Rhodium-Catalyzed Oxidative Decarboxylation Annulation Reactions of Mandelic Acids and Alkynes: An Efficient Synthetic Method for Indenones

Article abstract of DOI:10.1021/acs.organomet.7b00004

Efficient rhodium-catalyzed oxidative decarboxylation annulation reactions between mandelic acids and alkyne derivatives are described. The desired indenone products were obtained in medium to good yields under the optimized reaction conditions, which were a [RhCp*Cl₂]₂ catalyst (10.0 mol %) in combination with a PCy₃ ligand (10.0 mol %) and AgSbF₆ (10 mol %) and Cu(OAc)₂ (20 mol %) additives. Many functional groups are compatible with the reaction under the optimized reaction conditions. This strategy provides a promising method for the construction of indenones from cheap and commercially available starting materials.

Full text of DOI:10.1021/acs.organomet.7b00004

Article
pubs.acs.org/Organometallics
Rhodium-Catalyzed Oxidative Decarboxylation Annulation Reactions
of Mandelic Acids and Alkynes: An Efficient Synthetic Method for
Indenones
Xiaobo Yu,†,‡,∥ Yulian Duan,†,∥ Weijie Guo,†,∥ Tao Wang,† Qingxiao Xie,† Shutao Wu,†
Chenggong Jiang,† Zixiong Fan,† Jianhui Wang,*,†,∥ and Guiyan Liu*,§
†Department of Chemistry, College of Science, Tianjin University, Tianjin 300072, People’s Republic of China
‡College of Materials Science and Engineering, Jilin Institute of Chemical Technology, Jilin City 132022, People’s Republic of China
§Tianjin Key Laboratory of Structure and Performance for Functional Molecules; Key Laboratory of Inorganic-Organic Hybrid
Functional Material Chemistry; Ministry of Education; College of Chemistry, Tianjin Normal University, Tianjin 300387, People’s
Republic of China
∥Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, People’s Republic of China
S
* Supporting Information
ABSTRACT: Efficient rhodium-catalyzed oxidative decarboxylation annulation reactions between mandelic acids and alkyne
derivatives are described. The desired indenone products were obtained in medium to good yields under the optimized reaction
conditions, which were a [RhCp*Cl2]2 catalyst (10.0 mol %) in combination with a PCy3 ligand (10.0 mol %) and AgSbF6 (10
mol %) and Cu(OAc)2 (20 mol %) additives. Many functional groups are compatible with the reaction under the optimized
reaction conditions. This strategy provides a promising method for the construction of indenones from cheap and commercially
available starting materials.
Recently, transition-metal-catalyzed atom-economic C−H
bond activations have attracted much attention.4,5 Utilization of
the proximate effect by coordinating a functional group to a
metal center is often used as a strategy to achieve region-
selective ortho C−H bond activations. The annulation of
arenes with alkynes using a functional group directed ortho C−
H bond activation has been developed as a powerful synthetic
method for the construction of cyclic molecular structures.6−8
This method does not require ortho-bifunctionalized arenes as
substrates and therefore is more economical than traditional
cyclization reactions.
Various catalytic processes for the preparation of novel cyclic
compounds have been developed using directed C−H bond
activation, and some of these have successfully afforded
indenones.6−8 Kuninobu et al. were the first to report
annulations of imines with alkynes via C−H bond activation.6
This work inspired expansions of the annulation strategy for
various synthetic targets.7,8 For example, Kokubo et al. reported
a rhodium-catalyzed reaction of aroyl chlorides and alkynes to
give indenones.8a Later, Shi et al. reported the synthesis of
INTRODUCTION
■
Indenones are useful intermediates in organic synthesis because
they play important roles in the chemical, biological, and
material fields.1 Traditionally, indenones are usually synthesized
by Friedel−Crafts cyclizations.2 This method requires the use
of electron-rich aromatic reagents as the starting materials, and
therefore the scope of the reactions is limited. In addition, the
reaction conditions are relatively harsh and hazardous by-
products are often generated during the reactions. So, the
search for more effective methods with broader scopes for the
preparation of indenones has been a pursuit of chemists over
the past few decades. To this end, transition-metal-catalyzed
annulations of ortho-bifunctionalized arenes and alkynes have
been used to prepare indenones.3 The ortho-substitution group
usually includes halide,3a,d−f boronic acid,3b−e or nitrile
groups.3a,b These methods are not limited to electronic-rich
aromatic substrates, and many electron-deficient compounds
have been successfully used in these reactions. However, ortho-
bifunctionalized arenes are rare and expensive compounds that
are usually not readily available, and complicated prefunction-
alization processes are often required to obtain these arenes,
which is both time-consuming and costly.
Received: January 4, 2017
© XXXX American Chemical Society
A
DOI: 10.1021/acs.organomet.7b00004
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indenones via the annulation of benzimides and alkynes
through a rhodium-catalyzed C−H activation process.8b
Subsequently, the annulation of aldehydes,8c azomethine
ylides,8d and arylnitrones8e with alkynes via rhodium-catalyzed
C−H activations have all produced indenones (Scheme 1 A).
Table 1. Optimization of Reaction Conditions for the
Reaction of Mandelic Acids with Alkynes
a
Scheme 1. Rhodium-Catalyzed Synthesis of Indenones via
the Annulation of Ortho Arene C−H Bonds with Alkynes
1a
catalyst
2a
3a
yield
e
b
entry
additive
solvent
(%)
1
2
3
4
5
6
7
8
Pd(OAc)2
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
0
0
0
0
0
0
0
0
Pd(PPh3)4
Pd(dba)2
(PPh3)3RhCl
[Rh(COD)Cl]2
[IrCp*Cl2]2
[Ru(COD)Cl2]n
[RuCl2(p-
cymene)]2
9
[RhCp*Cl2]2
[RhCp*Cl2]2
[RhCp*Cl2]2
[RhCp*Cl2]2
[RhCp*Cl2]2
[RhCp*Cl2]2
[RhCp*Cl2]2
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
xylene
23
32
63
37
40
38
25
0
10
11
12
13
14
15
16
AgSbF6
AgSbF6
AgSbF6
AgSbF6
AgSbF6
Cu(OAc)2
CuCl
CuI
CuCl2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
AgSbF6
AgSbF6
AgSbF6
AgSbF6
AgSbF6
AgSbF6
c
17
[RhCp*Cl2]2
[RhCp*Cl2]2
[RhCp*Cl2]2
[RhCp*Cl2]2
[RhCp*Cl2]2
63
60
0
18
d
19
CH3CN
DCE
However, there are still some drawbacks in this synthesis
strategy, for example, the prior activation of the substrates or
multistep synthesis. The choice of a proper directing group to
achieve the designed annulation reactions via C−H activations
is still a challenge that needs to be overcome in order to expand
the scope of arene substrates.
