Construction of Halofunctionalized Indenes via a Cascade Prins-Nazarov Cyclization Promoted by Dual Roles of BX3

Article abstract of DOI:10.1002/adsc.201901266

Halofunctionalization of various unactivated arylalkynes to the corresponding 1H-indenes in the presence of a particular class of carboxaldehydes and boron trihalides (BX₃, X=F, Cl, Br, I) is described. A diverse array of halofunctionalized indenes substituted with a heterocycle has been synthesized regioselectively with BX₃ as a promotor for the carbocyclization and a source of X^? for halogenation. This reaction proceeds via a formal halogenative [4+1] cycloaddition between arylalkynes and carboxaldehydes promoted by boron trihalides to generate halofunctionalized indenes. The usefulness of the halofunctionalized indenes was demonstrated by their conversion to other derivatives via coupling, nucleophilic substitution, and oxidation. (Figure presented.).

Full text of DOI:10.1002/adsc.201901266

Title: Construction of Halofunctionalized Indenes via a Cascade Prins-
Nazarov Cyclization Promoted by Dual Roles of BX3
Authors: Sabera Sultana and Yong Rok Lee
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201901266
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10.1002/adsc.201901266
Advanced Synthesis & Catalysis
FULL PAPER
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Construction of Halofunctionalized Indenes via a Cascade
Prins-Nazarov Cyclization Promoted by Dual Roles of BX3
Sabera Sultanaa and Yong Rok Leea*
a School of Chemical Engineering, Yeungnam University, Gyeongsan 38541, Republic of Korea. E-mail: yrlee@yu.ac.kr;
Fax: +82-53-810-4631; Tel: +82-53-810-2529
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. Halofunctionalization of various unactivated cycloaddition between arylalkynes and carboxaldehydes
arylalkynes to the corresponding 1H-indenes in the presence promoted by boron trihalides to generate halofunctionalized
of a particular class of carboxaldehydes and boron trihalides indenes. The usefulness of the halofunctionalized indenes
(BX3, X = F, Cl, Br, I) is described. A diverse array of was demonstrated by their conversion to other derivatives
halofunctionalized indenes substituted with a heterocycle has via coupling, nucleophilic substitution, and oxidation.
been synthesized regioselectively with BX3 as a promotor
for the carbocyclization and a source of X– for halogenation.
This reaction proceeds via a formal halogenative [4+1]
Keywords: boron reagents; halogenation; carbaldehydes;
haloindenes; Nazarov cyclization
chemistry.[12] It has also been employed as
nucleophilic fluoride source as it is inexpensive,
Introduction
.
effective, and easy to handle.[13] BF3 OEt2-promoted
Indenes are an important class of compounds found
in many natural products and pharmaceuticals.[1]
Moreover, they are widely used as building blocks for
the synthesis of metallocene complexes and
functional materials.[2] Owing to the importance and
synthetic utility of indenes, many approaches based
on intra-[3] and intermolecular[4] cyclization reactions
have been reported for their synthesis. The general
approaches for preparing haloindenes include gold(I)-
catalyzed intramolecular cyclization of iodo-
ring opening reactions of epoxides or aziridines to
produce fluorinated compounds have been
.
reported[13a] however, BF3 OEt2-promoted Prins
reactions of arylalkynes with carboxaldehydes for the
synthesis of fluoroindenes have not yet been
.
developed. We envisioned that BF3 OEt2 can act as a
bifunctional reagent as a Lewis acid and a source of
F– for the construction of fluoroindenes via the
cascade Prins and Nazarov cyclization starting from
readily available arylalkynes and carboxaldehydes.
functionalized
alkynes,[5]
iodonium-promoted
cyclization of arylethynylmalonates,[6] palladium-
catalyzed
tandem
reaction of 2-
alkenylphenylacetylenes with CuX2 (X = Cl, Br),[7]
and reactions of o-(alkynyl)styrenes with NXS (X = I,
Br).[8] However, there is no report on any direct
approach for the synthesis of fluorine-containing
indenes on the cyclopentadiene moiety.
In the past decades, fluorine-containing organic
molecules were widely used in pharmaceuticals,
agrochemicals, and functional materials.[9] In this
regard, significant efforts have been made to develop
new methods for the formation of C-F bonds under
transition-metal-catalyzed or metal-free conditions.[10]
A number of nucleophilic or electrophilic fluorinating
reagents including HF complex, N-fluoropyridium
salts, NFSI, and Selectfluor, have been used.[10,11]
However, due to their poor solubility, selectivity, and
stability, there is a strong demand for milder and
more facile fluorinating reagents.
Scheme 1. Synthetic strategies to haloindenes via a
cascade Prins–Nazarov cyclization.
The Nazarov reaction is a powerful method for the
generation of cyclopentenones and heterocycles.[14]
Recently, the Frontier’s group reported a two-step
protocol for haloindene formation starting from
.
Boron trifluoride etherate (BF3 OEt2) has been
alkynols
and
aldehydes
using
widely used as a mild Lewis acid in synthetic organic
1
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10.1002/adsc.201901266
Advanced Synthesis & Catalysis
tetrabutylammoniumhalide
as
a
source
of
proton on the chromone ring at 7.37 ppm as a singlet.
halogenating agent in the cyclic ether formation
followed by halo-Nazarov cyclization (Scheme
With the optimized conditions in hand, we further
explored the generality of this cascade reaction
employing different symmetric arylethynes and
diverse 3-formylchromones (Scheme 2). To our
delight, various electron-donating and -withdrawing
groups were well tolerated under the standard
reaction conditions. For example, reaction of 1a with
3-formylchromones 2b-2d bearing 6-methyl, 6-NO2,
and both 6-Cl and 7-Me groups on the benzene ring
in the presence of halogenating reagents BX3 (X = F,
Cl, Br) smoothly afforded the corresponding
halogenated products 4a-c, 5a-c, and 6a-c with good
yields. In the 19F NMR of 4a, a signal appeared at -
129.9 ppm due to the formation of C(sp2)–F bond.
Further reactions of symmetric 1,2-diarylethylenes
1b-1d bearing an electron-donating group such as 4-
Me and electron-withdrawing groups (4-Br, 3-Br)
with 2a and 2e afforded 7a-c, iodo substituted indene
8, 9 and 10a-b in 59-89%, 53%, 54% and 63-67%
yields, respectively.
.
1a).[15] Herein, we report BF3 OEt2 and other BX3-
promoted cascade reactions of arylalkynes and
carboxaldehydes for the direct synthesis of diversely
functionalized haloindenes (X = F, Cl, Br, I) bearing
heterocycles on the cyclopentene ring (Scheme 1b).
Results and Discussion
Our study commenced with the reaction of 1,2-
diphenylethyne (1a) with 3-formylchromone (2a) in
the presence of different halogenating reagents and
solvents (Table 1). The initial attempt with AgBF4
(1.0 equiv) and CsF (1.0 equiv) was unsuccessful,
and the desired product 3a was not obtained (entries
1-2). When the reaction was carried out using
.
BF3 OEt2 (0.5-2.0 equiv) at room temperature, 3a was
obtained in 48-65% yield (entries 3-5). Elevating the
temperature in refluxing dichloromethane did not
increase the yield (entry 6), and changing the solvents
to THF, 1,4-dioxane, and acetonitrile completely shut
down the reaction (entries 7-9). To prepare
chloroindene 3b and bromoindene 3c, several chloro
and brominating reagents were also screened (entries
10-21). Among these only BCl3 and BBr3 provided 3b
and 3c in varying yields depending on the
stoichiometry of the reagents. In cases of further
reactions with CuI2, NIS, and BI3 (1.0–2.0 equiv),
only BI3 generated 3d (entries 22-25) in 40% yield.
1
The structure of compound 3a was assigned by H
NMR spectrum, which shows a characteristic signal
of a vinylic proton on the cyclopentadiene ring at
5.61 ppm as a broad singlet and a signal for the vinyl
Table 1. Optimization of the reaction conditions.[a]
Scheme 2. Substrate scope of symmetric arylethynes and
3-formylchromones. [a]Reaction conditions: 1 (0.5 mmol),
.
2 (0.5 mmol), DCM (1 mL), BF3 OEt2 (1.0 equiv.), 3 h; For
BCl3 or BBr3 (3.0 equiv.), reaction was completed during
the addition; BI3 (1.0 equiv.), 12 h. All the yields are
isolated yield.
On the other hand, the reaction of monosubstituted
1,2-arylphenylethynes 1e-1f bearing electron-
donating groups (4-Me and 4-n-Pr) with 2a in the
presence of BX3 (X = F, Cl, Br) regioselectively
provided the halogenated indenes 11a-c (64-89%)
and 12a-c (62-87%). However, treatment of 1g
bearing an electron-withdrawing group (4-Cl) with 2a
provided 13 in 48% yield (Scheme 3). Importantly,
only one of the two possible regioisomers was
selectively generated depending on the substituent
type. Electron-rich diarylalkynes provided products
bearing substituents on the indene moiety, whereas
[a]Reaction conditions: 1a (0.5 mmol), 2a (0.5 mmol) in
solvent (1 mL). [b]Isolated yields. [c]Reaction was
completed during the addition of reagents.
2
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10.1002/adsc.201901266
Advanced Synthesis & Catalysis
substrates with an electron-withdrawing group gave
the corresponding product bearing substituents on the
benzene ring at the indene moiety. Similarly, the
reaction of nonsymmetric disubstituted 1,2-
arylphenylethyne 1h with 2a provided halogenated
indenes 14a-b in 79 and 73% yields, respectively.
Further reactions of arylalkylacetylenes 1i or 1j with
2a provided the corresponding products 15-16 in 57-
86% yields. Reactions of 3-(phenylethynyl)thiophene
(1k) and 1-(phenylethynyl)naphthalene (1l) provided
17 and 18 in 72 and 92% yields, respectively. The
regiochemistry of the indenes was determined by
their 1H NMR analysis. Further structural
confirmation of these compounds was realized by a
single crystal X-ray crystallographic analysis of
structurally related compound 12c.
Further transformations of synthetic compound 3c
were next investigated at the C-3 position (Scheme 5).
The palladium-catalyzed cross-coupling and Stille
coupling of 3c afforded aryl-substituted products
34a-b (85 and 87%) and functionalized product 35 in
89% yield. Interestingly, 3c could undergo
nucleophilic substitution with ethanol in NaOH to
afford the corresponding ether product 36 in 55%
yield. Oxidation of 3c with CuO afforded 37 in 67%
yield.
Scheme 3. Substrate scope of nonsymmetric arylethynes.
[a]Reaction conditions: 1 (0.5 mmol), 2 (0.5 mmol), DCM
(1 mL), BF3 OEt2 (1.0 equiv.), 3 h; For BCl3 or BBr3 (3.0
equiv.), reaction was completed during the addition; BI3
(1.0 equiv.), 12 h. All the yields are isolated yield.
.
Scheme 4. Substrate scope of carboxaldehydes for the
formation of 3-haloindenes. [a]Reaction conditions: 1 (0.5
mmol), 2 (0.5 mmol), DCM (1 mL), BF3 OEt2 (1.0 equiv.),
3 h; For BCl3 or BBr3 (3.0 equiv.), reaction was completed
during the addition; BI3 (1.0 equiv.), 12 h. All the yields
are isolated yield.
.
Having established the general applicability of this
protocol, we were intrigued by the possibility of
using other carboxaldehydes such as 1-oxo-1H-
benzo[f]chromene-2-carbaldehyde (2f), 4-oxo-5-
phenyl-4H-pyran-3-carbaldehydes 2g-2i, 4-oxo-4H-
thiochromene-3-carbaldehydes 2j-2k, 2-oxo-2H-
chromene-3-carbaldehydes 2l-2m and 2-oxo-1,2-
dihydroquinoline-3-carbaldehydes 2n-2q (Scheme 4).
Gratifyingly, the reactions of 1a, 1b, and 1j with 2f-
2q in the presence of boron-based halogenating
reagents provided 19-33 in 35-94% yields. Notably,
the reactions of many substituted alkynes in the
.
presence of BF3 OEt2 were relatively selective and
provided a lower yield of products compared to BCl3
and BBr3, probably due to higher bond strength of B-
F than that of B-Cl and B-Br of other halogens.[16]
The use of phenylacetylene as a terminal alkyne
under standard reaction conditions failed to provide
the desired product, instead intractable mixtures were
obtained.
Scheme 5. Various transformation of synthetic compound
3c.
3
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10.1002/adsc.201901266
Advanced Synthesis & Catalysis
Additional reactions were also performed with
2a' affords intermediate 46. Subsequently, 46
converts into 3-halopentadienyl cation 47.
Cyclization of 4π-intermediate 47 to 48 followed by
deprotonation affords the observed product 3a. The
regiochemistry of the isolated compounds can be
explained by the electronic effects of the substituents.
other carbonyl compounds (Scheme 6). Treatment of
benzaldehyde (38) with 1a in the presence of
BF3∙OEt2 did not provide the desired 3-fluoroindene
39, instead 40 was isolated in 66% yield (Scheme
6a).[17] However, the reactions of 1a with electron-
rich benzaldehydes of o- or p-anisaldehyde In case of substrates with an electron-releasing group,
provided intractable mixtures. The reaction of intermediate 47a (Scheme 7) would be favourable,
trans-cinnamaldehyde (41) or 6-oxocyclohex-1-ene-
1-carbaldehyde (42) with 1a in the presence of
BF3∙OEt2 did not provide any desired products. In
these cases, the aldehydes were decomposed (Scheme
6b and 6c).The reaction of acetylacetone (43) with 1a
in the presence of BF3∙OEt2 afforded BF2-complexed
product 44 (83%) (Scheme 6d).[18] These results
suggest that using particular structural elements on
the substrate aldehydes such as 3-oxocarbaldehydes
is crucial for the current protocol.
affording products 11a-c and 12a-c. In contrast,
substrates with an electron-withdrawing substituent
would generate intermediate 47a' to provide the
cyclized product 13. In case of acetylene 1h, the
highly electron-donating ethoxy group plays a major
role to control the regioselectivity, affording products
14a-b. The regiochemistry of 14a-b with 7b-c and
11b-c was unambiguously confirmed by 1H NMRs.
Conclusion
In conclusion, we have developed a facile and
efficient synthetic one-step cascade protocol for the
regioselective synthesis of halofunctionalized indenes
relying on the dual role of BX3. The synthesized
halofunctionalized indenes can be further derivatized
at the C-3 position of the indene moiety through
coupling, nucleophilic substitution, and oxidation
reactions.
Experimental Section
Scheme 6. Reactions with other carbonyl compounds.
General remarks: All experiments were carried out in
open air. Merck precoated silica gel plates (Art. 5554) with
a fluorescent indicator were used for analytical TLC. Flash
column chromatography was performed using silica gel
9385 (Merck). The melting points are uncorrected and
were determined using micro-cover glasses on a Fisher-
Johns apparatus. 1H NMR spectra were recorded on a
Varian-VNS (600 MHz) spectrometer using the chemical
shift of the solvent at  = 7.24 ppm for CDCl3 or  = 0.00
ppm for TMS as a reference. 13C NMR spectra were
recorded on a Varian-VNS (150 MHz) spectrometer using
the chemical shift of the solvent at  = 77.0 ppm for CDCl3
as a reference. 19F NMR spectrum was recorded on a
Varian-VNS (564 MHz) spectrometer. Chemical shifts (δ)
are expressed in units of ppm and J values are given in Hz.
