125, 932, 622 cm ;
(s, 1H), 3.75 (s, 3H), 2.69 (s, 3H); C{ H} NMR (100
+
HRMS (EI) m/z: [M] Calcd for C21
Found 369.0974.
H
14 3
F NO
2
369.0977;
3
MHz, CDCl )  157.8, 148.9, 146.1, 145.3, 143.6, 139.5,
135.5, 135.2, 133.7, 129.9, 129.6, 129.2, 128.3, 128.3,
1
1
14.7, 111.9, 103.0, 63.9, 28.3; IR (film): 3061, 1651,
-
1
+
536, 1198, 1085, 920, 642 cm ; HRMS (EI) m/z: [M]
315.1259; Found 315.1258.
2
1
-Methoxy-3-(thiophen-2-yl)azuleno[1,2-c]pyridin-
(2H)-one (4k) : Yield : 45.5 mg (74%); R = 0.3
Calcd for C21
H
17NO
2
f
(
acetone : hexane = 1:7); Brown solid; Melting point : 159-
o 1
1
1
7
61 C; H NMR (400 MHz, CDCl
3
)  9.67 (d, J = 9.0 Hz,
2-Methoxy-5-methyl-3-phenylazuleno[1,2-c]pyridin-
1(2H)-one (4q) : Yield : 45.4 mg (72%); R = 0.3
(acetone : hexane = 1:7); Green solid; Melting point : 215-
H), 8.30 (d, J = 10.3 Hz, 1H), 7.71 (dd, J = 1.6 Hz, 1H),
.63 (t, J = 9.7 Hz, 1H), 7.56 (d, J = 9.4 Hz, 1H), 7.53 (dd,
f
o
1
J = 2.1 Hz, 1H), 7.36 (t, J = 9.6 Hz, 1H), 7.23 (s, 1H), 7.17
3
217 C; H NMR (400 MHz, CDCl )  9.63 (dd, J = 3.3 Hz,
13
1
(
dd, J = 3.0 Hz, 1H), 7.07 (s, 1H), 4.00 (s, 3H); C{ H}
)  157.7, 146.9, 144.8, 141.3,
39.1, 136.8, 136.3, 135.4, 133.8, 129.5, 129.3, 129.2,
27.5, 127.4, 114.0, 112.2, 101.4, 64.2; IR (film): 3072,
1H), 8.21 (d, J = 10.6 Hz, 1H), 7.73-7.71 (m, 2H), 7.56 (t,
J = 9.7 Hz, 1H), 7.52-7.49 (m, 3H), 7.46 (t, J = 9.8 Hz,
1H), 7.30 (t, J = 9.7 Hz, 1H), 6.76 (s, 1H), 3.76 (s, 3H),
NMR (100 MHz, CDCl
3
1
1
1
13
1
2.61 (s, 3H); C{ H} NMR (100 MHz, CDCl )  157.6,
3
-
1
652, 1530, 1295, 1206, 1112, 928, 634 cm ; HRMS (EI)
146.7, 145.7, 141.0, 139.9, 136.4, 134.5, 133.7, 133.5,
129.6, 129.4, 128.5, 128.3, 125.8, 119.1, 113.0, 101.3, 63.9,
10.0; IR (film): 3054, 1651, 1527, 1296, 1192, 929, 644
+
m/z: [M] Calcd for C18
H
13NO
2
S 307.0667; Found
3
07.0669.
-
1
+
cm ; HRMS (EI) m/z: [M] Calcd for C21H17NO
2
3
15.1259; Found 315.1262.
3
-Ethyl-2-methoxyazuleno[1,2-c]pyridin-1(2H)-one
= 0.3 (acetone : hexane =
(
4l) : Yield : 50.1 mg (99%); R
f
o
1
1
:7); Brown solid; Melting point : 133-135 C; H NMR
5-Chloro-2-methoxy-3-phenylazuleno[1,2-c]pyridin-
1(2H)-one (4r) : Yield : 57.5 mg (81%); R = 0.3 (acetone :
hexane = 1:7); Green solid; Melting point : 218-220 C; H
(
400 MHz, CDCl
3
)  9.63 (d, J = 8.9 Hz, 1H), 8.27 (d, J =
f
o
1
1
1
4
3
1
1
1
0.4 Hz, 1H), 7.59 (t, J = 9.7 Hz, 1H), 7.51 (t, J = 9.6 Hz,
H), 7.32 (t, J = 9.6 Hz, 1H), 7.15 (s, 1H), 6.57 (s, 1H),
.17 (s, 3H), 2.90 (t, J = 7.40 Hz, 2H), 1.39 (q, J = 4.9 Hz,
NMR (400 MHz, CDCl )  9.68 (dd, J = 3.4 Hz, 1H), 8.37
3
(d, J = 10.5 Hz, 1H), 7.76-7.72 (m, 2H), 7.70-7.65 (m, 1H),
7.56 (t, J = 9.8 Hz, 1H), 7.53-7.50 (m, 3H), 7.48-.743 (m,
13
1
H); C{ H} NMR (100 MHz, CDCl )  158.1, 148.9,
3
13
1
47.6, 144.6, 141.3, 136.2, 136.0, 134.7, 128.9, 127.0,
14.0, 111.7, 98.8, 64.4, 24.6, 12.8; IR (film): 3082, 1650,
1H), 6.84 (s, 1H), 3.76 (s, 3H); C{ H} NMR (100 MHz,
CDCl )  157.0, 147.0, 143.4797, 139.2, 137.9, 137.5,
3
-
1
+
531, 1197, 1119, 921, 621 cm ; HRMS (EI) m/z: [M]
135.7, 133.3, 133.2, 129.7, 129.6, 129.5, 128.4, 127.7,
112.3, 111.3, 100.1, 64.1; IR (film): 3057, 1658, 1525,
2
Calcd for C16H15NO 253.1103; Found 253.1099.