Organic compounds containing carboxylic acid functional
groups are used in various organic reactions. In recent years,
decarboxylative cross-coupling reactions have developed
rapidly.9 Mandelic acid and its derivatives are readily accessible
starting materials that can undergo decarboxylative cross-
coupling reactions to regioselectively construct new C−C
bonds in place of the carboxylate carbon when CO or CO2 is
extruded. In these reactions, the carboxylate group acts as a
temporary directing group for C−H activation.10 On the basis
of these results, we envisage that a decarboxylative annulation
reaction of mandelic acids and alkynes could occur through
directed ortho C−H activation as shown in Scheme 1B. Herein,
the decarboxylative annulation reaction of mandelic acids and
alkynes for the one-pot synthesis of indenones is reported.
d
20
0
d
21
Dioxane
0
a
Reaction conditions: 1a (0.1 mmol), 2a (0.12 mmol), catalyst (10
b
mol %) in 1 mL of toluene in air at 120 °C for 20 h. Additive (silver
c
salt: 10 mol %, copper salt: 20 mol %). Reaction time: 30 h.
d
e
Reaction temperature: 100 °C. Isolated yields.
salts were tested as additives. When 10 mol % AgSbF6 and 20
mol % Cu(OAc)2 were used, the yield of 3a increased to 63%
(entry 11). Other copper salts, such as CuCl, CuI, or CuCl2,
did not improve the reaction efficiency (entries 12−14).
Further experiments showed that [RhCp*Cl2]2, AgSbF6, and
Cu(OAc)2 are all indispensable for the reaction. In the absence
of AgSbF6, 3a was obtained in only 25% yield (entry 15) and
the reaction did not proceed when AgSbF6 and Cu(OAc)2 were
used in the absence of [RhCp*Cl2]2 (entry16).
Prolonging the reaction time to 30 h, with [RhCp*Cl2]2,
AgSbF6, and Cu(OAc)2, did not result in an increase in the
yield (entry17). Several other solvents, such as xylene, CH3CN,
dichloroethene (DCE), and dioxane, were also tested for this
oxidative decarboxylative annulation reaction. Xylene gave a
similar yield (60%) to toluene (entry 18). When CH3CN,
DCE, or dioxane was used as the solvent at different
temperatures, no products were observed (entries 19−21).
So, 10 mol % [RhCp*Cl2]2 in combination with 10 mol %
AgSbF6 and 20 mol % Cu(OAc)2 in toluene was selected as the
optimal catalyst system for this oxidative decarboxylation
annulation reaction.
RESULTS AND DISCUSSION
■
To achieve this reaction, mandelic acid (1a) and 1,2-
diphenylethyne (2a) were first used as the model substrates
to optimize the reaction conditions. First, different transition-
metal catalysts were tested, and the results are shown in Table 1
(entries 1−9). No desired products were obtained in toluene at
120 °C for 20 h with Pd(OAc)2, Pd(PPh3)4, Pd(dba)2,
(PPh3)3RhCl, [Rh(COD)Cl]2, [IrCp*Cl2]2, [Ru(COD)Cl2]n,
and [RuCl2(p-cymene)]2 (entries 1−8). When [RhCp*Cl2]2
was used as the catalyst under these same conditions, the
desired decarboxylative annulation product 3a was obtained in
low yield (23%) (entry 9).
Given the importance of phosphine ligands,11 a series of
phosphine ligands were examined for the oxidative decarbox-
ylation annulation reaction (Table 2). Initially, some bidentate
chelate phosphine ligands, such as 1,2-bis(diphenylphosphino)-
ethane (DPPE), 1,3-bis(diphenylphosphino)propane (DPPP),
rac-2,2′-bis(diphenylphosphino)-1,1′-binaphthalene (rac-
Adding AgSbF6 to the reaction system improved the yield to
32% (entry 10). In order to further increase the yield, copper
B
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a
6), and the electron-rich phosphine ligand (CH3OC6H4)3P
improved the reaction yield to 76% (entry 7). The most
favorable ligand was PCy3, which gave the desired product in
85% yield (entry 8). Therefore, the combination of
[RhCp*Cl2]2 and PCy3 ligand in the presence of AgSbF6 and
Cu(OAc)2 was selected as the optimized catalytic system for
the current transformation.
Table 2. Optimization of Reaction Conditions for Ligands
b
c
entry
ligand
DPPE
DPPP
yield (%)
1
2
3
4
5
6
7
8
65
64
67
68
66
70
76
85
Next, the reactions of 1a with various 1,2-diphenylethynes
bearing electron-donating or electron-withdrawing groups were
investigated under the optimized reaction conditions, and the
results are shown in Table 3. When 1a reacted with 1,2-
diphenylethyne (2a), the desired product 3a was obtained in
85% yield. The 1,2-diphenylethynes with methyl substituents in
different positions were well-tolerated and afforded the
corresponding products 3b−d in good yields (90%, 80%, and
76%, respectively). As a result of the regioselectivity of the
reaction, 3c is the major product (ratio of 3c and 3c′: 4:1).
Various alkoxy-substituted 1,2-diphenylethynes were also tested
in the reaction, and they gave 3e−g in good yields (83%, 86%,
and 85%, respectively). The regioselective ratio of 3e and 3e′
was 3:2. The reaction of 1a with the 1,2-diphenylethyne bearing
a tertiary-butyl group proceeded smoothly to give 3h in 87%
yield. The corresponding products 3i−m were obtained in 79−
83% yields when 1a was reacted with 1,2-diphenylethynes
bearing −F, −Cl, or −Br groups. The major products were 3i,
rac-BINAP
DPPF
PPh3
P(C6F5)3
(CH3OC6H4)3P
PCy3
a
Reaction conditions: 1a (0.1 mmol), 2a (0.12 mmol), [RhCp*Cl2]2
(10 mol %), AgSbF6 (10 mol %), and Cu(OAc)2 (20 mol %) in 1 mL
of toluene in air at 120 °C for 20 h. Phoshine ligand: 10 mol %.
b
c
Isolated yields.
BINAP), and 1,1′-bis(diphenylphosphino)ferrocene (DPPF),
were examined for the reaction. The product yields of the
reactions with these ligands increased slightly (64−68%, entries
1−4, Table 3). The use of PPh3 as a ligand also slightly
improved the reaction yield to 66% (entry 5). The electron-
deficient phosphine ligand P(C6F5)3 gave a yield of 70% (entry
a
Table 3. Decarboxylative Coupling and Annulation Reactions of Mandelic Acids with Alkynes
a
Reaction conditions: 1 (0.1 mmol), 2 (0.12 mmol), [RhCp*Cl2]2 (10 mol %), AgSbF6 (10 mol %), PCy3(10 mol %), and Cu(OAc)2 (20 mol %) in
1 mL of toluene at 120 °C under air for 20 h; isolated yields. Numbers in parentheses are the ratio of regioisomers (3:3′).