Multiplicities are abbreviated as follows: s = singlet, d =
doublet, t = triplet, q = quartet, brs = broad singlet, dd =
doublet of doublets, sept = septet, and m = multiplet. IR
spectra were recorded on a FTIR (BIO-RAD) and high-
resolution mass spectra were obtained on a JEOL JMS-700
spectrometer at the Korea Basic Science Institute.
Based on the literature report, a plausible
mechanism for the formation of 3a is proposed in
Scheme 7.[15] In the presence of BX3, 3-
formylchromone (2a) is converted into complex 2a'.
Tautomerization of 2a' by oxygen lone pairs forms
complex 45 via the release of X- from BX3.[19]
Intermolecular nucleophilic addition of X- to 1a
followed by alkyne attack on the carbonyl carbon of
General procedure for the Synthesis of 3-33 : To a
mixture of alkynes (1) (0.5 mmol) and carbaldehydes (2)
(0.5 mmol) in dichloromethane (1 mL) was added boron
reagents (1.0-3.0 equiv.) at room temperature; the mixture
was stirred as such. The progress of the reaction was
monitored by TLC. After the completion of the reaction,
the solvent was removed on a rotary evaporator and the
product was extracted with ethyl acetate (2 × 10 mL) and
then washed with brine (5 mL). The organic layer was
dried over Na2SO4 and evaporated to give the crude
product, which was purified by short column
chromatography over silica gel (EtOAc/hexane = 1:19) to
give the desired products.
General Procedure for the Preparation of 34a-b:
Compound 3c (0.5 mmol) was added to a solution of
Scheme 7. Proposed mechanism for the formation of 3a
and regiochemistry of the synthesized compounds.
4
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10.1002/adsc.201901266
Advanced Synthesis & Catalysis
arylboronic acids (1.5 mmol, 1.5 equiv.), Pd(OAc)2 (5.0
mol %), S-Phos (5.0 mol %), and K3PO4 (1.0 mmol, 2.0
equiv.) in toluene (2 mL). The solution was then stirred at
After the completion of the reaction, the solvent was
removed on a rotary evaporator and the product was
extracted with ethyl acetate (2 × 10 mL) and then washed
with brine (5 mL). The organic layer was dried over
Na2SO4 and evaporated to give the final compound as
brown viscous oils 43 in 83% yield (122 mg).
o
80 C for 12 h. After completion of reaction as indicated
by TLC, the solvent was evaporated and the residue was
purified over silica gel (EtOAc/hexane = 1:19) to give the
desired products 34a-b in 85-87% yields.
3-(3-Fluoro-2-phenyl-1H-inden-1-yl)-4H-chromen-4-
one (3a). The title compound (3a) was prepared according
to the general procedure. The product was obtained as a
General Procedure for the Preparation of 3-(3-(Furan-
2-yl)-2-phenyl-1H-inden-1-yl)-4H-chromen-4-one (35):
To a solution of bromoindene 3c (0.5 mmol, 207.0 mg) and
2-(tributylstannyl)furan (0.5 mmol, 178.5 mg) in THF (2
mL) was added Pd(PPh3)2Cl2 (5.0 mol %) at room
temperature; the mixture was then heated at 60 oC for 12 h.
The progress of the reaction was monitored by TLC. After
the completion of the reaction, the solvent was removed on
a rotary evaporator and the product was extracted with
ethyl acetate (2 × 10 mL) and then washed with brine (5
mL). The organic layer was dried over Na2SO4 and
evaporated to give the crude product, which was purified
by short column chromatography over silica gel
(EtOAc/hexane = 1:19) to give the desired product 35 in
89% yield (178 mg).
o
1
white solid, mp 185-186 C. Yield: 65% (115 mg). H
NMR (600 MHz, CDCl3)  8.34 (1H, dd, J = 8.1, 1.7 Hz),
7.63-7.60 (1H, m), 7.60-7.58 (2H, m), 7.50 (1H, d, J = 7.8
Hz), 7.44-7.41 (2H, m), 7.37 (1H, s), 7.34-7.30 (4H, m),
7.21-7.18 (2H, m), 5.61 (1H, brs); 13C NMR (150 MHz,
CDCl3)  177.7, 157.1 (d, J = 278.1 Hz), 156.3, 152.9,
144.5, 135.3 (d, J = 25.2 Hz), 133.6, 131.3 (d, J = 4.5 Hz),
128.7, 127.7, 127.7, 127.4, 127.2, 125.9, 125.2, 124.0 (d, J
= 2.7 Hz), 123.8, 122.6 (d, J = 1.2 Hz), 119.8 (d, J = 2.2
Hz), 118.1, 118.0 (d, J = 2.2 Hz), 40.7; IR (ATR) 3058,
1718, 1622, 1460, 1358, 1145, 1065, 944, 804, 748, 608
cm-1; HRMS m/z (M+) calcd for C24H15FO2: 354.1056.
Found: 354.1056.
General Procedure for the Preparation of 3-(3-Ethoxy-
2-phenyl-1H-inden-1-yl)-4H-chromen-4-one (36): To a
solution of bromoindene 3c (0.5 mmol, 207.0 mg) in
ethanol (2 mL) was added sodium hydroxide (0.5 mmol,
20.0 mg) at room temperature; the mixture was stirred for
10 min. The progress of the reaction was monitored by
TLC. After the completion of the reaction, the solvent was
removed on a rotary evaporator and the product was
extracted with ethyl acetate (2 × 10 mL) and then washed
with brine (5 mL). The organic layer was dried over
Na2SO4 and evaporated to give the crude product, which
was purified by short column chromatography over silica
gel (EtOAc/hexane = 1:19) to give the desired product 36
as red colour viscous oils in 55% yield (104 mg).
3-(3-Chloro-2-phenyl-1H-inden-1-yl)-4H-chromen-4-
one (3b). The title compound (3b) was prepared according
to the general procedure. The product was obtained as a
o
1
white solid, mp 158-159 C. Yield: 91% (168 mg). H
NMR (600 MHz, CDCl3)  8.18 (1H, d, J = 8.1 Hz), 7.64
(2H, d, J = 7.7 Hz), 7.46-7.41 (2H, m), 7.37 (1H, d, J = 7.5
Hz), 7.27-7.23 (4H, m), 7.18 (1H, s), 7.14-7.09 (3H, m),
5.67 (1H, brs); 13C NMR (150 MHz, CDCl3)  177.3,
156.1, 153.1, 144.8, 141.3, 139.8, 133.5, 132.7, 128.8,
128.5, 128.5, 127.9, 127.5, 126.9, 125.8, 125.1, 123.7,
123.4, 122.5, 119.5, 118.0, 45.2; IR (ATR) 3058, 1625,
1462, 1394, 1352, 1276, 1140, 935, 756, 601 cm-1; HRMS
m/z (M+) calcd for C24H15ClO2: 370.0761. Found:
370.0763.
General Procedure for the Preparation of 3-(1-Oxo-2-
phenyl-1H-inden-3-yl)-4H-chromen-4-one (37): To a
solution of bromoindene 3c (0.5 mmol, 207.0 mg) in DMF
(2 mL) was added CuO (0.5 mmol, 40.0 mg) and K2CO3
(0.5 mmol, 69.0 mg) at room temperature; the mixture was
stirred in open air for 12 h. The progress of the reaction
was monitored by TLC. After the completion of the
reaction, the product was extracted with ethyl acetate (2 ×
10 mL) and then washed with brine (5 mL). The organic
layer was dried over Na2SO4 and evaporated to give the
crude product, which was purified by short column
chromatography over silica gel (EtOAc/hexane = 1:19) to
give the desired product 37 as orange solid in 67% yield
(117 mg).
3-(3-Bromo-2-phenyl-1H-inden-1-yl)-4H-chromen-4-
one (3c). The title compound (3c) was prepared according
to the general procedure. The product was obtained as a
o
1
white solid, mp 153-154 C. Yield: 92% (190 mg). H
NMR (600 MHz, CDCl3)  8.29 (1H, d, J = 8.1 Hz), 7.75
(2H, d, J = 7.1 Hz), 7.57 (1H, dt, J = 8.4, 1.8 Hz), 7.52 (1H,
d, J = 7.6 Hz), 7.46 (1H, d, J = 7.5 Hz), 7.39-7.34 (4H, m),
7.31 (1H, s), 7.27-7.24 (2H, m), 7.21 (1H, t, J = 7.5 Hz),
5.75 (1H, brs); 13C NMR (150 MHz, CDCl3)  177.2,
156.1, 153.1, 145.1, 143.6, 142.6, 133.5, 133.4, 128.6,
128.4, 128.0, 127.5, 126.9, 125.8, 125.1, 123.7, 123.3,
122.4, 120.9, 118.7, 118.0, 46.6; IR (ATR) 3226, 1626,
1459, 1397, 1349, 1275, 1214, 926, 810, 755, 688 cm-1;
HRMS m/z (M+) calcd for C24H15BrO2: 414.0255. Found:
414.0256.
General Procedure for the Preparation of (2R)-2,3-
Diphenyl-2,3-dihydro-1H-inden-1-one (40): To
a
3-(3-Iodo-2-phenyl-1H-inden-1-yl)-4H-chromen-4-one
(3d). The title compound (3d) was prepared according to
the general procedure. The product was obtained as a white
mixture of diphenylacetylene (1a) (0.5 mmol. 89.0 mg)
and benzaldehye (38) (0.5 mmol, 53.0 mg) in
dichloromethane (1 mL) was added boron trifluoride
etherate (0.5 mmol, 1.0 equiv.) and heated the reaction
o
1
solid, mp 180-182 C. Yield: 40% (92 mg). H NMR (600
MHz, CDCl3)  8.25 (1H, d, J = 8.1 Hz), 7.68 (2H, d, J =
7.0 Hz), 7.60-7.57 (1H, m), 7.44 (1H, d, J = 7.5 Hz), 7.39-
7.34 (5H, m), 7.32-7.31 (1H, m), 7.28-7.26 (2H, m), 7.19
(1H, dt, J = 7.8, 1.2 Hz), 5.72 (1H, brs); 13C NMR (150
MHz, CDCl3)  177.1, 156.1, 153.1, 150.7, 145.0, 135.0,
133.6, 131.5, 128.8, 128.4, 128.2, 127.6, 126.9, 125.9,
125.2, 123.8, 123.3, 123.2, 122.4, 118.1, 94.9, 48.1; IR
(ATR) 2877, 1596, 1513, 1441, 1416, 1368, 1321, 1261,
1143, 1025, 927, 819, 756, 582 cm-1; HRMS m/z (M+)
calcd for C24H15IO2: 462.0117. Found: 462.0120.
o
upto 60 C for 12 h. The progress of the reaction was
monitored by TLC. After the completion of the reaction,
the solvent was removed on a rotary evaporator and the
product was extracted with ethyl acetate (2 × 10 mL) and
then washed with brine (5 mL). The organic layer was
dried over Na2SO4 and evaporated to give the crude
product, which was purified by short column
chromatography over silica gel (EtOAc/hexane = 1:19) to
give the desired product 40 as viscous oils in 66% (187
mg) yield.
3-(3-Fluoro-2-phenyl-1H-inden-1-yl)-6-methyl-4H-
chromen-4-one (4a). The title compound (4a) was
prepared according to the general procedure. The product
was obtained as a white solid and recrystallized with
hexane/ethylacetate, mp 162-163 oC. Yield: 66% (121 mg).
1H NMR (600 MHz, CDCl3)  8.13 (1H, s), 7.59 (2H, d, J
= 8.1 Hz), 7.50 (1H, d, J = 7.5 Hz), 7.44-7.40 (2H, m),
7.32 (4H, t, J = 7.9 Hz), 7.20-7.18 (3H, m), 5.61 (1H, brs),
General Procedure for the Preparation of 2,2-Difluoro-
4,6-dimethyl-2H-dioxaborinine (43): To a mixture of
diphenylacetylene (1a) (0.5 mmol, 89.0 mg) and pentane-
2,4-dione (42) (0.5 mmol, 50.0 mg) in dichloromethane (1
mL) was added boron trifluoride etherate (0.5 mmol, 1.0
equiv.) at room temperature; the mixture was stirred for 12
h. The progress of the reaction was monitored by TLC.
5
This article is protected by copyright. All rights reserved.

10.1002/adsc.201901266
Advanced Synthesis & Catalysis
2.46 (3H, s); 13C NMR (150 MHz, CDCl3)  177.7, 157.1
(d, J = 278.2 Hz), 154.5, 152.8, 144.6, 135.3 (d, J = 25.0
Hz), 135.2, 134.8, 131.3 (d, J = 4.6 Hz), 128.7, 127.7 (d, J
7.40-7.36 (4H, m), 7.27 (1H, t, J = 7.4 Hz), 7.24-7.22 (1H,
m), 5.72 (1H, brs); 13C NMR (150 MHz, CDCl3)  176.1,
158.9, 153.4, 144.7, 144.1, 141.4, 139.2, 132.4, 129.4,
= 5.7 Hz), 127.3, 127.2, 127.1, 125.1, 124.0 (d, J = 2.7 Hz), 128.7, 128.5, 128.2, 127.9, 127.9, 127.2, 123.8, 123.7,
123.5, 122.3 (d, J = 1.8 Hz), 119.8 (d, J = 2.2 Hz), 117.9 (d, 123.4, 122.8, 119.9, 119.8, 45.1; IR (ATR) 3295, 1651,
J = 2.2 Hz), 117.8, 40.7, 20.9; 19F NMR: (564 MHz,
1525, 1449, 1378, 1328, 1261, 1222, 1137, 1072, 991, 757,
CDCl3) δ -129.9 (1F, s); IR (ATR) 3068, 1719, 1612, 1462, 688, 591 cm-1; HRMS m/z (M+) calcd for C24H14ClNO4:
1359, 1155, 1061, 945, 801, 745, 609 cm-1; HRMS m/z
415.0611. Found: 415.0610.
(M+) calcd for C25H17FO2: 368.1213. Found: 368.1211.
3-(3-Bromo-2-phenyl-1H-inden-1-yl)-6-nitro-4H-
chromen-4-one (5c). The title compound (5c) was
prepared according to the general procedure. The product
X-Ray crystallographic data of compound 4a: Empirical
Formula- C25H17FO2, M = 368.38, Triclinic, Space group
P-1, a = 8.3916(10) Å, b = 9.3062(11) Å, c = 13.6203(13)
Å, V = 920.86(18) Å3, Z = 2, T = 223(2) K, ρcalcd = 1.329
Mg/m3, 2Өmax. = 28.487o, Refinement of 254 parameters on
4639 independent reflections out of 30629 collected
reflections (Rint = 0.0769) led to R1 = 0.0561 [I >2σ(I)],
wR2 = 0.1063 (all data) and S = 1.044 with the largest
difference peak and hole of 0.267 and -0.207 e.Å-3
respectively. The crystal structure has been deposited at the
o
was obtained as a white solid, mp 184-185 C. Yield: 77%
1
(176 mg). H NMR (600 MHz, CDCl3)  9.12 (1H, d, J =
2.8 Hz), 8.40 (1H, dd, J = 9.2, 2.8 Hz), 7.72 (2H, d, J = 7.5
Hz), 7.50 (1H, d, J = 7.6 Hz), 7.44-7.41 (2H, m), 7.39-7.35
(4H, m), 7.27 (1H, t, J = 7.4 Hz), 7.21 (1H, td, J = 7.5, 1.1
Hz), 5.67 (1H, brs); 13C NMR (150 MHz, CDCl3)  175.9,
158.8, 153.4, 144.6, 144.2, 142.9, 142.6, 133.1, 128.6,
128.2, 128.2, 127.8, 127.8, 127.1, 123.6, 123.5, 123.2,
Cambridge Crystallographic Data Centre (CCDC 1909137). 122.7, 121.0, 119.8, 119.3, 46.4; IR (ATR) 3290, 1653,
The data can be obtained free of charge via the Internet at
www.ccdc.cam.ac.uk/data_request/cif.