-
1
+
1
180, 1126, 938, 769, 610 cm ; HRMS (EI) m/z: [M]
2
Calcd for C20H14ClNO 335.0713; Found 355.0715.
3
-Butyl-2-methoxyazuleno[1,2-c]pyridin-1(2H)-one
= 0.3 (acetone : hexane =
(
4m) : Yield : 55.7 mg (99%); R
f
o
1
1
:7); Brown solid; Melting point : 97-99 C; H NMR (400
2-Methoxy-4-(3-methoxyphenyl)-3-(p-tolyl)azuleno[1,2-
c]pyridin-1(2H)-one (4s) : Yield : 50.5 mg (60%); R
0.3 (acetone : hexane = 1:7); Brown solid; Melting point :
MHz, CDCl
3
)  9.62 (d, J = 8.9 Hz, 1H), 8.26 (d, J = 10.5
f
=
Hz, 1H), 7.61-7.56 (m, 1H), 7.51 (t, J = 9.6 Hz, 1H), 7.32
o
1
(
3
td, J = 4.0 Hz, 1H), 7.13 (s, 1H), 6.56 (s, 1H), 4.16 (s, 3H), 188-190 C; H NMR (400 MHz, CDCl )  9.82 (d, J = 8.9
2
2

1
1
.85 (t, J = 7.70 Hz, 2H), 1.81-1.73 (m, 2H), 1.52-1.43 (m,
Hz, 1H), 8.25 (d, J = 10.4 Hz, 1H), 7.66 (t, J = 9.7 Hz, 1H),
7.59 (t, J = 9.7 Hz, 1H), 7.35 (t, J = 9.6 Hz, 1H), 7.23 (d, J
= 7.5 Hz, 2H), 7.19 (t, J = 7.9 Hz, 1H), 7.10-7.08 (m, 3H),
6.84 (d, J = 7.5 Hz, 1H), 6.80-6.77 (m, 1H), 6.73 (s, 1H),
1
3
1
3
H), 1.01-0.97 (m, 3H); C{ H} NMR (100 MHz, CDCl )
158.0, 147.6, 147.5, 144.5, 141.2, 136.1, 135.9, 134.5,
28.8, 126.9, 113.9, 111.6, 99.7, 64.3, 31.3, 30.6, 22.5,
4.0; IR (film): 3060, 1652, 1531, 1205, 1141, 921, 627
13
1
3.77 (s, 3H), 3.66 (s, 3H), 2.34 (s, 3H); C{ H} NMR (100
-
1
+
cm ; HRMS (EI) m/z: [M] Calcd for C18
H
19NO
2
3
MHz, CDCl )  159.4, 157.3, 147.9, 144.0, 143.4, 141.4,
2
81.1416; Found 281.1416.
138.5, 138.0, 137.0, 136.8, 136.1, 130.9, 129.2, 129.1,
1
1
1
29.1, 128.5, 127.1, 123.7, 116.5, 115.5, 114.0, 112.9,
12.5, 64.0, 55.3, 21.5; IR (film): 3051, 1653, 1508, 1236,
(
E)-2-methoxy-3-(prop-1-en-1-yl)azuleno[1,2-c]pyridin-
(2H)-one (4n) : Yield : 36.9 mg (78%); R = 0.3
acetone : hexane = 1:7); Brown solid; Melting point : 130-
-
1
+
036, 942, 656 cm ; HRMS (EI) m/z: [M] Calcd for
1
f
C
28
H
23NO
3
421.1678; Found 421.1680.