C
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3j, and 3k with regioselective ratios of 7:2, 3:1, and 4:1,
respectively. These halide-substituted products can be further
modified to give complex useful products.12
gives rhodacyclic intermediate C. The decarboxylation of
intermediate C gives the four-membered rhodacyclic inter-
mediate D and CO2. The replacement of the ligand by the
alkyne produces intermediate E, and further intramolecular
insertion of the alkyne into the Rh−C bond generates
intermediate F. Subsequently a reductive elimination occurs
to give the Rh(I) species and the product 3. Finally, the Rh(I)
species is oxidized by O2 in the presence of copper(II) to
regenerate the catalytically active species [LRhCp*(OAc)2],
which then is used in another catalytic cycle.
The 1,2-diphenylethynes with an electron-withdrawing
group, such as −CF3 or −OCF3, also gave the desired products
3n and 3o in 77% and 75% yields, respectively. However, the
yield for the 1,2-diphenylethyne bearing an ester group in the
para-position decreased slightly to 60% (3p). The 1,2-
diphenylethynes with an ester group in the ortho-position
also had a lower yield (55% for product 3q). The lower yields
for these substrates may be due to the side reactions that can
occur from the competitive complexion of the ester groups to
the rhodium metal centers. Other types of alkynes, such as 1,2-
di(naphthalen-1-yl)ethyne, also gave the corresponding prod-
uct 3r in 72% yield.
The effects of substituents on mandelic acid were also
studied (Table 3). Mandelic acid with a methyl group reacted
with alkyne 2a to give 3s in 80% yield. A −Ph- or a 1-naphthyl-
group-substituted mandelic acid reacted with alkyne 2a and
afforded the desired product 3t or 3u in 75% or 72% yield.
Mandelic acid bearing a methoxy or a −Br group also reacted to
give the desired product 3v or 3w in 65% and 70% yields,
respectively.
CONCLUSION
■
In summary, a rhodium-catalyzed oxidative decarboxylative
annulation of mandelic acids with alkynes has been developed.
Various substituted indenones were obtained in medium to
good yields under the optimized reaction conditions. A
plausible catalytic mechanism involving intramolecular C−H
activation, decarboxylation, and annulation has been proposed.
The current method opens up a straightforward one-step
synthetic pathway for various indenones from mandelic acids
and alkynes.
EXPERIMENTAL SECTION
■
On the basis of these experimental results and previous
reports,13 a plausible mechanism for the decarboxylative
annulation reactions of mandelic acids with alkynes is proposed
in Figure 1. First, the catalytically active species [LRhCp*-
1
General Information. H NMR, 19F NMR, and 13C NMR were
obtained on a 400 MHz spectrometer with CDCl3 as solvent. The
chemical shifts are reported in ppm relative to CDCl3 (δ = 7.26) for
1H NMR and relative to the central CDCl3 resonance (δ = 77.0) for
13C NMR. For 19F NMR, (trifluoromethyl)benzene was used as an
external standard. NMR data of known compounds are in agreement
with literature values. Coupling constants (J) are quoted in Hz at 400
MHz for 1H. Multiplicities are reported as follows: singlet (s), doublet
(d), doublet of doublets (dd), triplet (t), quartet (q), and multiplet
(m). Infrared spectra were recorded on a PerkinElmer model 1600
FT-IR spectrophotometer and Nicolet Magna 550 FT-IR spectropho-
tometer. High-resolution mass spectra (HRMS) were obtained on a
JEOL JMS-DX303 instrument. Elemental analyses were performed by
the Elemental Analysis Section of Tianjin University.
Materials and Methods. Unless otherwise noted, all reactions
were performed under an atmosphere of air with oven-dried glassware
and anhydrous solvents. Reactions were monitored by analytical thin-
layer chromatography on 0.20 mm silica gel plates, and spots were
detected by UV absorption. Silica gel (200−300 mesh) (from Yantai
Huagong Chem. Company, Ltd.) was used for flash chromatography.
The starting materials, various mandelic acids and 1,2-diphenylethynes,
were synthesized and purified according to the literature procedures.14
Other chemicals or reagents were obtained from commercial sources.
Experimental Procedure for the Rh-Catalyzed Synthesis of
Indenones via Mandelic Acids and Alkynes. To an oven-dried
screw-top vial were added substituted mandelic acid (0.1 mmol),
substituted alkyne (0.12 mmol), [RhCp*Cl2]2 (0.01 mmol, 6.18 mg),
PCy3 (0.01 mmol, 2.80 mg), AgSbF6 (0.01 mmol, 3.44 mg),
Cu(OAc)2 (0.02 mmol, 3.99 mg), and toluene (1 mL). The mixture
was vigorously stirred at 120 °C under air to the end of the reaction.
Organic solvents were removed in vacuo, and then the residue was
purified by a silica gel column chromatography to give the desired
product.
Figure 1. Mechanism for the decarboxylative annulation reactions of
2-Oxo-2-phenylacetic acid (A): Mandelic acid (0.1 mmol, 15.2
mg), [RhCp*Cl2]2 (0.01 mmol, 6.18 mg), AgSbF6 (0.01 mmol, 3.44
mg), Cu(OAc)2 (0.02 mmol, 3.99 mg), and toluene (1 mL) were used.
The mixture was stirred at 120 °C for 10 h under air. Organic solvents
were removed in vacuo, and then the residue was purified by a silica gel
column chromatography to give a white solid (13.8 mg, yield 92%). 1H
NMR (C2D6SO, 400 MHz): δ 7.88 (d, J = 7.12 Hz, 2H), 7.70 (t, J =
7.40 Hz, 1H), 7.57 (t, J = 7.60 Hz, 2H). 13C NMR (C2D6SO, 100
MHz): δ 191.98, 168.24, 134.71, 133.27, 129.71, 129.43. IR (KBr): ν
3441, 3060, 2463, 1683, 1591, 1229, 983, 712, 679 cm−1. Anal. Found
(calcd) for C8H6O3: C, 64.01 (64.00); H, 4.02 (4.03).
mandelic acids with alkynes.