1515, 1439, 1389, 1314, 1263, 1210, 1138, 1070, 992, 757,
687, 591 cm-1; HRMS m/z (M+) calcd for C24H14BrNO4:
459.0106. Found: 459.0104.
3-(3-Chloro-2-phenyl-1H-inden-1-yl)-6-methyl-4H-
chromen-4-one (4b). The title compound (4b) was
prepared according to the general procedure. The product
6-Chloro-3-(3-fluoro-2-phenyl-1H-inden-1-yl)-8-
methyl-4H-chromen-4-one (6a). The title compound (6a)
was prepared according to the general procedure. The
o
was obtained as a white solid, mp 166-167 C. Yield: 90%
(172 mg). 1H NMR (600 MHz, CDCl3)  8.10 (1H, s), 7.77
(2H, d, J = 7.8 Hz), 7.53 (1H, d, J = 7.2 Hz), 7.49 (1H, d, J
= 7.2 Hz), 7.38-7.34 (4H, m), 7.25-7.20 (3H, m), 7.13 (1H,
d, J = 9.0 Hz), 5.80 (1H, brs), 2.43 (3H, s); 13C NMR (150
MHz, CDCl3)  177.3, 154.3, 152.9, 144.9, 141.3, 139.8,
135.0, 134.7, 132.6, 128.7, 128.5, 128.4, 127.8, 127.4,
126.8, 125.0, 123.4, 123.3, 122.2, 119.4, 117.7, 45.2, 20.8;
IR (ATR) 3057, 1626, 1461, 1392, 1352, 1277, 1140, 935,
756, 605 cm-1; HRMS m/z (M+) calcd for C25H17ClO2:
384.0917. Found: 384.0913.
product was obtained as a white solid, mp 226-227 C.
o
1
Yield: 60% (120 mg). H NMR (600 MHz, CDCl3)  8.27
(1H, s), 7.56 (2H, d, J = 8.3 Hz), 7.47 (1H, d, J = 7.6 Hz),
7.43 (1H, d, J = 7.5 Hz), 7.33-7.29 (4H, m), 7.21-7.17 (3H,
m), 5.56 (1H, brs), 2.43 (3H, s); 13C NMR (150 MHz,
CDCl3)  176.6, 157.1 (d, J = 278.1 Hz), 154.5, 152.8,
144.34, 143.0, 135.3 (d, J = 25.2 Hz), 131.9, 131.2 (d, J =
4.5 Hz), 128.7, 127.7, 127.6, 127.5, 127.2, 125.5, 124.0 (d,
J = 2.2 Hz), 122.9, 122.6, 119.8, 119.7 (d, J = 1.9 Hz),
118.0 (d, J = 2.2 Hz), 40.7, 20.7; IR (ATR) 3054, 1716,
1625, 1450, 1357, 1146, 1063, 945, 804, 749, 609 cm-1;
HRMS m/z (M+) calcd for C25H16ClFO2: 402.0823. Found:
402.0822.
3-(3-Bromo-2-phenyl-1H-inden-1-yl)-6-methyl-4H-
chromen-4-one (4c). The title compound (4c) was
prepared according to the general procedure. The product
o
was obtained as a white solid, mp 175-176 C. Yield: 92%
6-Chloro-3-(3-chloro-2-phenyl-1H-inden-1-yl)-8-
methyl-4H-chromen-4-one (6b). The title compound (6b)
was prepared according to the general procedure. The
(196 mg). 1H NMR (600 MHz, CDCl3)  7.92 (1H, s), 7.62
(2H, d, J = 8.2 Hz), 7.36 (1H, d, J = 7.4 Hz), 7.32 (1H, d, J
= 7.5 Hz), 7.22-7.19 (4H, m), 7.11-7.05 (3H, m), 6.97 (1H,
d, J = 8.5 Hz), 5.62 (1H, brs), 2.27 (3H, s); 13C NMR (150
MHz, CDCl3)  177.1, 154.2, 152.9, 145.0, 143.5, 142.4,
135.0, 134.7, 133.3, 128.5, 128.3, 127.9, 127.4, 126.8,
124.9, 123.2, 123.2, 121.9, 120.7, 118.5, 117.6, 46.4, 20.8;
IR (ATR) 3216, 1626, 1452, 1397, 1341, 1272, 1224, 926,
811, 756, 685 cm-1; HRMS m/z (M+) calcd for C25H17BrO2:
428.0412. Found: 428.0414.
o
product was obtained as a white solid, mp 185-186 C.
1
Yield: 77% (160 mg). H NMR (600 MHz, CDCl3)  8.23
(1H, s), 7.74 (2H, d, J = 7.2 Hz), 7.53 (1H, d, J = 7.2 Hz),
7.46 (1H, d, J = 7.5 Hz), 7.39-7.35 (3H, m), 7.26-7.21 (3H,
m), 7.12 (1H, s), 5.74 (1H, brs), 2.40 (3H, s); 13C NMR
(150 MHz, CDCl3)  176.2, 154.4, 153.0, 144.7, 142.9,
141.3, 139.7, 132.6, 131.8, 128.9, 128.5, 128.5, 127.9,
127.5, 127.0, 125.4, 123.4, 122.7, 122.5, 119.7, 119.6, 45.1,
20.6; IR (ATR) 3258, 1627, 1452, 1384, 1351, 1276, 1141,
965, 756, 611 cm-1; HRMS m/z (M+) calcd for
C25H16Cl2O2: 418.0527. Found: 418.0526.
3-(3-Fluoro-2-phenyl-1H-inden-1-yl)-6-nitro-4H-
chromen-4-one (5a). The title compound (5a) was
prepared according to the general procedure. The product
o
was obtained as a white solid, mp 190-191 C. Yield: 62%
3-(3-Bromo-2-phenyl-1H-inden-1-yl)-6-chloro-7-
1
(123 mg). H NMR (600 MHz, CDCl3)  9.21 (1H, d, J =
methyl-4H-chromen-4-one (6c). The title compound (6c)
was prepared according to the general procedure. The
2.8 Hz), 8.44 (1H, dd, J = 9.1, 2.8 Hz), 7.56 (2H, d, J = 7.2
Hz), 7.48-7.42 (4H, m), 7.36-7.33 (3H, m), 7.21 (2H, t, J =
7.5 Hz), 5.56 (1H, brs); 13C NMR (150 MHz, CDCl3) 
176.4, 159.0, 157.2 (d, J = 278.1 Hz), 153.2, 144.8, 143.7,
135.3 (d, J = 25.5 Hz), 131.0 (d, J = 4.9 Hz), 128.9, 127.9,
127.7, 127.6, 127.6, 127.4, 127.4, 123.9 (d, J = 2.5 Hz),
123.8, 122.8, 119.9, 119.3 (d, J = 3.1 Hz), 118.2 (d, J = 2.2
Hz), 40.6; IR (ATR) 3293, 1650, 1525, 1449, 1379, 1318,
1262, 1212, 1138, 1070, 991, 756, 686, 591 cm-1; HRMS
m/z (M+) calcd for C24H14FNO4: 399.0907. Found:
399.0909.
o
product was obtained as a white solid, mp 181-182 C.
1
Yield: 79% (182 mg). H NMR (600 MHz, CDCl3)  8.09
(1H, s), 7.62 (2H, d, J = 7.8 Hz), 7.40 (1H, d, J = 7.6 Hz),
7.31 (1H, d, J = 7.5 Hz), 7.27-7.22 (3H, m), 7.14 (1H, t, J
= 7.7 Hz), 7.09 (2H, t, J = 7.2 Hz), 6.98 (1H, s), 5.59 (1H,
brs), 2.27 (3H, s); 13C NMR (150 MHz, CDCl3)  176.0,
154.3, 153.0, 144.9, 143.4, 142.8, 142.5, 133.3, 131.8,
128.6, 128.4, 128.0, 127.6, 126.9, 125.4, 123.2, 122.7,
122.2, 120.9, 119.7, 118.8, 46.4, 20.6; IR (ATR) 3064,
1628, 1564, 1458, 1393, 1339, 1265, 1214, 1071, 1064,
929, 836, 756, 587 cm-1; HRMS m/z (M+) calcd for
C25H16BrClO2: 462.0022. Found: 462.0025.
3-(3-Chloro-2-phenyl-1H-inden-1-yl)-6-nitro-4H-
chromen-4-one (5b). The title compound (5b) was
prepared according to the general procedure. The product
3-(3-Fluoro-6-methyl-2-(p-tolyl)-1H-inden-1-yl)-4H-
chromen-4-one (7a). The title compound (7a) was
prepared according to the general procedure. The product
o
was obtained as a white solid, mp 175-176 C. Yield: 73%
1
(151 mg). H NMR (600 MHz, CDCl3)  9.16 (1H, d, J =
o
2.8 Hz), 8.42 (1H, dd, J = 9.1, 2.8 Hz), 7.72 (2H, d, J = 7.6
Hz), 7.53 (1H, d, J = 7.5 Hz), 7.45 (2H, d, J = 9.0 Hz),
was obtained as a white solid, mp 195-196 C. Yield: 59%
1
(112 mg). H NMR (600 MHz, CDCl3)  8.35 (1H, d, J =
6
This article is protected by copyright. All rights reserved.

10.1002/adsc.201901266
Advanced Synthesis & Catalysis
o
7.4 Hz), 7.62 (1H, dt, J = 7.8, 1.2 Hz), 7.46-7.41 (3H, m),
7.36 (1H, s), 7.32-7.29 (3H, m), 7.12 (3H, d, J = 7.9 Hz),
5.53 (1H, brs), 2.31 (3H, s), 2.29 (3H, s); 13C NMR (150
MHz, CDCl3)  177.8, 156.8 (d, J = 277.0 Hz), 156.3,
153.0, 137.2, 136.9, 133.6, 129.4, 128.7, 128.1, 127.5 (d, J
product was obtained as a white solid, mp 194-195 C.
1
Yield: 63% (165 mg). H NMR (600 MHz, CDCl3)  8.28
(1H, d, J = 7.8 Hz), 7.65-7.62 (1H, m), 7.59-7.57 (3H, m),
7.50 (1H, dd, J = 8.4, 1.8 Hz), 7.48-7.45 (2H, m), 7.42 (1H,
t, J = 7.8 Hz), 7.37 (1H, d, J = 7.8 Hz), 7.32 (1H, d, J = 8.4
= 6.3 Hz), 125.9, 125.5, 125.1, 124.8 (d, J = 3.4 Hz), 124.1, Hz), 7.29 (1H, s), 5.68 (1H, brs); 13C NMR (150 MHz,
123.9, 122.9, 118.7, 118.1, 117.5 (d, J = 2.4 Hz), 40.4,
21.6, 21.2; IR (ATR) 3158, 1712, 1623, 1460, 1354, 1155,
1045, 935, 804, 748, 618 cm-1; HRMS m/z (M+) calcd for
C26H19FO2: 382.1369. Found: 382.1372.
CDCl3)  177.1, 156.2, 153.3, 146.4, 140.3, 139.2, 133.9,
131.9, 131.2, 130.9, 130.0, 128.8, 126.8, 126.0, 125.4,
123.7, 122.4, 121.7, 121.4, 121.0, 118.1, 45.1; IR (ATR)
3064, 1625, 1561, 1452, 1392, 1341, 1285, 1211, 1081,
1014, 927, 814, 753, 589 cm-1; HRMS m/z (M+) calcd for
C24H13Br2ClO2: 525.8971. Found: 525.8974.
3-(3-Chloro-6-methyl-2-(p-tolyl)-1H-inden-1-yl)-4H-
chromen-4-one (7b). The title compound (7b) was
prepared according to the general procedure. The product
3-(3,6-Dibromo-2-(4-bromophenyl)-1H-inden-1-yl)-4H-
chromen-4-one (10b). The title compound (10b) was
prepared according to the general procedure. The product
o
was obtained as a white solid, mp 191-192 C. Yield: 88%
1
(175 mg). H NMR (600 MHz, CDCl3)  8.31 (1H, d, J =
o
8.4 Hz), 7.62 (2H, d, J = 8.4 Hz), 7.60-7.58 (1H, m), 7.41-
7.38 (2H, m), 7.30-7.27 (3H, m), 7.17-7.14 (3H, m), 5.72
(1H, brs), 2.32 (3H, s), 2.29 (3H, s); 13C NMR (150 MHz,
CDCl3)  177.5, 156.2, 153.2, 145.1, 138.9, 138.7, 137.7,
136.9, 133.5, 130.0, 129.2, 128.3, 128.2, 128.2, 125.9,
125.1, 124.2, 123.8, 122.9, 119.1, 118.1, 44.9, 21.5, 21.2;
IR (ATR) 3158, 1625, 1464, 1353, 1354, 1276, 1151, 937,
757, 601 cm-1; HRMS m/z (M+) calcd for C26H19ClO2:
398.1074. Found: 398.1073.
was obtained as a white solid, mp 188-190 C. Yield: 67%
1
(190 mg). H NMR (600 MHz, CDCl3)  8.26 (1H, d, J =
7.2 Hz), 7.62 (1H, dt, J = 6.6, 1.8 Hz), 7.58 (2H, d, J = 8.4
Hz), 7.55 (1H, s), 7.50 (1H, d, J = 8.4 Hz), 7.47-7.45 (2H,
m), 7.41 (1H, t, J = 7.8 Hz), 7.35 (1H, d, J = 7.8 Hz), 7.32
(1H, d, J = 8.4 Hz), 7.29 (1H, s), 5.65 (1H, brs); 13C NMR
(150 MHz, CDCl3)  177.0, 156.2, 153.3, 146.6, 143.0,
141.5, 133.9, 132.0, 131.8, 130.9, 130.1, 126.6, 126.0,
125.4, 123.6, 122.6, 122.3, 121.5, 121.4, 118.4, 118.1,
46.6; IR (ATR) 3064, 1624, 1568, 1458, 1392, 1349, 1275,
1214, 1071, 1004, 926, 816, 753, 589 cm-1; HRMS m/z
(M+) calcd for C24H13Br3O2: 569.8466. Found: 569.8470.
3-(3-Bromo-6-methyl-2-(p-tolyl)-1H-inden-1-yl)-4H-
chromen-4-one (7c). The title compound (7c) was
prepared according to the general procedure. The product
o
was obtained as a white solid, mp 240-242 C. Yield: 89%
3-(3-Fluoro-2-(p-tolyl)-1H-inden-1-yl)-4H-chromen-4-
one (11a). The title compound (11a) was prepared
according to the general procedure. The product was
obtained as a white solid, mp 243-244 oC. Yield: 64% (117
1
(196 mg). H NMR (600 MHz, CDCl3)  8.30 (1H, d, J =
7.8 Hz), 7.64 (2H, d, J = 8.4 Hz), 7.59-7.57 (1H, m), 7.40-
7.37 (2H, m), 7.30 (1H, s), 7.28-7.26 (2H, m), 7.18-7.15
(3H, m), 5.70 (1H, brs), 2.33 (3H, s), 2.29 (3H, s); 13C
NMR (150 MHz, CDCl3)  177.4, 156.2, 153.2, 145.2,
142.4, 140.1, 137.8, 136.9, 133.5, 130.6, 129.2, 128.5,
128.2, 125.9, 125.1, 124.1, 123.8, 122.7, 120.4, 118.0,
118.0, 46.2, 21.4, 21.2; IR (ATR) 3164, 1628, 1564, 1458,
1390, 1349, 1265, 1214, 1072, 1004, 925, 818, 756, 599
cm-1; HRMS m/z (M+) calcd for C26H19BrO2: 442.0567.