(
o
1
1
1
32 C; H NMR (400 MHz, CDCl
H), 8.24 (d, J = 10.4 Hz, 1H), 7.60-7.48 (m, 3H), 7.31 (t,
3
)  9.61 (d, J = 8.8 Hz,
2-Methoxy-4-methyl-3-phenylazuleno[1,2-c]pyridin-
1(2H)-one (4t) : Yield : 44.7 mg (71%); R = 0.3 (acetone :
hexane = 1:7); Brown solid; Melting point : 168-170 C;
1
J = 9.6 Hz, 1H), 7.15 (s, 1H), 6.85 (s, 1H), 6.73 (d, 1H),
f
o
6
.62-6.53 (m, 1H), 4.09 (s, 3H), 2.01 (dd, J = 5.7 Hz, 3H);
13
1
C{ H} NMR (100 MHz, CDCl
43.6, 141.4, 136.3, 136.0, 134.8, 133.9, 129.0, 127.1,
22.4, 114.1, 112.1, 98.1, 64.2, 19.2; IR (film): 3060, 1652, J = 9.7 Hz, 1H), 7.54-7.45 (m, 5H), 7.40 (t, J = 9.7 Hz,
3
)  157.6, 147.3, 144.7,
H NMR (400 MHz, CDCl
3
)  9.82 (d, J = 9.0 Hz, 1H),
1
1
1
8.39 (d, J = 10.3 Hz, 1H), 7.69 (t, J = 9.8 Hz, 1H), 7.59 (t,
-
1
+
13
1
531, 1205, 1141, 921, 627 cm ; HRMS (EI) m/z: [M]
265.1103; Found 265.1105.
1H), 7.31 (s, 1H), 3.8 (s, 3H), 2.22 (s, 1H); C{ H} NMR
Calcd for C17
H
15NO
2
(100 MHz, CDCl
3
)  157.3, 148.7, 144.1, 142.7, 141.3,
37.0, 136.7, 136.0, 132.7, 130.2, 129.0, 128.9, 128.3,
27.1, 114.2, 110.9, 108.6, 63.9, 14.9; IR (film): 3056,
1
1
1
(
(
E)-2-methoxy-3-styrylazuleno[1,2-c]pyridin-1(2H)-one
4o) : Yield : 64.2 mg (98%); R = 0.3 (acetone : hexane =
:7); Brown solid; Melting point : 171-173 C; H NMR
-
1
649, 1531, 1340, 1206, 948, 647 cm ; HRMS (EI) m/z:
f
+
o
1
[M] Calcd for C21
H
17NO
2
315.1259; Found 315.1260.
1
(
3
400 MHz, CDCl )  9.65 (d, J = 8.9 Hz, 1H), 8.28 (d, J =
1
7
1
1
1
1
1
0.4 Hz, 1H), 7.62-7.58 (m, 3H), 7.52 (t, J = 9.7 Hz, 1H),
3-Butyl-2-methoxy-4-methylazuleno[1,2-c]pyridin-
1(2H)-one (4u) : Yield : 48.4 mg (82%); R = 0.3
(acetone : hexane = 1:7); Brown solid; Melting point : 137-
.45-7.41 (m, 4H), 7.38-7.31 (m, 2H), 7.21 (s, 1H), 7.10 (s,
f
1
3
1
H), 4.13 (s, 3H); C{ H} NMR (100 MHz, CDCl ) 
3
o
1
57.6, 146.9, 144.8, 143.2, 141.4, 136.6, 136.4, 136.2,
35.3, 135.2, 129.2, 129.1, 129.1, 127.4, 127.3, 119.1,
139 C; H NMR (400 MHz, CDCl
1H), 8.30 (d, J = 10.4 Hz, 1H), 7.60 (t, J = 9.7 Hz, 1H),
3
)  9.68 (d, J = 8.9 Hz,
14.4, 112.2, 98.7, 64.4; IR (film): 3060, 1652, 1531, 1205, 7.52 (t, J = 9.6 Hz, 1H), 7.33 (t, J = 9.6 Hz, 1H), 7.23 (s,
-
1
+
141, 921, 627 cm ; HRMS (EI) m/z: [M] Calcd for
327.1259; Found 327.1261.
1H), 4.16 (s, 3H), 2.89 (t, J = 7.9 Hz, 2H), 2.42 (s, 3H),
1.73-1.65 (m, 2H), 1.52-1.43 (m, 2H), 1.69 (t, J = 3.4 Hz,
22 2
C H17NO
13
1
13
1
3
H); C{ H} NMR (100 MHz, CDCl
3
)
C{ H} NMR
(
100 MHz, CDCl
3
)  157.5, 149.0, 144.2, 144.0, 141.4,
2
1
-Methoxy-8-methyl-3-phenylazuleno[1,2-c]pyridin-
(2H)-one (4p) : Yield : 37.8 mg (60%); R = 0.3
1
3
36.2, 136.1, 135.0, 128.9, 126.9, 113.5, 110.6, 106.6, 64.4,
1.3, 28.2, 22.9, 14.0, 13.9; IR (film): 3076, 1648, 1532,
f
(
acetone : hexane = 1:7); Brown solid; Melting point : 201-
1
0
This article is protected by copyright. All rights reserved.

Advanced Synthesis & Catalysis
10.1002/adsc.202001082
-
1
+
1
383, 1293, 920, 627 cm ; HRMS (EI) m/z: [M] Calcd
295.1572; Found 295.1571.
Aguilar, M. Contel, R. Navarro, E. P. Urriolabeitia,
Organometallics 2007, 26, 4604-4611.
for C19H21NO
2
CCDC-1923064 (3a) and CCDC-1946573 (4a) contains
the supplementary crystallographic data for this paper.
These data can be obtained free of charge from The
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Acknowledgements
This work was supported by the National Research Foundation of
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