(OAc)2] is generated from the reaction of [RhCp*Cl2]2 and
AgSbF6 in the presence of Cu(OAc)2 and the PCy3 ligand. The
reaction then begins with the oxidation of 1a to 2-oxo-2-
phenylacetic acid (A) by O2 from the air in the presence of
Cu(OAc)2. Next, the ligand exchange of [LRhCp*(OAc)2]
with A generates intermediate B. The intramolecular C−H
bond activation in B followed by the release of HOAc then
D
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1
2,3-Diphenyl-1H-inden-1-one (3a): This was purified by column
yield 33%). Mp: 154−156 °C. H NMR (CDCl3, 400 MHz): δ 7.59
(d, J = 7.01 Hz, 1H), 7.43−7.36 (m, 6H), 7.31−7.27 (m, 1H), 7.19−
7.13 (m, 2H), 6.88 (d, J = 7.69 Hz, 1H), 6.81−6.79 (m, 2H), 3.64 (s,
3H). 13C NMR (CDCl3, 100 MHz): δ 196.32, 159.09, 155.55, 145.16,
133.43, 132.74, 132.18, 131.93, 130.71, 129.27, 129.04, 128.98, 128.77,
128.44, 122.95, 122.47, 121.27, 114.88, 114.08, 54.99. IR (KBr): ν
3676, 3058, 2933, 2838, 2362, 1710, 1595, 1453, 1344, 1286, 1249,
1175, 1043, 752, 698 cm−1. Anal. Found (calcd) for C22H16O2: C,
84.58 (84.59); H, 5.17 (5.16).
chromatography to provide a red solid (24.0 mg, yield 85%). The
1
compound 3a is known, and the H NMR and the 13C NMR spectra
of the compound are in agreement with a previous report.15 1H NMR
(CDCl3, 400 MHz): δ 7.61 (d, J = 6.97 Hz, 1H), 7.44−7.37 (m, 6H),
7.33−7.27 (m, 6H), 7.17 (d, J = 7.21 Hz, 1H). 13C NMR (CDCl3, 100
MHz): δ 196.37, 155.23, 145.11, 133.36, 132.61, 132.27, 131.51,
130.65, 129.90, 129.22, 128.87, 128.71, 128.42, 127.99, 127.66, 122.87,
121.18. IR (KBr): ν 3741, 3438, 3064, 2920, 2357, 1707, 1612, 1453,
1351, 1182, 1071, 914, 842, 701 cm−1. Anal. Found (calcd) for
C21H14O: C, 89.35 (89.34); H, 5.00 (5.00).
2,3-Bis(4-methoxyphenyl)-1H-inden-1-one (3f): This was purified
by column chromatography to provide a red solid (29.4 mg, yield
1
2,3-Di-p-tolyl-1H-inden-1-one (3b): This was purified by column
86%). The compound 3f is known, and the H NMR and the 13C
chromatography to provide a red solid (27.9 mg, yield 90%). The
NMR spectra of the compound are in agreement with a previous
report.15 1H NMR (CDCl3, 400 MHz): δ 7.58 (d, J = 6.89 Hz, 1H),
7.40−7.37 (m, 3H), 7.31−7.27 (m, 3H), 7.20 (d, J = 7.25 Hz, 1H),
6.97 (d, J = 8.71 Hz, 2H), 6.85 (d, J = 8.81 Hz, 2H), 3.89 (s, 3H), 3.83
(s, 3H). 13C NMR (CDCl3, 100 MHz): δ 196.95, 160.29, 159.09,
153.75, 145.49, 133.22, 131.50, 131.26, 131.03, 130.16, 128.58, 127.12,
125.13, 123.43, 122.68, 120.92, 114.20, 113.67, 55.17. IR (KBr): ν
3451, 2924, 2363, 1703, 1607, 1506, 1458, 1293, 1249, 1177, 1028,
789 cm−1. Anal. Found (calcd) for C23H18O3: C, 80.69 (80.68); H,
5.31 (5.30).
1
compound 3b is known, and the H NMR and the 13C NMR spectra
of the compound are in agreement with a previous report.15 1H NMR
(CDCl3, 400 MHz): δ 7.59 (d, J = 6.98 Hz, 1H), 7.37−7.28 (m, 4H),
7.25−7.16 (m, 5H), 7.11 (d, J = 7.78 Hz, 2H), 2.43 (s, 3H), 2.35 (s,
3H). 13C NMR (CDCl3, 100 MHz): δ 196.67, 154.71, 145.38, 139.27,
137.44, 133.23, 131.97, 130.86, 129.83, 129.79, 129.40, 129.34, 128.77,
128.65, 128.42, 127.92, 122.71, 121.06, 21.46, 21.29. IR (KBr): ν 3621,
2923, 1710, 1603, 1508, 1496, 1349, 1190, 1070, 1021, 819, 742 cm−1.
Anal. Found (calcd) for C23H18O: C, 88.98 (89.00); H, 5.84 (5.85).
2-(2,6-Dimethylphenyl)-3-phenyl-1H-inden-1-one (3c): This was
purified by column chromatography to provide a red solid (19.8 mg,
2,3-Bis(4-ethoxyphenyl)-1H-inden-1-one (3g): This was purified
by column chromatography to provide a red solid (31.5 mg, yield
1
1
yield 64%). Mp: 128−130 °C. H NMR (CDCl3, 400 MHz): δ 7.62
85%). The compound 3g is known, and the H NMR and the 13C
(d, J = 6.86 Hz, 1H), 7.37 (d, J = 6.49 Hz, 3H), 7.32−7.27 (m, 4H),
7.22−7.13 (m, 3H), 6.86 (d, J = 7.04 Hz, 1H), 2.39 (s, 3H), 2.05 (s,
3H). 13C NMR (CDCl3, 100 MHz): δ 196.68, 156.08, 146.01, 135.63,
133.63, 132.43, 131.26, 130.73, 130.36, 129.62, 129.02, 128.82, 128.04,
127.67, 122.64, 121.23, 20.99, 19.35. IR (KBr): ν 3451, 2924, 2857,
1708, 1603, 1494, 1457, 1343, 1265, 1173, 1080, 1027, 813, 756, 685
cm−1. HRMS calcd for C23H18O: 310.1358, found 310.1357. Anal.
Found (calcd) for C23H18O: C, 89.01 (89.00); H, 5.84 (5.85).
3-(2,6-Dimethylphenyl)-2-phenyl-1H-inden-1-one (3c′): This was
purified by column chromatography to provide a red solid (5.0 mg,
NMR spectra of the compound are in agreement with a previous
report.16 1H NMR (CDCl3, 400 MHz): δ 7.58−7.56 (m, 1H), 7.39−
7.35 (m, 3H), 7.29−7.24 (m, 3H), 7.19 (d, J = 7.22 Hz, 1H), 6.95−
6.91 (m, 2H), 6.83−6.81 (m, 2H), 4.12−4.02 (m, 4H), 1.49−1.41 (m,
6H). 13C NMR (CDCl3, 100 MHz): δ 196.96, 159.69, 158.47, 153.73,
153.73, 145.52, 133.18, 131.24, 131.06, 130.15, 128.53, 124.97, 123.29,
122.63, 120.91, 114.65, 114.16, 63.51, 63.32, 14.82, 14.79. IR (KBr): ν
3577, 2976, 2928, 2365, 1706, 1607, 1464, 1343, 1292, 1176, 1078,
1041, 920, 825, 767, 665 cm−1. Anal. Found (calcd) for C25H22O3: C,
81.05 (81.06); H, 6.00 (5.99).