Found: 442.0568.
1
mg). H NMR (600 MHz, CDCl3)  8.35 (1H, d, J = 7.8
Hz), 7.62 (1H, dt, J = 8.4, 1.2 Hz), 7.56 (2H, d, J = 7.8 Hz),
7.43 (1H, d, J = 7.2 Hz), 7.37 (1H, s), 7.32-7.30 (5H, m),
7.18 (1H, t, J = 7.2 Hz), 7.12 (1H, d, J = 7.2 Hz), 5.56 (1H,
brs), 2.31 (3H, s); 13C NMR (150 MHz, CDCl3)  177.8,
157.3 (d, J = 278.1 Hz), 156.3, 153.0, 144.8, 137.4, 133.6,
131.5 (d, J = 4.3 Hz), 129.4, 128.7, 128.1, 127.5 (d, J = 6.9
Hz), 126.9, 125.9, 125.2, 124.8, 123.9, 122.8, 118.7, 118.1,
117.7 (d, J = 2.2 Hz), 40.4, 21.6; IR (ATR) 3053, 1719,
1612, 1455, 1358, 1135, 1035, 944, 805, 748, 618 cm-1;
HRMS m/z (M+) calcd for C25H17FO2: 368.1213. Found:
368.1216.
3-(3-Iodo-6-methyl-2-(p-tolyl)-1H-inden-1-yl)-6-
isopropyl-4H-chromen-4-one (8). The title compound (8)
was prepared according to the general procedure. The
o
product was obtained as a white solid, mp 178-179 C.
1
Yield: 53% (140 mg). H NMR (600 MHz, CDCl3)  8.12
5-(3-Chloro-2-(p-tolyl)-1H-inden-1-yl)-2,3-dihydro-4H-
pyran-4-one (11b). The title compound (11b) was
prepared according to the general procedure. The product
(1H, s), 7.58 (2H, d, J = 7.8 Hz), 7.46 (1H, d, J = 9.0 Hz),
7.31-7.26 (2H, m), 7.22-7.21 (2H, m), 7.17-7.14 (3H, m),
5.70 (1H, brs), 3.01 (1H, sept, J = 7.2 Hz), 2.33 (3H, s),
was obtained as a white solid, mp 179- 180 oC. Yield: 89%
2.29 (3H, s), 1.29 (6H, d, J = 7.2 Hz); 13C NMR (150 MHz, (170 mg). H NMR (600 MHz, CDCl3)  8.19 (1H, d, J =
1
CDCl3)  177.4, 154.6, 153.1, 149.5, 146.0, 145.7, 142.6,
137.9, 136.8, 132.5, 132.1, 129.1, 128.6, 128.2, 123.9,
123.5, 122.7, 122.5, 122.4, 117.9, 93.9, 47.8, 33.7, 23.9,
23.8, 21.3, 21.2; IR (ATR) 2871, 1588, 1512, 1451, 1419,
1356, 1310, 1261, 1143, 1012, 927, 816, 757, 588 cm-1;
HRMS m/z (M+) calcd for C29H25IO2: 532.0899. Found:
532.0901.
7.8 Hz), 7.62 (2H, d, J = 7.2 Hz), 7.42 (1H, dt, J = 7.8, 1.2
Hz), 7.29 (1H, dd, J = 7.8, 3.0 Hz), 7.26-7.17 (5H, m),
7.12-7.08 (2H, m), 7.05 (1H, d, J = 7.8 Hz), 5.63 (1H, brs),
2.20 (3H, s); 13C NMR (150 MHz, CDCl3)  177.2, 156.0,
153.1, 145.2, 142.4, 140.0, 137.0, 133.4, 129.1, 128.5,
128.4, 128.2, 127.8, 125.8, 125.0, 124.0, 123.7, 122.5,
120.5, 118.7, 118.0, 46.3, 21.3; IR (ATR) 3051, 1625,
1463, 1395, 1351, 1275, 1144, 955, 756, 611 cm-1; HRMS
m/z (M+) calcd for C25H17ClO2: 384.0917. Found:
384.0920.
3-(5-Bromo-2-(3-bromophenyl)-3-chloro-1H-inden-1-
yl)-4H-chromen-4-one (9). The title compound (9) was
prepared according to the general procedure. The product
o
was obtained as a white solid, mp 240-242 C. Yield: 54%
3-(3-Bromo-2-(p-tolyl)-1H-inden-1-yl)-4H-chromen-4-
one (11c). The title compound (11c) was prepared
according to the general procedure. The product was
obtained as a white solid, mp 180-182 oC. Yield: 88% (188
1
(141 mg). H NMR (600 MHz, CDCl3)  8.26 (1H, d, J =
7.8 Hz), 7.95 (1H, s), 7.65 (1H, s), 7.61 (1H, dt, J = 6.6,
1.2 Hz), 7.53 (1H, d, J = 7.2 Hz), 7.41-7.37 (2H, m), 7.34-
7.27 (4H, m), 7.210 (1H, t, J = 8.4 Hz), 5.63 (1H, brs); 13
C
mg). H NMR (600 MHz, CDCl3)  8.18 (1H, d, J = 7.8
1
NMR (150 MHz, CDCl3)  177.0, 156.1, 153.1, 143.0,
140.0, 134.3, 133.8, 131.3, 131.2, 130.2, 130.1, 129.5,
128.9, 127.2, 125.9, 125.4, 125.0, 123.6, 123.0, 122.7,
121.7, 121.6, 118.1, 45.2; IR (ATR) 3062, 1627, 1565,
1458, 13921, 1339, 1265, 1224, 1071, 1014, 966, 813, 755,
590 cm-1; HRMS m/z (M+) calcd for C24H13Br2ClO2:
525.8971. Found: 525.8969.
Hz), 7.63 (2H, d, J = 7.8 Hz), 7.43 (1H, t, J = 6.6 Hz),
7.28-7.21 (4H, m), 7.18-7.17 (2H, m), 7.12 (2H, d, J = 7.8
Hz), 7.06 (1H, d, J = 7.8 Hz), 5.61 (1H, brs), 2.21 (3H, s);
13C NMR (150 MHz, CDCl3)  177.2, 156.0, 153.1, 145.2,
142.4, 140.0, 137.0, 133.5, 133.4, 128.5, 128.4, 128.2,
127.8, 125.8, 125.0, 124.0, 123.7, 122.5, 120.5, 118.7,
118.0, 46.3, 21.4; IR (ATR) 3024, 1624, 1563, 1468, 1321,
13411, 1275, 1214, 1071, 1034, 927, 811, 756, 585 cm-1;
HRMS m/z (M+) calcd for C25H17BrO2: 428.0412. Found:
428.0409.
3-(6-Bromo-2-(4-bromophenyl)-3-chloro-1H-inden-1-
yl)-4H-chromen-4-one (10a). The title compound (10a)
was prepared according to the general procedure. The
7
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10.1002/adsc.201901266
Advanced Synthesis & Catalysis
3-(3-Fluoro-2-(4-propylphenyl)-1H-inden-1-yl)-4H-
chromen-4-one (12a). The title compound (12a) was
prepared according to the general procedure. The product
1045, 933, 832, 748, 618 cm-1; HRMS m/z (M+) calcd for
C24H14ClFO2: 388.0666. Found: 388.0663.
o
was obtained as a white solid, mp 125-126 C. Yield: 62%
3-(3-Chloro-2-(4-ethoxyphenyl)-6-methyl-1H-inden-1-
yl)-4H-chromen-4-one (14a). The title compound (14a)
was prepared according to the general procedure. The
1
(122 mg). H NMR (600 MHz, CDCl3)  8.35 (1H, d, J =
7.8 Hz), 7.62 (1H, dt, J = 8.4, 1.8 Hz), 7.56 (2H, d, J = 7.8
Hz), 7.43 (1H, t, J = 7.8 Hz), 7.37 (1H, s), 7.34-7.29 (5H,
m), 7.17 (1H, t, J = 7.2 Hz), 7.13 (1H, d, J = 7.8 Hz), 5.57
(1H, brs), 2.54 (2H, t, J = 8.4 Hz), 1.61-1.53 (2H, m), 0.88
(3H, t, J = 7.2 Hz); 13C NMR (150 MHz, CDCl3)  177.8,
157.3 (d, J = 278.1 Hz), 156.3, 153.0, 144.9, 142.5, 133.6,
133.0 (d, J = 24.5 Hz), 131.6, 128.7, 127.6, 127.6 (d, J =
5.7 Hz), 126.9, 126.0, 125.2, 124.2, 123.9, 122.8, 118.9,
118.1, 117.7 (d, J = 1.9 Hz), 40.5, 38.2, 24.8, 13.8; IR
(ATR) 3048, 1719, 1621, 1470, 1368, 1141, 1035, 955,
814, 748, 608 cm-1; HRMS m/z (M+) calcd for C27H21FO2:
396.1526. Found: 396.1528.
o
product was obtained as a white solid, mp 179-180 C.
1
Yield: 79% (169 mg). H NMR (600 MHz, CDCl3)  8.30
(1H, d, J = 7.8 Hz), 7.61 (2H, d, J = 7.2 Hz), 7.58 (1H, t, J
= 8.4 Hz), 7.40-7.37 (2H, m), 7.31 (1H, s), 7.28 (1H, d, J =
8.4 Hz), 7.14 (2H, d, J = 8.4 Hz), 7.06 (1H, s), 6.89 (1H,
dd, J = 8.4, 1.8 Hz), 5.71 (1H, brs), 4.01-3.94 (2H, m),
2.29 (3H, s), 1.34 (3H, t, J = 7.2 Hz); 13C NMR (150 MHz,
CDCl3)  177.4, 158.8, 156.2, 153.3, 146.7, 137.7, 137.5,
134.3, 133.5, 130.1, 129.2, 128.2, 127.9, 125.9, 125.1,
123.8, 123.0, 120.1, 118.0, 113.8, 110.3, 63.8, 45.0, 21.2,
14.7; IR (ATR) 3021, 1629, 1568, 1462, 1321, 1340, 1275,
1213, 1061, 1033, 924, 812, 757, 587 cm-1; HRMS m/z
(M+) calcd for C27H21ClO3: 428.1179. Found: 428.1181.
3-(3-Chloro-2-(4-propylphenyl)-1H-inden-1-yl)-4H-
chromen-4-one (12b). The title compound (12b) was
prepared according to the general procedure. The product
3-(3-Bromo-2-(4-ethoxyphenyl)-6-methyl-1H-inden-1-
yl)-4H-chromen-4-one (14b). The title compound (14b)
was prepared according to the general procedure. The
o
was obtained as a white solid, mp 145-146 C. Yield: 87%
1
(179 mg). H NMR (600 MHz, CDCl3)  8.19 (1H, d, J =
o
7.8 Hz), 7.62 (2H, d, J = 7.8 Hz), 7.42 (1H, dt, J = 8.4, 1.8
Hz), 7.31 (1H, d, J = 7.8 Hz), 7.26-7.19 (4H, m), 7.16 (1H,
s), 7.11-7.06 (3H, m), 5.65 (1H, brs), 2.43 (2H, t, J = 7.8
Hz), 1.51-1.42 (2H, m), 0.77 (3H, t, J = 7.2 Hz); 13C NMR
(150 MHz, CDCl3)  177.3, 156.1, 153.2, 145.1, 142.1,
139.1, 138.9, 133.4, 132.8, 128.9, 128.4, 128.4, 127.7,
127.7, 125.8, 125.0, 123.7, 123.6, 122.7, 119.2, 118.0, 44.9,
38.0, 24.7, 13.7; IR (ATR) 3158, 1626, 1462, 1354, 1353,
1276, 1150, 936, 755, 601 cm-1; HRMS m/z (M+) calcd for
C27H21ClO2: 412.1230. Found: 412.1230.
product was obtained as a white solid, mp 164-165 C.
1
Yield: 73% (172 mg). H NMR (600 MHz, CDCl3)  8.28
(1H, d, J = 7.8 Hz), 7.62-7.57 (3H, m), 7.40-7.34 (2H, m),
7.31 (1H, s), 7.28 (1H, d, J = 8.4 Hz), 7.14 (2H, d, J = 8.4
Hz), 7.03 (1H, s), 6.88 (1H, dd, J = 9.2, 2.4 Hz), 5.67 (1H,
brs), 4.01-3.94 (2H, m), 2.28 (3H, s), 1.34 (3H, t, J = 7.2
Hz); 13C NMR (150 MHz, CDCl3)  177.3, 158.8, 156.2,
153.3, 146.8, 141.2, 137.6, 137.6, 133.5, 130.7, 129.2,
128.3, 125.9, 125.1, 123.8, 122.8, 121.4, 118.0, 117.6,
113.8, 110.1, 63.8, 46.4, 21.3, 14.7; IR (ATR) 3021, 1629,
1568, 1462, 1321, 1340, 1275, 1213, 1061, 1033, 924, 812,
757, 587 cm-1; HRMS m/z (M+) calcd for C27H21BrO3:
472.0674. Found: 472.0675.
3-(3-Bromo-2-(4-propylphenyl)-1H-inden-1-yl)-4H-
chromen-4-one (12c). The title compound (12c) was
prepared according to the general procedure. The product
was obtained as a white solid and recrystallized with
hexane/ethylacetate, mp 149-150 oC. Yield: 86% (196 mg).
1H NMR (600 MHz, CDCl3)  8.29 (1H, d, J = 8.4 Hz),
7.72 (2H, d, J = 7.8 Hz), 7.59 (1H, dt, J = 7.2, 1.8 Hz),
7.41-7.38 (2H, m), 7.35-7.31 (3H, m), 7.29 (1H, d, J = 8.4
Hz), 7.25-7.22 (2H, m), 7.18 (1H, d, J = 7.8 Hz), 5.72 (1H,
brs), 2.55 (2H, t, J = 7.2 Hz), 1.62-1.55 (2H, m), 0.88 (3H,
t, J = 7.2 Hz); 13C NMR (150 MHz, CDCl3)  177.4, 156.2,
153.3, 145.4, 142.7, 142.2, 140.4, 133.6, 133.5, 128.6,
128.4, 127.9, 127.8, 125.9, 125.1, 123.8, 123.6, 122.6,
120.6, 118.8, 118.1, 46.3, 38.1, 24.8, 13.8; IR (ATR) 3014,
1626, 1561, 1468, 1382, 1359, 1275, 1213, 1070, 1004,
925, 814, 756, 569 cm-1; HRMS m/z (M+) calcd for
C27H21BrO2: 456.0725. Found: 456.0726.
3-(3-Chloro-2-methyl-1H-inden-1-yl)-4H-chromen-4-
one (15a). The title compound (15a) was prepared
according to the general procedure. The product was
obtained as a white solid, mp 146-147 oC. Yield: 73% (112
1
mg). H NMR (600 MHz, CDCl3)  8.29 (1H, d, J = 8.4
Hz), 7.65 (1H, dt, J = 7.2, 1.8 Hz), 7.43-7.37 (3H, m),
7.33-7.30 (3H, m), 7.16 (1H, t, J = 7.2 Hz), 5.01 (1H, brs),
2.02 (3H, s); 13C NMR (150 MHz, CDCl3)  177.3, 156.3,
152.8, 144.3, 141.8, 140.2, 133.6, 128.3, 127.3, 125.9,
125.8, 125.2, 123.7, 123.2, 122.3, 118.6, 118.1, 46.9, 12.4;
IR (ATR) 1728, 1627, 1461, 1392, 1344, 1216, 1140, 1036,
944, 848, 755 cm-1; HRMS m/z (M+) calcd for
C19H13ClO2: 308.0604. Found: 308.0601.
3-(3-Iodo-2-methyl-1H-inden-1-yl)-4H-chromen-4-one
(15b). The title compound (15b) was prepared according to
the general procedure. The product was obtained as a white
solid, mp 146-147 oC. Yield: 57% (113 mg). 1H NMR (600
MHz, CDCl3)  8.19 (1H, d, J = 7.8 Hz), 7.55-7.52 (1H,
m), 7.31 (1H, t, J = 7.8 Hz), 7.28 (1H, d, J = 8.4 Hz), 7.23-
7.19 (2H, m), 7.15 (2H, t, J = 7.8 Hz), 7.03 (1H, t, J = 7.2
Hz), 4.96 (1H, brs), 1.97 (3H, s); 13C NMR (150 MHz,
CDCl3)  177.0, 156.2, 152.8, 150.6, 145.1, 144.9, 133.6,
127.4, 125.9, 125.9, 125.2, 123.7, 122.9, 122.2, 121.8,
118.0, 94.9, 48.7, 17.3; IR (ATR) 1729, 1628, 1467, 1395,
1314, 1236, 1142, 1037, 945, 847, 757 cm-1; HRMS m/z
(M+) calcd for C19H13IO2: 399.9960. Found: 399.9961.
X-Ray crystallographic data of compound 12c:
Empirical Formula- C27H21BrO2, M = 457.35, Triclinic,
Space group P-1, a = 9.5557(9) Å, b = 10.1329(8) Å, c =
11.2305(10) Å, V = 1056.67(16) Å3, Z = 2, T = 223(2) K,
ρcalcd = 1.437 Mg/m3, 2Өmax. = 28.382o, Refinement of 272
parameters on 5292 independent reflections out of 34874
collected reflections (Rint = 0.0317) led to R1 = 0.0364 [I
>2σ(I)], wR2 = 0.0960 (all data) and S = 1.039 with the
largest difference peak and hole of 1.133 and -0.583 e.Å-3
respectively. The crystal structure has been deposited at the
Cambridge Crystallographic Data Centre (CCDC 1909140).
The data can be obtained free of charge via the Internet at
www.ccdc.cam.ac.uk/data_request/cif.
3-(2-Butyl-3-Chloro-1H-inden-1-yl)-4H-chromen-4-one
(16a). The title compound (16a) was prepared according to
the general procedure. The product was obtained as a
3-(2-(4-Chlorophenyl)-3-fluoro-1H-inden-1-yl)-4H-
chromen-4-one (13). The title compound (13) was
prepared according to the general procedure. The product
1
colorless liquid. Yield: 85% (167 mg). H NMR (600 MHz,
o
was obtained as a white solid, mp 142-143 C. Yield: 48%
CDCl3)  8.31 (1H, d, J = 7.2 Hz), 7.62 (1H, dt, J = 9.0,
1.8 Hz), 7.42-7.34 (4H, m), 7.32-7.29 (2H, m), 7.15 (1H, t,
J = 7.2 Hz), 5.17 (1H, brs), 2.74-2.69 (1H, m), 2.20-2.13
(1H, m), 1.60-1.53 (1H, m), 1.51-1.45 (1H, m), 1.39-1.26
(2H, m), 0.88 (3H, t, J = 7.2 Hz); 13C NMR (150 MHz,
CDCl3)  177.0, 156.1, 152.7, 144.7, 144.3, 141.5, 133.5,
128.3, 128.0, 127.1, 125.8, 125.1, 123.6, 123.1, 122.1,
118.6, 117.9, 44.7, 30.7, 26.2, 22.3, 13.6; IR (ATR) 2929,
2862, 1725, 1641, 1462, 1335, 1275, 1217, 1143, 1110,
(93 mg). 1H NMR (600 MHz, CDCl3)  8.33 (1H, d, J =7.8
Hz), 7.63 (1H, dt, J = 7.2, 1.2 Hz), 7.51 (2H, d, J = 8.4 Hz),
7.47 (1H, d, J =7.2 Hz), 7.44-7.42 (2H, m), 7.34-7.31 (3H,
m), 7.28 (2H, d, J = 9.0 Hz) 7.21 (1H, t, J =7.2 Hz), 5.56
(1H, brs); 13C NMR (150 MHz, CDCl3)  177.6, 157.3 (d,
J = 278.2 Hz), 156.2, 153.0, 144.4, 135.1 (d, J = 24.1 Hz),
133.8, 132.9, 129.8, 129.0, 128.9, 128.8, 127.5, 127.5,
125.9, 125.3, 124.0, 123.7, 122.3, 118.9, 118.1 (d, J = 2.1
Hz), 40.6; IR (ATR) 3054, 1717, 1627, 1450, 1358, 1245,
8
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10.1002/adsc.201901266
Advanced Synthesis & Catalysis
988, 861, 758, 603 cm-1; HRMS m/z (M+) calcd for
126.6, 125.3, 124.0, 119.8, 117.9 (d, J = 1.3 Hz), 117.5,
117.1, 40.7; IR (ATR) 2877, 1590, 1516, 1440, 1415, 1353,
1321, 1256, 1131, 1033, 926, 812, 759, 587 cm-1; HRMS
m/z (M+) calcd for C28H17FO2: 404.1213. Found: 404.1213.
C22H19ClO2: 350.1074 Found: 350.1073.
3-(3-Bromo-2-butyl-1H-inden-1-yl)-4H-chromen-4-one
(16b). The title compound (16b) was prepared according to
the general procedure. The product was obtained as a
2-(3-Chloro-2-phenyl-1H-inden-1-yl)-1H-
1
colorless liquid. Yield: 86% (169 mg). H NMR (600 MHz, benzo[f]chromen-1-one (19b). The title compound (19b)
CDCl3)  8.31 (1H, d, J = 6.6 Hz), 7.64 (1H, dt, J = 7.2,
1.2 Hz), 7.42 (1H, t, J = 7.8 Hz), 7.39-7.36 (2H, m), 7.33-
7.30 (3H, m), 7.14 (1H, t, J = 7.8 Hz), 5.16 (1H, brs), 2.71-
2.66 (1H, m), 2.20-2.16 (1H, m), 1.60-1.52 (1H, m), 1.51-
1.45 (1H, m), 1.38-1.28 (2H, m), 0.88 (3H, t, J = 7.8 Hz);
13C NMR (150 MHz, CDCl3)  177.0, 156.2, 152.8, 147.9,
145.0, 142.6, 133.6, 128.0, 127.2, 125.9, 125.2, 123.7,
123.1, 122.1, 119.8, 118.6, 118.0, 45.7, 30.7, 27.8, 22.4,
13.7; IR (ATR) 2928, 2862, 1723, 1643, 1461, 1337, 1276,
1218, 1142, 1111, 987, 863, 756, 605 cm-1; HRMS m/z
(M+) calcd for C22H19BrO2: 394.0568. Found: 394.0569.
was prepared according to the general procedure. The
o
product was obtained as a white solid, mp 185-186 C.
1
Yield: 94% (197 mg). H NMR (600 MHz, CDCl3)  10.2
(1H, d, J = 8.4 Hz), 7.97 (1H, d, J = 9.0 Hz), 7.86 (1H, d, J
= 8.4 Hz), 7.82-7.78 (3H, m), 7.62 (1H, d, J = 7.2 Hz),
7.57-7.54 (2H, m), 7.39-7.34 (4H, m), 7.30 (1H, d, J = 9.6
Hz), 7.25-7.20 (2H, m), 5.96 (1H, brs); 13C NMR (150
MHz, CDCl3)  178.8, 157.4, 150.6, 145.1, 141.4, 139.9,
135.4, 132.8, 130.6, 130.5, 129.3, 128.9, 128.6, 128.6,
128.2, 127.9, 127.5, 127.1, 127.0, 126.7, 125.3, 123.5,
119.6, 117.5, 117.1, 45.3; IR (ATR) 2874, 1595, 1512,
1440, 1405, 1356, 1304, 1250, 1140, 1004, 928, 815, 755,
584 cm-1; HRMS m/z (M+) calcd for C28H17ClO2:
420.0917. Found: 420.0916.
3-(2-Butyl-3-iodo-1H-inden-1-yl)-4H-chromen-4-one
(16c). The title compound (16c) was prepared according to
the general procedure. The product was obtained as a
1
colorless liquid. Yield: 67% (167 mg). H NMR (600 MHz, 2-(3-Iodo-2-phenyl-1H-inden-1-yl)-1H-
CDCl3)  8.22 (1H, s), 7.57 (1H, dt, J = 7.2, 1.8 Hz), 7.35
(1H, t, J = 7.8 Hz), 7.31 (1H, d, J = 9.0 Hz), 7.26-7.23 (1H,
m), 7.21-7.16 (3H, m), 7.05 (1H, dt, J = 7.2, 1.2 Hz), 5.13
(1H, brs), 2.57-2.52 (1H, m), 2.19-2.15 (1H, m), 1.52-1.45
(1H, m), 1.42-1.36 (1H, m), 1.30-1.21 (2H, m), 0.80 (3H, t,
J = 7.2 Hz); 13C NMR (150 MHz, CDCl3)  177.0, 156.2,
154.7, 152.9, 145.5, 144.9, 133.6, 127.4, 126.1, 126.0,
125.2, 123.8, 123.0, 122.3, 122.0, 118.1, 95.1, 46.6, 31.0,
30.9, 22.5, 13.8; IR (ATR) 2928, 2852, 1727, 1642, 1432,
1345, 1276, 1218, 1142, 1112, 987, 862, 757, 605 cm-1;
HRMS m/z (M+) calcd for C22H19IO2: 442.0430 Found:
442.0432.
benzo[f]chromen-1-one (19c). The title compound (19c)
was prepared according to the general procedure. The
o
product was obtained as a white solid, mp 185-187 C.
Yield: 42% (107 mg). 1H NMR (600 MHz, CDCl3)  10.14
(1H, d, J = 7.8 Hz), 7.97 (1H, d, J = 9.0 Hz), 7.85 (1H, d, J
= 7.8 Hz), 7.78 (1H, t, J = 7.8 Hz), 7.72 (2H, d, J = 7.8 Hz),
7.61 (1H, t, J = 7.8 Hz), 7.48-7.46 (2H, m), 7.40-7.34 (4H,
m), 7.29 (1H, d, J = 9.0 Hz), 7.26 (1H, t, J = 7.2 Hz), 7.19
(1H, t, J = 7.8 Hz), 5.92 (1H, brs); 13C NMR (150 MHz,
CDCl3)  178.6, 157.4, 150.8, 150.76, 145.6, 145.0, 135.4,
135.0, 130.6, 130.5, 129.3, 128.8, 128.5, 128.4, 128.4,
128.2, 127.6, 127.1, 126.9, 126.6, 125.0, 123.3, 117.5,
117.1, 94.9, 48.1; IR (ATR) 2873, 1595, 1512, 1442, 1406,
1358, 1301, 1251, 1143, 1005, 927, 818, 755, 584 cm-1;
HRMS m/z (M+) calcd for C28H17IO2: 512.0273. Found:
512.0276.
3-(3-Chloro-2-(thiophen-3-yl)-1H-inden-1-yl)-4H-
chromen-4-one (17). The title compound (17) was
prepared according to the general procedure. The product
o
was obtained as a white solid, mp 157-158 C. Yield: 72%
(135 mg). 1H NMR (600 MHz, CDCl3)  8.30 (1H, dd, J =
7.8, 1.8 Hz), 7.66 (2H, dd, J = 7.2, 1.2 Hz), 7.59 (1H, dt, J
= 7.2, 1.2 Hz), 7.40-7.34 (4H, m), 7.29-7.23 (3H, m), 7.03
(1H, d, J = 4.8 Hz), 5.52 (1H, s); 13C NMR (150 MHz,
CDCl3)  177.3, 156.2, 152.7, 146.9, 144.6, 140.1, 133.7,
133.3, 128.8, 128.7, 127.8, 127.5, 126.2, 125.8, 125.2,
123.5, 122.2, 118.0, 117.7, 44.5; IR (ATR) 1624, 1460,
1385, 1353, 1205, 1134, 899, 761, 682 cm-1; HRMS m/z
(M+) calcd for C22H13ClO2S: 376.0325. Found: 376.0326.
3-(3-Fluoro-2-phenyl-1H-inden-1-yl)-5-(p-tolyl)-4H-
pyran-4-one (20a). The title compound (20a) was
prepared according to the general procedure. The product
o
was obtained as a white solid, mp 177-178 C. Yield: 40%
1
(78 mg). H NMR (600 MHz, CDCl3)  7.76 (1H, s), 7.58
(2H, d, J = 7.8 Hz), 7.55 (1H, d, J = 7.8 Hz), 7.48 (2H, d, J
= 7.2 Hz), 7.43 (1H, d, J = 7.8 Hz), 7.38-7.32 (3H, m),
7.27-7.20 (5H, m), 5.59 (1H, brs), 2.39 (3H, s); 13C NMR
(150 MHz, CDCl3)  177.0, 157.1 (d, J = 278.1 Hz), 152.4,
152.1, 144.2, 138.5, 135.4, 135.2, 131.3 (d, J = 4.3 Hz),
129.2, 129.1, 128.8, 128.6, 128.1, 128.0, 127.7 (d, J = 6.1
Hz), 127.5, 127.2 (d, J = 4.3 Hz), 124.2 (d, J = 1.6 Hz),
119.6, 117.9 (d, J = 1.9 Hz), 40.7, 21.2; IR (ATR) 1642,
1611, 1509, 1453, 1328, 1256, 1156, 1086, 1023, 968, 897,
754, 689, 508 cm-1; HRMS m/z (M+) calcd for C27H19FO2:
394.1369. Found: 394.1371.
3-(3-Chloro-2-(naphthalen-1-yl)-1H-inden-1-yl)-4H-
chromen-4-one (18). The title compound (18) was
prepared according to the general procedure. The product
o
was obtained as a white solid, mp 190-192 C. Yield: 92%
1
(193 mg). H NMR (600 MHz, CDCl3)  9.31 (1H, d, J =
9.0 Hz), 8.29 (1H, d, J = 8.4 Hz), 7.83 (1H, d, J = 8.4 Hz),
7.73 (2H, d, J = 7.2 Hz), 7.68 (1H, d, J = 8.4 Hz), 7.56-
7.52 (3H, m), 7.46 (1H, dt, J = 7.2, 1.2 Hz), 7.37-7.34 (3H,
3-(3-Chloro-2-phenyl-1H-inden-1-yl)-5-(p-tolyl)-4H-
m), 7.27-7.21 (3H, m), 5.81 (1H, brs); 13C NMR (150 MHz, pyran-4-one (20b). The title compound (20b) was
CDCl3)  177.2, 156.1, 153.3, 144.6, 142.3, 134.2, 133.7,
133.5, 133.0, 129.4, 128.9, 128.8, 128.4, 128.1, 127.9,
127.8, 126.1, 125.8, 125.4, 125.1, 123.7, 123.2, 121.8,
121.4, 118.0, 45.3; IR (ATR) 3058, 1625, 1452, 1394,
1352, 1276, 1140, 1046, 995, 757, 686 cm-1; HRMS m/z
(M+) calcd for C28H17ClO2: 420.0917. Found: 420.0920.
prepared according to the general procedure. The product
o
was obtained as a white solid, mp 137-138 C. Yield: 87%
1
(178 mg). H NMR (600 MHz, CDCl3)  7.76 (2H, d, J =
8.4 Hz), 7.72 (1H, s), 7.54 (2H, t, J = 8.4 Hz), 7.45 (2H, d,
J = 7.8 Hz), 7.42-7.38 (3H, m), 7.30 (1H, dt, J = 6.6, 1.2
Hz), 7.26 (3H, d, J = 7.8 Hz), 7.21 (1H, s), 5.78 (1H, brs),
2.39 (3H, s); 13C NMR (150 MHz, CDCl3)  176.7, 152.3,
152.2, 144.6, 141.3, 139.6, 138.4, 132.7, 129.2, 129.0,
129.0, 128.6, 128.5, 128.0, 128.0, 128.0, 127.6, 127.0,
123.6, 119.6, 45.1, 21.2; IR (ATR) 1642, 1612, 1511, 1455,
1328, 1257, 1155, 1086, 1024, 966, 896, 754, 688, 535,
508 cm-1; HRMS m/z (M+) calcd for C27H19ClO2:
410.1074. Found: 410.1073.
2-(3-Chloro-2-phenyl-1H-inden-1-yl)-1H-
benzo[f]chromen-1-one (19a). The title compound (19a)
was prepared according to the general procedure. The
o
product was obtained as a white solid, mp 185-186 C.