1
yield 16%). Mp: 128−130 °C. H NMR (CDCl3, 400 MHz): δ 7.60
2,3-Bis(4-tert-butylphenyl)-1H-inden-1-one (3h): This was purified
(d, J = 6.82 Hz, 1H), 7.38−7.33 (m, 3H), 7.31−7.24 (m, 4H), 7.18−
7.11 (m, 3H), 6.84 (d, J = 7.78 Hz, 1H), 2.37 (s, 3H), 2.03 (s, 3H).
13C NMR (CDCl3, 100 MHz): δ 196.70, 156.10, 146.04, 135.64,
133.64, 132.50, 132.45, 132.29, 131.28, 130.73, 130.38, 129.62, 129.03,
128.83, 128.15, 128.04, 127.68, 122.65, 121.24, 21.00, 19.35. IR (KBr):
ν 3451, 2924, 2857, 1708, 1603, 1494, 1457, 1343, 1265, 1173, 1080,
1027, 813, 756, 685 cm−1. Anal. Found (calcd) for C23H18O: C, 89.02
(89.00); H, 5.85 (5.85).
by column chromatography to provide a red solid (34.3 mg, yield
1
87%). The compound 3h is known, and the H NMR and the 13C
NMR spectra of the compound are in agreement with a previous
report.17 1H NMR (CDCl3, 400 MHz): δ 7.60 (d, J = 7.06 Hz, 1H),
7.47 (d, J = 8.49 Hz, 2H), 7.40−7.33 (m, 4H), 7.32−7.28 (m, 4H),
7.19 (d, J = 7.21 Hz, 1H), 1.41 (s, 9H), 1.35 (s, 9H). 13C NMR
(CDCl3, 100 MHz): δ 196.86, 154.63, 152.36, 150.46, 145.55, 133.21,
131.74, 130.87, 129.84, 129.53, 128.59, 128.24, 127.87, 125.54, 124.93,
122.66, 121.21, 34.81, 34.55, 31.23, 31.16. IR (KBr): ν 3455, 2527,
1638, 1412, 1389, 1168, 1107, 1055, 1025, 947, 894, 756 cm−1. Anal.
Found (calcd) for C29H30O: C, 88.29 (88.28); H, 7.65 (7.66).
2-(4-Fluorophenyl)-3-phenyl-1H-inden-1-one (3i): This was puri-
fied by column chromatography to provide a red solid (18.6 mg, yield
2,3-Di-m-tolyl-1H-inden-1-one (3d): This was purified by column
chromatography to provide a red solid (23.6 mg, yield 76%). The
1
compound 3d is known, and the H NMR and the 13C NMR spectra
of the compound are in agreement with a previous report.16 1H NMR
(CDCl3, 400 MHz): δ 7.59 (d, J = 7.78 Hz, 1H), 7.38−7.34 (m, 1H),
7.31−7.27 (m, 2H), 7.22−7.06 (m, 6H), 6.95 (d, J = 7.53 Hz, 1H),
6.89 (d, J = 7.14 Hz, 1H), 2.16 (s, 3H), 2.10 (s, 3H). 13C NMR
(CDCl3, 100 MHz): δ 196.20, 157.55, 145.88, 137.06, 135.92, 135.79,
133.47, 132.25, 130.97, 130.69, 130.53, 130.23, 128.85, 128.82, 128.10,
125.77, 125.35, 122.84, 121.45, 20.62, 20.14. IR (KBr): ν 3566, 2923,
1709, 1607, 1456, 1337, 1258, 1175, 1068, 1036, 926, 851, 743 cm−1.
Anal. Found (calcd) for C23H18O C, 89.02 (89.00); H, 5.84 (5.85).
2-(3-Methoxyphenyl)-3-phenyl-1H-inden-1-one (3e): This was
purified by column chromatography to provide a red solid (15.6 mg,
1
62%). The compound 3i is known, and the H NMR and the 13C
NMR spectra of the compound are in agreement with a previous
report.18 1H NMR (CDCl3, 400 MHz): δ 7.62 (d, J = 7.01 Hz, 1H),
7.43−7.38 (m, 3H), 7.34−7.27 (m, 6H), 7.16−7.11 (m, 3H). 13C
NMR (CDCl3, 100 MHz): δ 196.20, 163.08 (d, J = 248 Hz), 154.16,
145.00, 133.45, 132.60, 131.76, 130.58, 130.50, 129.92, 129.05, 128.40,
128.16, 127.87, 123.05, 121.02, 116.02 (d, J = 22 Hz). 19F NMR (376
MHz, CDCl3): δ −110.74 (s, 1F). IR (KBr): ν 3694, 3059, 2925,
2362, 1708, 1603, 1508, 1455, 1345, 1230, 1158, 1072, 850, 756, 703
cm−1. Anal. Found (calcd) for C21H13FO: C, 83.96 (83.98); H, 4.37
(4.36).
1
yield 50%). Mp: 154−156 °C. H NMR (CDCl3, 400 MHz): δ 7.61
(d, J = 6.72 Hz, 1H), 7.44−7.33 (m, 3H), 7.31−7.28 (m, 5H), 7.21 (d,
J = 6.78 Hz, 1H), 7.01−6.96 (m, 2H), 6.93−6.92 (m, 1H), 3.74 (s,
3H). 13C NMR (CDCl3, 100 MHz): δ 196.44, 159.72, 155.14, 145.18,
133.97, 133.44, 132.49, 130.74, 130.71, 129.93, 129.91, 128.93, 128.04,
127.75, 122.95, 121.29, 120.82, 115.13, 113.73, 55.20. IR (KBr): ν
3676, 3058, 2933, 2838, 2362, 1710, 1595, 1453, 1344, 1286, 1249,
1175, 1043, 752, 698 cm−1. HRMS: calcd for C22H16O2 312.1150,
found 312.1153. Anal. Found (calcd) for C22H16O2 C, 84.57 (84.59);
H, 5.16 (5.16).