1
Yield: 63% (127 mg). H NMR (600 MHz, CDCl3)  10.2
(1H, d, J = 7.8 Hz), 7.96 (1H, d, J = 8.4 Hz), 7.87 (1H, d, J
= 8.4 Hz), 7.84 (1H, t, J = 7.8 Hz), 7.65-7.61 (4H, m), 7.47
(1H, d, J = 7.2 Hz), 7.38 (1H, s), 7.35-7.29 (4H, m), 7.22-
7.19 (2H, m), 5.79 (1H, brs); 13C NMR (150 MHz, CDCl3)
 179.1, 157.5, 157.2 (d, J = 277.9 Hz), 150.3, 144.6,
135.4, 135.2, 131.4 (d, J = 4.2 Hz), 130.6, 130.5, 129.3,
128.7, 128.2, 127.7 (d, J = 6.3 Hz), 127.3, 127.2, 127.1,
3-(3-Bromo-2-phenyl-1H-inden-1-yl)-5-(p-tolyl)-4H-
pyran-4-one (20c). The title compound (20c) was
prepared according to the general procedure. The product
1
was obtained as viscous oils. Yield: 88% (199 mg). H
NMR (600 MHz, CDCl3)  7.76 (2H, d, J = 7.8 Hz), 7.72
9
This article is protected by copyright. All rights reserved.

10.1002/adsc.201901266
Advanced Synthesis & Catalysis
(1H, d, J = 1.2 Hz), 7.53 (2H, d, J = 7.8 Hz), 7.44 (2H, d, J
= 6.6 Hz), 7.42-7.40 (2H, m), 7.36-7.31 (1H, m), 7.26-7.25
(3H, m), 7.22 (1H, d, J = 7.2 Hz), 7.08-7.04 (1H, m), 5.75
(1H, brs), 2.39 (3H, s); 13C NMR (150 MHz, CDCl3) 
176.6, 157.4, 152.3, 152.2, 143.4, 142.6, 138.5, 133.4,
129.5, 129.2, 129.0, 128.7, 128.6, 128.5, 128.1, 127.6,
127.4, 127.0, 123.5, 120.9, 118.9, 49.4, 21.2; IR (ATR)
1643, 1614, 1514, 1456, 1328, 1257, 1157, 1087, 1025,
967, 898, 764, 698, 578, 537 cm-1; HRMS m/z (M+) calcd
for C27H19BrO2: 454.0568. Found: 454.0566.
3-(3-Chloro-2-phenyl-1H-inden-1-yl)-4H-thiochromen-
4-one (23a). The title compound (23a) was prepared
according to the general procedure. The product was
obtained as a white solid, mp 174-176 oC. Yield: 86% (165
mg). 1H NMR (600 MHz, CDCl3)  8.66 (1H, s), 7.73 (2H,
d, J = 7.8 Hz), 7.55-7.54 (2H, m), 7.50 (1H, d, J = 7.8 Hz),
7.47-7.45 (1H, m), 7.38-7.34 (2H, m), 7.32 (2H, t, J = 7.8
Hz), 7.24-7.22 (1H, m), 7.19-7.17 (2H, m), 6.13 (1H, brs);
13C NMR (150 MHz, CDCl3)  178.9, 145.6, 144.5, 142.8,
137.1, 134.5, 133.8, 133.6, 131.6, 131.2, 129.1, 128.7,
128.4, 128.0, 127.7, 127.5, 126.9, 126.5, 123.3, 120.9,
118.8, 50.8; IR (ATR) 3067, 1759, 1637, 1607, 1585, 1582,
1452, 1405, 1343, 1231, 1092, 987, 931, 759, 685, 592,
521 cm-1; HRMS m/z (M+) calcd for C24H15ClOS:
386.0532. Found: 386.0532.
3-(3-Chloro-2-phenyl-1H-inden-1-yl)-5-(4-
methoxyphenyl)-4H-pyran-4-one
(21).
The
title
compound (21) was prepared according to the general
procedure. The product was obtained as a white solid, mp
o
1
160-162 C. Yield: 91% (193 mg). H NMR (600 MHz,
CDCl3)  7.67 (2H, d, J = 7.8 Hz), 7.62 (1H, s), 7.46-7.41
(4H, m), 7.33-7.29 (3H, m), 7.21 (1H, t, J = 7.8 Hz), 7.16
(1H, t, J = 8.4 Hz), 7.11 (1H, s), 6.89 (2H, d, J = 8.4 Hz),
5.69 (1H, brs), 3.75 (3H, s); 13C NMR (150 MHz, CDCl3)
 176.8, 159.8, 152.2, 152.0, 144.6, 141.3, 139.6, 132.7,
129.9, 129.0, 128.7, 128.6, 128.5, 128.0, 127.8, 127.6,
127.0, 123.6, 123.2, 119.6, 113.9, 55.3, 45.2; IR (ATR)
3070, 1640, 1608, 1510, 1456, 1335, 1290, 1246, 1180,
1033, 967, 899, 830, 756, 688, 574 cm-1; HRMS m/z (M+)
calcd for C27H19ClO3: 426.1023. Found: 426.1025.
3-(3-Bromo-2-phenyl-1H-inden-1-yl)-4H-thiochromen-
4-one (23b). The title compound (23b) was prepared
according to the general procedure. The product was
obtained as a white solid, mp 165-166 oC. Yield: 84% (180
mg). 1H NMR (600 MHz, CDCl3)  8.61 (1H, s), 7.67 (2H,
d, J = 7.8 Hz), 7.50-7.48 (2H, m), 7.45 (1H, d, J = 7.8 Hz),
7.41-7.40 (1H, m), 7.33 (1H, d, J = 7.2 Hz), 7.30-7.25 (3H,
m), 7.17-7.11 (3H, m), 6.08 (1H, brs); 13C NMR (150 MHz,
CDCl3)  179.0, 145.4, 141.5, 140.7, 137.2, 134.5, 134.0,
132.9, 131.6, 131.2, 129.1, 129.0, 128.5, 128.5, 127.9,
127.7, 127.4, 126.9, 126.5, 123.4, 119.6, 49.5; IR (ATR)
3167, 1752, 1637, 1601, 1585, 1581, 1453, 1405, 1343,
1231, 1092, 987, 931, 756, 681, 593, 522 cm-1; HRMS m/z
(M+) calcd for C24H15BrOS: 430.0027. Found: 430.0024.
3-(3-Fluoro-2-phenyl-1H-inden-1-yl)-5-(4-
fluorophenyl)-4H-pyran-4-one (22a). The title compound
(22a) was prepared according to the general procedure.
The product was obtained as a white solid, mp 150-152 oC.
1
Yield: 35% (69 mg). H NMR (600 MHz, CDCl3)  7.76
6-Chloro-3-(3-chloro-2-phenyl-1H-inden-1-yl)-4H-
thiochromen-4-one (24a). The title compound (24a) was
prepared according to the general procedure. The product
(1H, s), 7.58-7.57 (3H, m), 7.53 (1H, d, J = 7.2 Hz), 7.43
(1H, d, J = 7.2 Hz), 7.38-7.32 (3H, m), 7.28 (1H, s), 7.25-
7.20 (3H, m), 7.14 (2H, t, J = 9.0 Hz), 5.57 (1H, brs); 13C
NMR (150 MHz, CDCl3)  176.9, 163.0 (d, J = 247.2 Hz),
157.2 (d, J = 278.2 Hz), 152.6, 152.3, 144.0, 135.3, 131.3
(d, J = 4.6 Hz), 130.6, 130.5, 128.8, 128.3, 128.2, 127.7 (d,
J = 6.3 Hz), 127.6, 127.3 (d, J = 5.7 Hz), 127.0 (d, J = 3.4
Hz), 124.1, 119.6, 118.0 (d, J = 2.1 Hz), 115.6 (d, J = 21.5
Hz), 40.7; IR (ATR) 1643, 1615, 1510, 1453, 1318, 1256,
1167, 1077, 1026, 968, 899, 766, 699, 588, 547 cm-1;
HRMS m/z (M+) calcd for C26H16F2O2: 398.1118. Found:
398.1118.
o
was obtained as a white solid, mp 194-195 C. Yield: 84%
(176 mg). 1H NMR (600 MHz, CDCl3)  8.53 (1H, s), 7.60
(2H, d, J = 7.8 Hz), 7.40 (1H, d, J = 7.2 Hz), 7.36 (1H, dd,
J = 8.4, 2.4 Hz), 7.26-7.19 (5H, m), 7.11-7.04 (3H, m),
5.98 (1H, brs); 13C NMR (150 MHz, CDCl3)  177.9,
145.0, 141.5, 140.5, 135.2, 134.5, 134.3, 134.1, 132.7,
132.6, 131.6, 129.2, 128.7, 128.5, 128.5, 128.4, 127.9,
127.5, 126.9, 123.3, 119.6, 49.4; IR (ATR) 3061, 1752,
1617, 1617, 1586, 1584, 1452, 1405, 1343, 1231, 1093,
986, 931, 759, 684, 592, 520 cm-1; HRMS m/z (M+) calcd
for C24H14Cl2OS: 420.0142. Found: 420.0144.
3-(3-Chloro-2-phenyl-1H-inden-1-yl)-5-(4-
fluorophenyl)-4H-pyran-4-one (22b). The title compound
(22b) was prepared according to the general procedure.
The product was obtained as a white solid, mp 184-185 oC.
3-(3-Bromo-2-phenyl-1H-inden-1-yl)-6-chloro-4H-
thiochromen-4-one (24b). The title compound (24b) was
prepared according to the general procedure. The product
1
o
Yield: 86% (178 mg). H NMR (600 MHz, CDCl3)  7.64
was obtained as a white solid, mp 180-181 C. Yield: 87%
(2H, d, J = 7.8 Hz), 7.60 (1H, s), 7.44-7.42 (4H, m), 7.31-
7.27 (3H, m), 7.20 (1H, t, J = 7.2 Hz), 7.14 (1H, t, J = 7.2
Hz), 7.12 (1H, s), 7.02 (2H, t, J = 7.8 Hz), 5.65 (1H, brs);
13C NMR (150 MHz, CDCl3)  176.5, 162.9 (d, J = 247.2
Hz), 152.5 (d, J = 4.5 Hz), 144.4, 141.3, 139.5, 132.6,
130.5 (d, J = 7.9 Hz), 129.1, 128.6, 128.5, 128.2, 128.1,
128.0, 127.6, 127.0, 126.9 (d, J = 3.4 Hz), 123.5, 119.6,
115.5, 115.4, 45.1; IR (ATR) 1645, 1610, 1512, 1454,
1318, 1257, 1156, 1089, 1026, 977, 899, 766, 699, 598,
547 cm-1; HRMS m/z (M+) calcd for C26H16ClFO2:
414.0823. Found: 414.0826.
(201 mg). 1H NMR (600 MHz, CDCl3)  8.63 (1H, s), 7.71
(2H, d, J = 7.2 Hz), 7.50 (2H, d, J = 8.4 Hz), 7.40 (1H, dd,
J = 6.6, 1.8 Hz), 7.37-7.31 (4H, m), 7.25-7.17 (3H, m),
6.08 (1H, brs); 13C NMR (150 MHz, CDCl3)  177.9,
144.3, 142.8, 135.2, 134.5, 134.3, 134.0, 133.5, 132.7,
131.6, 128.7, 128.6, 128.5, 128.1, 128.0, 127.6, 127.0,
123.3, 122.2, 121.0, 119.0, 50.7; IR (ATR) 3077, 1753,
1632, 1606, 1584, 1581, 1453, 1402, 1313, 1230, 1091,
977, 932, 759, 684, 592, 521 cm-1; HRMS m/z (M+) calcd
for C24H14BrClOS: 463.9637. Found: 463.9641.
3-(2-Butyl-3-chloro-1H-inden-1-yl)-4H-thiochromen-4-
one (25a). The title compound (25a) was prepared
according to the general procedure. The product was
3-(3-Bromo-2-phenyl-1H-inden-1-yl)-5-(4-
fluorophenyl)-4H-pyran-4-one (22c). The title compound
(22c) was prepared according to the general procedure.
The product was obtained as a white solid, mp 178-179 oC.
1
obtained as viscous oils. Yield: 81% (148 mg). H NMR
(600 MHz, CDCl3)  8.69 (1H, s), 7.61-7.54 (3H, m), 7.38
(1H, d, J = 7.8 Hz), 7.32-7.27 (2H, m), 7.13 (2H, t, J = 7.8
Hz), 5.53 (1H, brs), 2.71-2.66 (1H, m), 2.13-2.08 (1H, m),
1.56-1.42 (2H, m), 1.37-1.24 (2H, m), 0.86 (3H, t, J = 7.2
Hz); 13C NMR (150 MHz, CDCl3)  178.9, 145.5, 145.3,
141.6, 137.1, 134.0, 133.8, 131.6, 131.2, 129.2, 128.6,
127.8, 127.1, 126.5, 125.9, 123.4, 118.6, 49.0, 30.7, 26.4,
22.4, 13.7; IR (ATR) 2928, 2863, 1725, 1641, 1462, 1345,
1275, 1216, 1143, 1100, 989, 860, 759, 602 cm-1; HRMS
m/z (M+) calcd for C22H19ClOS: 366.0845. Found:
366.0844.
1
Yield: 89% (203 mg). H NMR (600 MHz, CDCl3)  7.66
(2H, d, J = 7.2 Hz), 7.62 (1H, s), 7.45-7.41 (4H, m), 7.33-
7.30 (3H, m), 7.23 (1H, t, J = 7.2 Hz), 7.17-7.14 (2H, m),
7.03 (2H, t, J = 8.4 Hz), 5.63 (1H, brs); 13C NMR (150
MHz, CDCl3)  176.4, 162.9 (d, J = 247.2 Hz), 152.4,
144.6, 143.3, 142.6, 133.4, 130.5 (d, J = 8.1 Hz), 128.7,
128.5, 128.2, 128.1, 127.9, 127.7, 127.0, 126.9 (d, J = 3.3
Hz), 123.4, 120.9, 119.0, 115.5, 115.4, 46.5; IR (ATR)
1644, 1614, 1512, 1457, 1318, 1256, 1137, 1086, 1023,
977, 878, 754, 688, 579 cm-1; HRMS m/z (M+) calcd for
C26H16BrFO2: 458.0318. Found: 458.0316.
10
This article is protected by copyright. All rights reserved.

10.1002/adsc.201901266
Advanced Synthesis & Catalysis
3-(3-Bromo-2-butyl-1H-inden-1-yl)-4H-thiochromen-4-
one (25b). The title compound (25b) was prepared
according to the general procedure. The product was
3-(2-Butyl-3-chloro-1H-inden-1-yl)-2H-chromen-2-one
(28a). The title compound (28a) was prepared according to
the general procedure. The product was obtained as a white
solid, mp 123-124 oC. Yield: 80% (140 mg). 1H NMR (600
MHz, CDCl3)  7.47 (1H, dt, J = 8.4, 1.8 Hz), 7.40 (1H, d,
J = 7.8 Hz), 7.38 (1H, d, J = 7.2 Hz), 7.35-7.32 (2H, m),
7.28 (1H, d, J = 7.8 Hz), 7.21-7.17 (2H, m), 7.06 (1H, s),
5.02 (1H, brs), 2.77-2.72 (1H, m), 2.19-2.15 (1H, m), 1.60-
1.45 (2H, m), 1.40-1.29 (2H, m), 0.89 (3H, t, J = 7.8 Hz);
13C NMR (150 MHz, CDCl3)  162.1, 153.1, 144.2, 144.1,
141.5, 138.5, 131.2, 129.1, 127.6, 127.5, 126.9, 126.1,
124.3, 123.2, 119.1, 118.8, 116.4, 48.7, 30.7, 26.4, 22.4,
13.7; IR (ATR) 2955, 1706, 1604, 1454, 1376, 1247, 1170,
1058, 937, 894, 754, 654, 614, 527 cm-1; HRMS m/z (M+)
calcd for C22H19ClO2: 350.1074. Found: 350.1071.
1
obtained as viscous oils. Yield: 79% (161 mg). H NMR
(600 MHz, CDCl3)  8.68 (1H, d, J = 7.8 Hz), 7.62-7.56
(3H, m), 7.35 (1H, d, J = 7.8 Hz), 7.31 (1H, t, J = 7.2 Hz),
7.25 (1H, d, J = 7.2 Hz), 7.12 (2H, t, J = 7.8 Hz), 5.52 (1H,
brs), 2.68-2.63 (1H, m), 2.14-2.09 (1H, m), 1.55-1.41 (2H,
m), 1.36-1.26 (2H, m), 0.86 (3H, t, J = 7.2 Hz); 13C NMR
(150 MHz, CDCl3)  178.9, 148.9, 145.8, 142.8, 137.1,
134.1, 133.7, 131.7, 131.2, 129.2, 127.8, 127.2, 126.6,
126.0, 123.3, 119.8, 118.9, 49.9, 30.8, 28.0, 22.5, 13.8; IR
(ATR) 2927, 2867, 1729, 1642, 1452, 1355, 1276, 1217,
1142, 1103, 987, 862, 757, 612 cm-1; HRMS m/z (M+)
calcd for C22H19BrOS: 410.0340. Found: 410.0342.
3-(3-Chloro-2-phenyl-1H-inden-1-yl)-2H-chromen-2-
one (26a). The title compound (26a) was prepared
according to the general procedure. The product was
obtained as a white solid, mp 214-215 oC. Yield: 83% (153
3-(3-Bromo-2-butyl-1H-inden-1-yl)-2H-chromen-2-one
(28b). The title compound (28b) was prepared according to
the general procedure. The product was obtained as a white
solid, mp 124-125 oC. Yield: 79% (155 mg). 1H NMR (600
MHz, CDCl3)  7.47 (1H, dt, J = 8.4, 1.8 Hz), 7.38-7.32
(4H, m), 7.28 (1H, d, J = 7.2 Hz), 7.21-7.16 (2H, m), 7.03
(1H, s), 5.01 (1H, brs), 2.74-2.69 (1H, m), 2.19-2.14 (1H,
m), 1.59-1.53 (1H, m), 1.50-1.44 (1H, m), 1.38-1.28 (2H,
m), 0.88 (3H, t, J = 7.8 Hz); 13C NMR (150 MHz, CDCl3)
 162.0, 153.1, 147.7, 144.5, 142.7, 138.5, 131.4, 127.6,
127.6, 126.8, 126.2, 124.4, 123.2, 120.0, 119.4, 119.1,
1
mg). H NMR (600 MHz, CDCl3)  7.77 (2H, d, J = 7.2
Hz), 7.55 (1H, d, J = 7.8 Hz), 7.52 (1H, d, J = 7.2 Hz),
7.41-7.36 (4H, m), 7.27-7.24 (3H, m), 7.14 (1H, d, J = 7.2
Hz), 7.10 (1H, d, J = 7.8 Hz), 7.07 (1H, s), 5.64 (1H, brs);
13C NMR (150 MHz, CDCl3)  162.1, 153.0, 144.1, 141.6,
139.9, 138.8, 132.7, 131.1, 129.4, 128.6, 128.5, 128.1,
127.8, 127.6, 127.1, 127.0, 124.2, 123.3, 119.7, 119.1,
116.3, 49.3; IR (ATR) 3070, 1640, 1608, 1510, 1456, 1335, 116.4, 49.6, 30.8, 28.0, 22.5, 13.7; IR (ATR) 2956, 1706,
1290, 1246, 1180, 1033, 967, 899, 830, 756, 688, 574, 540
cm-1; HRMS m/z (M+) calcd for C24H15ClO2: 370.0761.
Found: 370.0762.
1603, 1453, 1377, 1248, 1171, 1053, 936, 899, 755, 654,
613, 528 cm-1; HRMS m/z (M+) calcd for C22H19BrO2:
394.0568. Found: 394.0565.
3-(3-Bromo-2-phenyl-1H-inden-1-yl)-2H-chromen-2-
one (26b). The title compound (26b) was prepared
according to the general procedure. The product was
obtained as a white solid, mp 198-199 oC. Yield: 86% (178
3-(3-Bromo-2-phenyl-1H-inden-1-yl)-4-chloro-2H-
chromen-2-one (29). The title compound (29) was
prepared according to the general procedure. The product
o
was obtained as a white solid, mp 195-196 C. Yield: 78%
1
1
mg). H NMR (600 MHz, CDCl3)  7.67 (2H, d, J = 7.8
(174 mg). H NMR (600 MHz, CDCl3)  7.93 (1H, d, J =
Hz), 7.43 (1H, d, J = 7.2 Hz), 7.39 (1H, d, J = 7.8 Hz),
7.30-7.25 (4H, m), 7.17-7.11 (3H, m), 7.03 (1H, d, J = 7.8
Hz), 6.98 (2H, t, J = 7.2 Hz), 5.50 (1H, brs); 13C NMR
(150 MHz, CDCl3)  162.0, 152.9, 144.3, 143.6, 142.8,
138.9, 133.3, 131.1, 128.6, 128.5, 128.1, 127.8, 127.5,
8.4 Hz), 7.64 (2H, d, J = 8.4 Hz), 7.55 (1H, d, J = 7.8 Hz),
7.48 (1H, t, J = 7.8 Hz), 7.42 (1H, t, J = 7.5 Hz), 7.35-7.31
(3H, m), 7.27-7.21 (3H, m), 7.15 (1H, d, J = 8.2 Hz), 5.75
(1H, brs); 13C NMR (150 MHz, CDCl3)  161.2, 155.0,
151.4, 144.1, 144.0, 142.1, 140.8, 133.9, 132.3, 128.7,
127.1, 126.8, 124.2, 123.2, 121.0, 119.3, 119.0, 116.3, 50.6; 128.6, 128.3, 128.1, 127.9, 126.4, 124.7, 121.9, 121.1,
IR (ATR) 3072, 1641, 1606, 1513, 1457, 1337, 1293, 1242,
1180, 1033, 964, 890, 832, 756, 689, 574, 542 cm-1;
HRMS m/z (M+) calcd for C24H15BrO2: 414.0255. Found:
414.0257.
119.1, 118.3, 116.5, 55.3; IR (ATR) 3071, 1642, 1601,
1500, 1466, 1334, 1291, 1241, 1187, 1034, 968, 890, 831,
755, 687, 575, 541 cm-1; HRMS m/z (M+) calcd for
C24H14BrClO2: 447.9866. Found: 447.9864.
3-(3-Chloro-6-methyl-2-(p-tolyl)-1H-inden-1-yl)-2H-
chromen-2-one (27a). The title compound (27a) was
prepared according to the general procedure. The product
3-(3-Chloro-2-phenyl-1H-inden-1-yl)quinolin-2(1H)-
one (30). The title compound (30) was prepared according
to the general procedure. The product was obtained as a
o
o
1
was obtained as a white solid, mp 220-221 C. Yield: 82%
white solid, mp 245-247 C. Yield: 84% (154 mg). H
NMR (600 MHz, CDCl3, DMSO)  11.72 (1H, brs), 7.76
(2H, d, J = 7.2 Hz), 7.43-7.41 (2H, m), 7.28-7.20 (5H, m),
7.14-7.10 (3H, m), 6.95-6.89 (2H, m), 5.80 (1H, brs); 13C
NMR (150 MHz, CDCl3, DMSO)  162.3, 144.7, 140.7,
140.4, 137.2, 134.8, 132.3, 130.4, 129.0, 127.8, 127.6,
127.6, 127.0, 126.6, 126.5, 126.1, 122.7, 121.1, 118.8,
118.6, 114.6, 47.8; IR (ATR) 3076, 1643, 1605, 1518,
1447, 1343, 1290, 1249, 1184, 1034, 966, 881, 831, 758,
681, 572, 540 cm-1; HRMS m/z (M+) calcd for
1
(163 mg). H NMR (600 MHz, CDCl3)  7.67 (2H, d, J =
7.8 Hz), 7.42-7.37 (2H, m), 7.35 (1H, s), 7.26 (1H, d, J =
8.4 Hz), 7.20-7.17 (3H, m), 7.14 (1H, d, J = 7.2 Hz), 7.10-
7.07 (2H, m), 5.59 (1H, brs), 2.35 (3H, s), 2.30 (3H, s); 13C
NMR (150 MHz, CDCl3)  162.1, 152.9, 144.3, 139.1,
138.8, 138.6, 137.8, 137.1, 131.0, 129.9, 129.3, 128.6,
128.4, 128.3, 127.6, 127.4, 124.1, 124.1, 119.3, 119.2,
116.2, 48.9, 21.4, 21.1; IR (ATR) 3071, 1640, 1603, 1511,
1453, 1331, 1290, 1246, 1180, 1035, 968, 899, 831, 756,
683, 574, 541 cm-1; HRMS m/z (M+) calcd for C26H19ClO2: C24H16ClNO: 369.0920. Found: 369.0922.
398.1074. Found: 398.1075.
3-(3-Chloro-2-phenyl-1H-inden-1-yl)-1-methylquinolin-
3-(3-Bromo-6-methyl-2-(p-tolyl)-1H-inden-1-yl)-2H-
chromen-2-one (27b). The title compound (27b) was
prepared according to the general procedure. The product
2(1H)-one (31a). The title compound (31a) was prepared
according to the general procedure. The product was
obtained as a white solid, mp 174-175 oC. Yield: 84% (160
o
1
was obtained as a white solid, mp 205-206 C. Yield: 85%
mg). H NMR (600 MHz, CDCl3)  7.82 (2H, d, J = 7.8
1
(187 mg). H NMR (600 MHz, CDCl3)  7.56 (2H, d, J =
Hz), 7.56-7.53 (2H, m), 7.40-7.33 (4H, m), 7.22-7.17 (4H,
m), 7.06-7.01 (2H, m), 6.00 (1H, brs), 3.79 (3H, s); 13C
NMR (150 MHz, CDCl3)  162.5, 145.4, 141.5, 140.9,
138.9, 134.7, 133.1, 130.8, 129.9, 128.6, 128.5, 128.3,
128.3, 127.7, 127.3, 126.7, 123.4, 121.9, 120.2, 119.4,
113.7, 49.3, 30.0; IR (ATR) 3073, 1644, 1602, 1511, 1457,
1333, 1291, 1241, 1181, 1032, 966, 891, 831, 757, 685,
573, 541 cm-1; HRMS m/z (M+) calcd for C25H18ClNO:
383.1077. Found: 383.1076.
7.2 Hz), 7.29-7.25 (2H, m), 7.21 (1H, s), 7.13 (1H, d, J =
8.4 Hz), 7.09-7.03 (4H, m), 6.98 (1H, t, J = 7.2 Hz), 6.95
(1H, s), 5.45 (1H, brs), 2.25 (3H, s), 2.19 (3H, s); 13C
NMR (150 MHz, CDCl3)  162.2, 152.9, 144.5, 142.5,
140.3, 138.7, 137.9, 137.0, 131.0, 130.6, 129.2, 128.5,
128.4, 127.5, 127.2, 124.1, 124.0, 120.5, 119.2, 118.5,
116.2, 50.2, 21.4, 21.2; IR (ATR) 3075, 1640, 1603, 1511,
1456, 1335, 1291, 1246, 1180, 1023, 977, 890, 835, 759,
689, 574, 541 cm-1; HRMS m/z (M+) calcd for C26H19BrO2:
442.0568. Found: 442.0572.
11
This article is protected by copyright. All rights reserved.

10.1002/adsc.201901266
Advanced Synthesis & Catalysis
3-(3-Bromo-2-phenyl-1H-inden-1-yl)-1-methylquinolin-
2(1H)-one (31b). The title compound (31b) was prepared
according to the general procedure. The product was
obtained as a white solid, mp 172-173 oC. Yield: 83% (177
3-(2,3-Diphenyl-1H-inden-1-yl)-4H-chromen-4-one
(34a). The title compound (34a) was prepared according to
the general procedure. The product was obtained as a white
solid, mp 212-214 oC. Yield: 85% (175 mg). 1H NMR (600
MHz, CDCl3)  8.32 (1H, d, J = 7.2 Hz), 7.59 (1H, dt, J =
7.2, 1.8 Hz), 7.54 (1H, d, J = 7.2 Hz), 7.44-7.36 (7H, m),
7.28 (1H, d, J = 8.4 Hz), 7.25-7.24 (2H, m), 7.20-7.15 (3H,
m), 7.13-7.10 (2H, m), 7.09-7.06 (1H, m), 5.84 (1H, brs);
13C NMR (150 MHz, CDCl3)  177.6, 156.2, 153.1, 147.1,
144.7, 143.1, 141.7, 135.3, 134.6, 133.4, 129.4, 129.1,
128.8, 128.2, 127.6, 127.1, 127.0, 125.9, 125.9, 125.0,
123.9, 123.7, 123.1, 120.7, 118.0, 46.2; IR (ATR) 3016,
1628, 1461, 1391, 1277, 1212, 1138, 849, 754, 692 cm-1;
HRMS m/z (M+) calcd for C30H20O2: 412.1463. Found:
412.1460.