3-(4-Fluorophenyl)-2-phenyl-1H-inden-1-one (3i′): This was
purified by column chromatography to provide a red solid (5.4 mg,
1
yield 18%). The compound 3i′ is known, and the H NMR and the
13C NMR spectra of the compound are in agreement with a previous
report.18 1H NMR (CDCl3, 400 MHz): δ 7.61 (d, J = 6.99 Hz, 1H),
7.47−7.44 (m, 3H), 7.42−7.38 (m, 3H), 7.33−7.27 (m, 3H), 7.16 (d, J
= 7.21 Hz, 1H), 7.00−6.96 (m, 2H). 13C NMR (CDCl3, 100 MHz): δ
196.39, 162.31 (d, J = 246 Hz), 155.24, 145.14, 133.51, 132.56, 131.77,
131.69, 131.33, 130.61, 129.40, 129.02, 128.88, 128.41, 123.02, 121.28,
115.19 (d, J = 21 Hz). 19F NMR (376 MHz, CDCl3): δ −113.36 (s,
3-(3-Methoxyphenyl)-2-phenyl-1H-inden-1-one (3e′): This was
purified by column chromatography to provide a red solid (10.3 mg,
E
DOI: 10.1021/acs.organomet.7b00004
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Article
1F). IR (KBr): ν 3694, 3059, 2925, 2362, 1708, 1603, 1508, 1455,
1345, 1230, 1158, 1072, 850, 756, 703 cm−1. Anal. Found (calcd) for
C21H13FO: C, 83.97 (83.98); H, 4.37 (4.36).
131.45, 131.42, 130.42, 130.00, 129.88, 129.79, 129.32, 123.77, 123.24,
122.35, 121.14. IR (KBr): ν 3062, 2924, 2852, 1711, 1605, 1458, 1342,
1265, 1182, 1068, 1010, 922, 831, 766, 677 cm−1. Anal. Found (calcd)
for C21H12Br2O: C, 57.29 (57.31); H, 2.76 (2.75).
2-(4-Chlorophenyl)-3-phenyl-1H-inden-1-one (3j): This was puri-
2,3-Bis(4-(trifluoromethyl)phenyl)-1H-inden-1-one (3n): This was
fied by column chromatography to provide a red solid (19.6 mg, yield
1
62%). The compound 3j is known, and the H NMR and the 13C
purified by column chromatography to provide a red solid (32.2 mg,
1
yield 77%). The compound 3n is known, and the H NMR and the
NMR spectra of the compound are in agreement with a previous
report.18 1H NMR (CDCl3, 400 MHz): δ 7.62 (d, J = 6.93 Hz, 1H),
7.43−7.39 (m, 3H), 7.36−7.24 (m, 8H), 7.14 (d, J = 7.19 Hz, 1H).
13C NMR (CDCl3, 100 MHz): δ 196.10, 153.82, 144.78, 135.19,
133.50, 132.75, 131.09, 130.36, 129.92, 129.88, 129.14, 129.09, 128.35,
128.18, 127.94, 123.13, 120.98. IR (KBr): ν 3676, 2923, 2363, 1710,
1489, 1346, 1180, 1091, 1016, 848, 759 cm−1. Anal. Found (calcd) for
C21H13ClO: C, 79.64 (79.62); H, 4.13 (4.14).
13C NMR spectra of the compound are in agreement with a previous
report.17 1H NMR (CDCl3, 400 MHz): δ 7.72 (d, J = 8.04 Hz, 2H),
7.64 (d, J = 6.98 Hz, 1H), 7.55−7.50 (m, 4H), 7.45−7.41 (m, 1H),
7.37−7.34 (m, 3H), 7.12 (d, J = 7.17 Hz, 1H). 13C NMR (CDCl3, 100
MHz): δ 195.28, 155.01, 144.30, 135.93, 133.89, 133.80, 131.54 (q, J =
32 Hz), 130.20, 130.15, 129.77, 128.82, 126.09 (q, J = 3.70 Hz),
125.21 (q, J = 3.70 Hz), 123.97 (q, J = 269 Hz), 123.72 (q, J = 271
Hz), 123.61, 121.44. 19F NMR (376 MHz, CDCl3): δ −62.77 (s, 3F),
−62.86 (s, 3F). IR (KBr): ν 3624, 2920, 2362, 1710, 1603, 1457, 1340,
1273, 1182, 1071, 1027, 914, 846, 757, 692 cm−1. Anal. Found (calcd)
for C23H12F6O: C, 66.02 (66.04); H, 2.88 (2.89).
3-(4-Chlorophenyl)-2-phenyl-1H-inden-1-one (3j′): This was
purified by column chromatography to provide a red solid (6.6 mg,
1
yield 21%). The compound 3j′ is known, and the H NMR and the
13C NMR spectra of the compound are in agreement with a previous
report.18 1H NMR (CDCl3, 400 MHz): δ 7.61 (d, J = 6.98 Hz, 1H),
7.47−7.45 (m, 3H), 7.42−7.38 (m, 3H), 7.34−7.30 (m, 1H), 7.28−
7.22 (m, 4H), 7.17 (d, J = 7.18 Hz, 1H). 13C NMR (CDCl3, 100
MHz): δ 196.12, 155.73, 144.97, 133.70, 133.53, 132.38, 131.21,
131.07, 130.58, 129.50, 129.17, 129.13, 128.91, 128.35, 123.05, 121.39.
IR (KBr): ν 3676, 2923, 2363, 1710, 1489, 1346, 1180, 1091, 1016,
848, 759 cm−1. Anal. Found (calcd) for C21H13ClO: C, 79.63 (79.62);
H, 4.13 (4.14).
2,3-Bis(4-(trifluoromethoxy)phenyl)-1H-inden-1-one (3o): This
was purified by column chromatography to provide a red solid (33.8
mg, yield 75%). Mp: 95−97 °C. 1H NMR (CDCl3, 400 MHz): δ 7.61
(d, J = 7.02 Hz, 1H), 7.44−7.39 (m, 3H), 7.35−7.27 (m, 5H), 7.15−
7.12 (m, 3H). 13C NMR (CDCl3, 100 MHz): δ 195.76, 154.26, 149.34
(q, J = 101 Hz), 144.58, 133.72, 131.45, 131.36, 130.85, 130.35,
130.13, 129.43, 128.93, 123.36, 121.25, 120.59, 120.37 (q, J = 256 Hz).
19F NMR (376 MHz, CDCl3): δ −57.73 (s, 6F). IR (KBr): ν 3567,
2920, 2362, 1713, 1612, 1410, 1347, 1262, 1171, 1019, 922, 830, 743,
696 cm−1. HRMS: calcd for C23H12F6O3 450.0691, found 450.0687.
Anal. Found (calcd) for C23H12F6O3: C, 61.35 (61.34); H, 2.68 (2.69).
Diethyl 4,4′-(1-oxo-1H-indene-2,3-diyl)dibenzoate (3p). This was
purified by column chromatography to provide a red solid (25.6 mg,
yield 60%). Mp: 131−133 °C. 1H NMR (CDCl3, 400 MHz): δ 8.11−
8.09 (m, 2H), 7.95−7.92 (m, 2H), 7.63 (d, J = 6.82 Hz, 1H), 7.45−
7.39 (m, 3H), 7.36−7.30 (m, 3H), 7.13 (d, J = 7.21 Hz, 1H), 4.44−
4.33 (m, 4H), 1.43−1.36 (m, 6H). 13C NMR (CDCl3, 100 MHz): δ
194.35, 165.87, 155.49, 144.54, 140.78, 136.91, 134.93, 133.78, 131.43,
130.15, 129.83, 129.58, 129.34, 128.44, 123.45, 121.43, 61.29, 60.98,
14.31. IR (KBr): ν 3579, 2926, 2367, 1717, 1605, 1458, 1367, 1276,
1182, 1073, 1021, 925, 833, 768, 708 cm−1. HRMS: calcd for
C27H22O5 426.1467, found 426.1461. Anal. Found (calcd) for
C27H22O5: C, 76.06 (76.04); H, 5.19 (5.20).
2-(4-Bromophenyl)-3-phenyl-1H-inden-1-one (3k): This was
purified by column chromatography to provide a red solid (23.8 mg,
1
yield 66%). The compound 3k is known, and the H NMR and the
13C NMR spectra of the compound are in agreement with a previous
report.19 1H NMR (CDCl3, 400 MHz): δ 7.60 (d, J = 6.98 Hz, 1H),
7.56 (d, J = 8.46 Hz, 2H), 7.42−7.39 (m, 2H), 7.32−7.27 (m, 7H),
7.13 (d, J = 7.23 Hz, 1H). 13C NMR (CDCl3, 100 MHz): δ 196.10,
153.84, 144.76, 133.51, 132.79, 132.10, 131.61, 130.57, 130.37, 130.15,
129.89, 129.11, 128.20, 127.97, 123.48, 123.15, 120.99. IR (KBr): ν
3060, 2924, 2360, 1709, 1597, 1487, 1455, 1346, 1182, 1071, 1013,
917, 845, 697 cm−1. Anal. Found (calcd) for C21H13BrO: C, 69.84
(69.82); H, 3.62 (3.63).
3-(4-Bromophenyl)-2-phenyl-1H-inden-1-one (3k′): This was
purified by column chromatography to provide a red solid (6.1 mg,
1
yield 17%). The compound 3k′ is known, and the H NMR and the
Dimethyl 2,2′-(1-oxo-1H-indene-2,3-diyl)dibenzoate (3q): This
13C NMR spectra of the compound are in agreement with a previous
report.19 1H NMR (CDCl3, 400 MHz): δ 7.58 (d, J = 8.14 Hz, 1H),
7.44−7.42 (m, 3H), 7.40−7.36 (m, 5H), 7.32−7.28 (m, 1H), 7.15 (d, J
= 8.50 Hz, 3H). 13C NMR (CDCl3, 100 MHz): δ 196.03, 155.79,
145.00, 133.55, 132.40, 131.50, 131.30, 131.13, 130.60, 129.66, 129.51,
129.16, 128.93, 128.34, 123.07, 122.07, 121.41. IR (KBr): ν 3060,
2924, 2360, 1709, 1597, 1487, 1455, 1346, 1182, 1071, 1013, 917, 845,
697 cm−1. Anal. Found (calcd) for C21H13BrO: C, 69.83 (69.82); H,
3.62 (3.63).
was purified by column chromatography to provide a red solid (21.9
1
mg, yield 55%). Mp: 180−182 °C. H NMR (CDCl3, 400 MHz): δ
8.09−8.06 (m, 1H), 8.00−7.97 (m, 1H), 7.58−7.56 (m, 1H), 7.45−
7.42 (m, 2H), 7.33−7.28 (m, 3H), 7.25−7.22 (m, 2H), 7.06−7.04 (m,
1H), 6.72 (d, J = 7.17 Hz, 1H), 3.84 (s, 3H), 3.72 (s, 3H). 13C NMR
(CDCl3, 100 MHz): δ 195.14, 167.59, 167.14, 155.01, 146.25, 134.79,
134.12, 133.43, 132.71, 132.26, 131.69, 131.41, 131.14, 130.38, 130.24,
130.00, 128.82, 128.33, 127.81, 123.03, 119.95, 52.25, 52.13. IR (KBr):
ν 3667, 2950, 2362, 1721, 1669, 1436, 1345, 1271, 1187, 1075, 1040,
925, 853, 760, 681 cm−1. HRMS: calcd for C25H18O5 398.1154, found
398.1152. Anal. Found (calcd) for C25H18O5: C, 75.35 (75.37); H,
4.56 (4.55).
2,3-Bis(4-chlorophenyl)-1H-inden-1-one (3l): This was purified by
column chromatography to provide a red solid (27.7 mg, yield 79%).
1
The compound 3l is known, and the H NMR and the 13C NMR
spectra of the compound are in agreement with a previous report.17 1H
NMR (CDCl3, 400 MHz): δ 7.61 (d, J = 6.93 Hz, 1H), 7.45−7.39 (m,
3H), 7.35−7.31 (m, 3H), 7.29−7.27 (m, 2H), 7.23−7.20 (m, 2H),
7.14 (d, J = 7.21 Hz, 1H). 13C NMR (CDCl3, 100 MHz): δ 195.76,
154.27, 144.63, 135.51, 134.03, 133.67, 133.64, 131.52, 131.18, 130.84,
130.47, 129.83, 129.33, 129.31, 128.53, 123.26, 121.16. IR (KBr): ν
3531, 2963, 2872, 2360, 1725, 1604, 1462, 1391, 1288, 1120, 1084,
1016, 965, 863, 725, 658 cm−1. Anal. Found (calcd) for C21H12Cl2O:
C, 71.82 (71.81); H, 3.44 (3.44).
2,3-Di(naphthalen-1-yl)-1H-inden-1-one (3r): This was purified by
column chromatography to provide a red solid (27.5 mg, yield 72%).
1
Mp: 252−254 °C. H NMR (CDCl3, 400 MHz): δ 7.97 (d, J = 8.31
Hz, 1H), 7.89−7.70 (m, 6H), 7.57−7.42 (m, 3H), 7.38−7.28 (m, 5H),
7.22−7.07 (m, 2H), 6.86−6.76 (m, 1H). 13C NMR (CDCl3, 100
MHz): δ 196.17, 146.19, 141.26, 137.00, 135.03, 133.64, 133.49,
133.49, 130.49, 129.39, 129.06, 128.52, 128.19, 127.75, 126.20, 126.18,
126.09, 126.04, 126.01, 125.96, 125.93, 125.87, 125.80, 125.77, 125.76,
125.57, 125.52, 125.48, 123.03, 122.16. IR (KBr): ν 3534, 2927, 1710,
1597, 1456, 1328, 1259, 1178, 1080, 1021, 967, 775, 695 cm−1.