1
mg). H NMR (600 MHz, CDCl3)  7.82 (2H, d, J = 7.8
Hz), 7.53 (1H, d, J = 7.8 Hz), 7.50 (1H, d, J = 7.8 Hz),
7.41-7.33 (4H, m), 7.24-7.19 (4H, m), 7.12-7.03 (2H, m),
5.97 (1H, brs), 3.78 (3H, s); 13C NMR (150 MHz, CDCl3)
 162.5, 145.6, 144.7, 142.7, 138.9, 134.9, 133.8, 130.6,
129.9, 128.7, 128.4, 128.3, 127.89, 127.3, 126.7, 123.3,
121.9, 120.7, 120.2, 118.5, 113.7, 50.6, 30.1; IR (ATR)
3075, 1643, 1601, 1517, 1455, 1331, 1290, 1248, 1187,
1031, 967, 890, 834, 756, 683, 572, 540 cm-1; HRMS m/z
(M+) calcd for C25H18BrNO: 427.0572. Found: 427.0576.
3-(3-Chloro-2-phenyl-1H-inden-1-yl)-1,6-
dimethylquinolin-2(1H)-one (32a). The title compound
(32a) was prepared according to the general procedure.
The product was obtained as a white solid, mp 173-174 oC.
3-(2-Phenyl-3-(p-tolyl)-1H-inden-1-yl)-4H-chromen-4-
one (34b). The title compound (34b) was prepared
according to the general procedure. The product was
obtained as a white solid, mp 224-225 oC. Yield: 87% (185
1
Yield: 80% (158 mg). H NMR (600 MHz, CDCl3)  7.81
1
(2H, d, J = 7.8 Hz), 7.55-7.52 (2H, m), 7.38-7.33 (3H, m),
7.25-7.20 (3H, m), 7.16 (1H, d, J = 8.4 Hz), 7.01 (2H, s),
6.00 (1H, brs), 3.80 (3H, s), 2.26 (3H, s); 13C NMR (150
MHz, CDCl3)  162.5, 145.5, 141.6, 141.0, 137.1, 134.5,
133.2, 131.5, 131.2, 130.7, 128.6, 128.4, 128.2, 127.7,
127.3, 126.8, 123.4, 120.3, 119.4, 113.7, 49.4, 30.1, 20.3;
IR (ATR) 3073, 1644, 1602, 1511, 1457, 1333, 1291, 1241,
1181, 1032, 966, 891, 831, 757, 685, 573, 541 cm-1;
HRMS m/z (M+) calcd for C26H20ClNO: 397.1233. Found:
397.1235.
mg). H NMR (600 MHz, CDCl3)  8.32 (1H, d, J = 8.4
Hz), 7.58 (1H, t, J = 8.4 Hz), 7.54 (1H, d, J = 7.8 Hz), 7.39
(1H, t, J = 7.8 Hz), 7.35 (1H, s), 7.30-7.21 (9H, m), 7.17-
7.14 (1H, m), 7.13 (2H, dt, J = 6.6, 1.2 Hz), 7.7.09-7.06
(1H, m), 5.83 (1H, brs), 2.41 (3H, s); 13C NMR (150 MHz,
CDCl3)  177.7, 156.2, 153.1, 147.1, 144.8, 142.7, 141.7,
137.3, 134.7, 133.4, 132.2, 129.5, 129.2, 129.1, 128.2,
127.0, 126.9, 125.9, 125.8, 125.0, 123.9, 123.6, 123.2,
120.7, 118.0, 46.1, 21.3; IR (ATR) 3017, 1628, 1462, 1395,
1278, 1213, 1134, 845, 753, 691 cm-1; HRMS m/z (M+)
calcd for C31H22O2: 426.1620. Found: 426.1622.
3-(3-Bromo-2-phenyl-1H-inden-1-yl)-1,6-
dimethylquinolin-2(1H)-one (32b). The title compound
(32b) was prepared according to the general procedure.
The product was obtained as a white solid, mp 171-172 oC.
3-(3-(Furan-2-yl)-2-phenyl-1H-inden-1-yl)-4H-
chromen-4-one (35). The title compound (35) was
prepared according to the general procedure. The product
1
o
Yield: 78% (171 mg). H NMR (600 MHz, CDCl3)  7.80
was obtained as a white solid, mp 164-165 C. Yield: 89%
1
(2H, d, J = 7.8 Hz), 7.53 (1H, d, J = 7.8 Hz), 7.50 (1H, d, J
= 6.0 Hz), 7.38-7.33 (3H, m), 7.25-7.16 (5H, m), 7.03 (1H,
m), 5.96 (1H, brs), 3.79 (3H, s), 2.27 (3H, s); 13C NMR
(150 MHz, CDCl3)  162.4, 145.8, 144.8, 142.8, 137.1,
134.7, 133.9, 131.5, 131.2, 130.5, 128.7, 128.3, 128.3,
127.8, 127.3, 126.8, 123.4, 120.7, 120.3, 118.5, 113.7, 50.7,
30.1, 20.3; IR (ATR) 3071, 1644, 1602, 1518, 1456, 1330,
1291, 1247, 1186, 1032, 966, 891, 832, 757, 680, 571, 541
cm-1; HRMS m/z (M+) calcd for C26H20BrNO: 441.0728.
Found: 441.0728.
(178 mg). H NMR (600 MHz, CDCl3)  8.19 (1H, d, J =
7.8 Hz), 7.69 (1H, d, J = 7.8 Hz), 7.50 (1H, dt, J = 7.2, 1.8
Hz), 7.42-7.39 (2H, m), 7.31-7.24 (5H, m), 7.21-7.16 (3H,
m), 7.13-7.09 (2H, m), 6.40-6.38 (2H, m), 5.72 (1H, brs);
13C NMR (150 MHz, CDCl3)  177.3, 156.2, 153.4, 149.1,
146.9, 144.9, 142.5, 141.8, 135.2, 133.4, 130.2, 129.0,
128.3, 127.5, 127.2, 126.0, 125.9, 125.0, 123.8, 123.6,
122.8, 121.6, 118.0, 111.1, 109.9, 47.1; IR (ATR) 3070,
1626, 1568, 1452, 1395, 1351, 1251, 1153, 1018, 937, 804,
745, 698, 592 cm-1; HRMS m/z (M+) calcd for C28H18O3:
402.1256. Found: 402.1258.
1-Benzyl-3-(3-chloro-2-phenyl-1H-inden-1-yl)quinolin-
2(1H)-one (33a). The title compound (33a) was prepared
according to the general procedure. The product was
obtained as a white solid, mp 175-176 oC. Yield: 81% (185
3-(3-Ethoxy-2-phenyl-1H-inden-1-yl)-4H-chromen-4-
one (36). The title compound (36) was prepared according
to the general procedure. The product was obtained as a
1
1
mg). H NMR (600 MHz, CDCl3)  7.71 (2H, d, J = 7.8
red colour viscous oils. Yield: 55% (104 mg). H NMR
Hz), 7.42-7.38 (2H, m), 7.22-7.17 (3H, m), 7.12-7.02 (7H,
m), 7.00-6.94 (4H, m), 6.76 (1H, t, J = 7.2 Hz), 5.94 (1H,
brs), 5.53-5.37 (2H, m); 13C NMR (150 MHz, CDCl3) 
162.76, 145.4, 141.7, 141.4, 138.3, 136.1, 135.3, 133.1,
130.7, 129.9, 128.6, 128.6, 128.4, 128.3, 127.7, 127.3,
127.1, 126.8, 126.4, 126.2, 123.3, 121.9, 120.4, 119.4,
114.4, 49.2, 46.3; IR (ATR) 3074, 1641, 1603, 1510, 1454,
1331, 1290, 1243, 1184, 1031, 967, 890, 831, 754, 684,
571, 540 cm-1; HRMS m/z (M+) calcd for C31H22ClNO:
459.1390. Found: 459.1388.
(600 MHz, CDCl3)  8.05 (1H, dd, J = 7.8, 1.2 Hz), 7.93
(1H, d, J = 8.4 Hz), 7.48-7.35 (6H, m), 7.21 (1H, t, J = 7.2
Hz), 7.15 (1H, d, J = 6.6 Hz), 7.09-7.05 (2H, m), 6.88 (1H,
s), 6.81 (1H, d, J = 8.4 Hz), 5.67 (1H, s), 3.39-3.33 (1H,
m), 2.82-2.77 (1H, m), 0.97 (3H, t, J = 7.2 Hz); 13C NMR
(150 MHz, CDCl3)  185.4, 156.4, 145.8, 142.7, 141.9,
139.1, 137.6, 135.9, 135.4, 133.0, 130.1, 127.9, 127.7,
127.1, 126.9, 125.1, 123.2, 121.8, 121.1, 117.5, 100.1, 64.3,
42.8, 14.8; IR (ATR) 2980, 1669, 1603, 1458, 1293, 1205,
1081, 985, 927, 746, 699 cm-1; HRMS m/z (M+) calcd for
C26H20O3: 380.1412. Found: 380.1414.
1-Benzyl-3-(3-bromo-2-phenyl-1H-inden-1-yl)quinolin-
2(1H)-one (33b). The title compound (33b) was prepared
according to the general procedure. The product was
obtained as a white solid, mp 170-171 oC. Yield: 72% (181
3-(1-Oxo-2-phenyl-1H-inden-3-yl)-4H-chromen-4-one
(37). The title compound (37) was prepared according to
the general procedure. The product was obtained as a
1
o
1
mg). H NMR (600 MHz, CDCl3)  7.87 (2H, d, J = 7.8
orange solid, mp 205-206 C. Yield: 67% (117 mg). H
NMR (600 MHz, CDCl3)  8.30 (1H, d, J = 8.4 Hz), 7.79
(1H, s), 7.72 (1H, dt, J = 7.8, 1.2 Hz), 7.55 (1H, d, J = 7.2
Hz), 7.49-7.46 (2H, m), 7.37-7.33 (3H, m), 7.30 (2H, d, J
Hz), 7.59 (1H, d, J = 7.8 Hz), 7.53 (1H, d, J = 7.8 Hz),
7.43 (1H, t, J = 7.8 Hz), 7. 38 (2H, t, J = 7.8 Hz), 7.38-7.23
(9H, m), 7.18-7.16 (2H, m), 7.03 (1H, t, J = 7.2 Hz), 6.09
(1H, brs), 5.74-5.60 (2H, m); 13C NMR (150 MHz, CDCl3)
 162.6, 145.3, 143.1, 139.7, 138.4, 136.1, 133.8, 130.6,
130.0, 128.8, 128.7, 128.5, 128.3, 127.9, 127.4, 127.2,
126.8, 126.5, 126.3, 122.0, 120.8, 118.4, 115.0, 114.6, 50.6,
46.4, 35.7; IR (ATR) 3075, 1646, 1601, 1511, 1456, 1321,
1291, 1241, 1185, 1034, 965, 896, 834, 754, 683, 577, 541
cm-1; HRMS m/z (M+) calcd for C31H22BrNO: 503.0885.
Found: 503.0882.
= 6.6 Hz), 7.27-7.23 (2H, m), 6.99 (1H, d, J = 7.2 Hz); 13
C
NMR (150 MHz, CDCl3)  195.6, 175.6, 156.1, 154.9,
147.6, 144.7, 135.8, 134.2, 133.9, 130.2, 129.9, 129.5,
128.9, 128.4, 128.1, 126.3, 125.8, 124.0, 122.9, 121.7,
118.8, 118.2; IR (ATR) 1704, 1591, 1453, 1336, 1276,
1129, 1066, 927, 857, 753 cm-1; HRMS m/z (M+) calcd for
C24H14O3: 350.0943. Found: 350.0945.
12
This article is protected by copyright. All rights reserved.

10.1002/adsc.201901266
Advanced Synthesis & Catalysis
(2R)-2,3-Diphenyl-2,3-dihydro-1H-inden-1-one
(40).
[5] P. Morán-Poladura, E. Rubio, J. M. González, Angew.
Chem. 2015, 127, 3095; Angew. Chem., Int. Ed. 2015,
54, 3052.
The title compound (40) was prepared according to the
general procedure. The product was obtained as viscous
1
oils. Yield: 66% (187 mg). H NMR (600 MHz, CDCl3) 
7.91 (1H, d, J = 7.8 Hz), 7.64 (1H, dt, J = 7.2, 1.2 Hz),
7.49 (1H, t, J = 7.8 Hz), 7.34-7.27 (7H, m), 7.13-7.10 (4H,
m), 4.60 (1H, d, J = 4.8 Hz), 3.84 (1H, d, J = 4.8 Hz); 13C
NMR (150 MHz, CDCl3)  205.1, 156.0, 142.4, 138.4,
136.0, 135.3, 128.8, 128.8, 128.7, 128.2, 128.2, 127.8,
127.1, 126.6, 123.9, 64.5, 54.7; IR (ATR) 3027, 1711,
1598, 1492, 1452, 1279, 1214, 1033, 752, 686 cm-1;
HRMS m/z (M+) calcd for C21H16O: 284.1201. Found:
284.1203.
[6] Z. A. Khan, T. Wirth, Org. Lett. 2009, 11, 229.
[7] S. Ye, K. Gao, H. Zhou, X. Yang, J. Wu, Chem.
Commun. 2009, 5406.
[8] R. Sanz, A. Martínez, P. García-García, M. A.
Fernández-Rodríguez, M. A. Rashid, F. Rodríguez,
Chem. Commun. 2010, 46, 7427.
2,2-Difluoro-4,6-dimethyl-2H-dioxaborinine (44). The
title compound (44) was prepared according to the general
procedure. The product was obtained as brown viscous oils.
[9] a) K. Mꢀller, C. Faeh, F. Diederich, Science 2007, 317,
1881; b) S. Purser, P. R. Moore, S. Swallow, V.
Gouverneur, Chem. Soc. Rev. 2008, 37, 320; c) S. M.
Ametamey, M. Honer, P. A. Schubiger, Chem. Rev.
2008, 108, 1501; d) D. E. Yerien, S. Bonesi, A. Postigo,
Org. Biomol. Chem. 2016, 14, 8398.
1
Yield: 83% (122 mg). H NMR (600 MHz, CDCl3)  5.96
(1H, s), 2.26 (6H, s); 13C NMR (150 MHz, CDCl3)  192.3,
101.8, 24.0; IR (ATR) 3192, 2261, 1550, 1380, 1359, 1138,
1074, 812, 506 cm-1; HRMS m/z (M+) calcd for
C5H7BF2O2: 148.0507. Found: 148.0505.
[10] a) P. A. Champagne, J. Desroches, J.-D. Hamel, M.
Vandamme, J.-F. Paquin, Chem. Rev. 2015, 115, 9073;
b) T. Furuya, A. S. Kamlet, T. Ritter, Nature 2011, 473,
470. c) P. Alonso, P. Pardo, R. Fontaneda, F. J.
Fananás, F. Rodríguez, Chem. Eur. J. 2017, 23, 13158;
d) A. Venkateswarlu, M. Kanakaraju, A. C. Kunwar, Y.
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Acknowledgements
This work was supported by the National Research Foundation of
Korea (NRF) grant funded by the Korean government (MSIT)
(2018R1A2B2004432), the Priority Research Centers Program
(2014R1A6A1031189), and the Korean Ministry of Education,
Science and Technology (2012M3A7B4049675).
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FULL PAPER
Construction of Halofunctionalized Indenes via
a Cascade Prins-Nazarov Cyclization Promoted
by Dual Roles of BX3
Adv. Synth. Catal. Year, Volume, Page – Page
Sabera Sultanaa and Yong Rok Leea*
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