HRMS: calcd for C29H18O 382.1358, found 382.1355. Anal. Found
(calcd) for C29H18O: C, 91.05 (91.07); H, 4.75 (4.74).
2,3-Bis(4-bromophenyl)-1H-inden-1-one (3m): This was purified
by column chromatography to provide a red solid (35.0 mg, yield
1
80%). The compound 3m is known, and the H NMR and the 13C
NMR spectra of the compound are in agreement with a previous
report.17 1H NMR (CDCl3, 400 MHz): δ 7.62−7.58 (m, 2H), 7.47−
7.38 (m, 4H), 7.35−7.27 (m, 4H), 7.18−7.12 (m, 2H). 13C NMR
(CDCl3, 100 MHz): δ 195.61, 154.28, 144.52, 133.63, 132.27, 132.08,
5-Methyl-2,3-diphenyl-1H-inden-1-one (3s): This was purified by
column chromatography to provide a red solid (23.7 mg, yield 80%).
1
Mp: 174−176 °C. H NMR (CDCl3, 400 MHz): δ 7.51 (d, J = 7.27
Hz, 1H), 7.45−7.43 (m, 3H), 7.41−7.38 (m, 2H), 7.29−7.27 (m, 5H),
F
DOI: 10.1021/acs.organomet.7b00004
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7.10 (d, J = 7.29 Hz, 1H), 6.96 (s, 1H), 2.38 (s, 3H). 13C NMR
(CDCl3, 100 MHz): δ 196.16, 154.92, 145.71, 144.37, 132.89, 132.80,
130.87, 129.96, 129.13, 128.91, 128.76, 128.50, 128.37, 128.00, 127.64,
123.04, 122.51, 22.08. IR (KBr): ν 3572, 2921, 2360, 1703, 1602,
1468, 1357, 1274, 1187, 1070, 1034, 921, 837, 733, 695 cm−1. Anal.
Found (calcd) for C22H16O: C, 89.17 (89.16); H, 5.44 (5.44).
2,3,6-Triphenyl-1H-inden-1-one (3t): This was purified by column
chromatography to provide a red solid (26.9 mg, yield 75%). Mp:
ACKNOWLEDGMENTS
■
This work was supported by grants from the NSFC (21572155,
21372175).
REFERENCES
■
(1) (a) Larock, R. C.; Doty, M. J. J. Org. Chem. 1993, 58, 4579−4583.
(b) Harada, Y.; Nakanishi, J.; Fujihara, H.; Tobisu, M.; Fukumoto, Y.;
Chatani, N. J. Am. Chem. Soc. 2007, 129, 5766−5771. (c) Irvine, S.;
Kerr, W. J.; McPherson, A. R.; Pearson, C. M. Tetrahedron 2008, 64,
926−935. (d) Hussain, M.; Hung, N. T.; Khera, R. A.; Villinger, A.;
Langer, P. Tetrahedron Lett. 2011, 52, 184−187. (e) Zhang, J.-L.; Yang,
F.; Wu, Y.-J. Appl. Organomet. Chem. 2011, 25, 675−679.
1
181−183 °C. H NMR (CDCl3, 400 MHz): δ 7.89 (d, J = 1.72 Hz,
1H), 7.63 (d, J = 7.2 Hz, 2H), 7.45−7.38 (m, 7H), 7.33−7.21 (m,
8H). 13C NMR (CDCl3, 100 MHz): δ 196.28, 155.38, 143.99, 142.25,
139.91, 132.80, 131.66, 131.56, 130.78, 129.96, 129.35, 128.93, 128.81,
128.50, 128.09, 127.89, 127.77, 126.77, 121.94, 121.60. IR (KBr): ν
3361, 2925, 1707, 1603, 1464, 1345, 1260, 1078, 967, 844, 767, 728,
697 cm−1. HRMS: calcd for C27H18O 358.1358, found 358.1365. Anal.
Found (calcd) for C27H18O: C, 90.46 (90.47); H, 5.07 (5.06).
6-(Naphthalen-1-yl)-2,3-diphenyl-1H-inden-1-one (3u): This was
purified by column chromatography to provide a red solid (29.4 mg,
yield 72%). Mp: 194−196 °C. 1H NMR (CDCl3, 400 MHz): δ 7.91−
7.86 (m, 3H), 7.75−7.70 (m, 1H), 7.52−7.37 (m, 7H), 7.35−7.23 (m,
9H). 13C NMR (CDCl3, 100 MHz): δ 196.11, 154.98, 146.40, 145.50,
139.28, 133.71, 133.11, 132.56, 131.20, 130.75, 130.44, 129.99, 129.64,
129.26, 128.79, 128.50, 128.48, 128.39, 128.08, 127.79, 126.61, 126.39,
125.99, 125.52, 125.26, 123.25, 122.90. IR (KBr): ν 2926, 2845, 1727,
1601, 1464, 1377, 1262, 1160, 1033, 809, 780, 753 cm−1. HRMS: calcd
for C31H20O 408.1514, found 408.1521. Anal. Found (calcd) for
C31H20O: C, 91.17 (91.15); H, 4.93 (4.94).
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5-Methoxy-2,3-diphenyl-1H-inden-1-one (3v): This was purified
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1
65%). The compound 3v is known, and the H NMR and the 13C
NMR spectra of the compound are in agreement with a previous
report.17 1H NMR (CDCl3, 400 MHz): δ 7.54 (d, J = 7.24 Hz, 1H),
7.41−7.36 (m, 5H), 7.25−7.22 (m, 5H), 6.81−6.79 (m, 2H), 3.86 (s,
3H). 13C NMR (CDCl3, 100 MHz): δ 195.21, 164.70, 153.39, 148.31,
130.62, 129.28, 128.72, 128.44, 128.02, 127.82, 125.99, 123.16, 110.70,
110.59, 55.83. IR (KBr): ν 3568, 2957, 2856, 2362, 1706, 1610, 1478,
1349, 1273, 1222, 1071, 1023, 791, 738, 698 cm−1. Anal. Found
(calcd) for C22H16O2: C, 84.61 (84.59); H, 5.15 (5.16).
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5-Bromo-2,3-diphenyl-1H-inden-1-one (3w): This was purified by
column chromatography to provide a red solid (25.2 mg, yield 70%).
1
The compound 3w is known, and the H NMR and the 13C NMR
spectra of the compound are in agreement with a previous report.17 1H
NMR (CDCl3, 400 MHz): δ 7.46−7.42 (m, 5H), 7.37−7.34 (m, 2H),
7.27−7.26 (m, 6H). 13C NMR (CDCl3, 100 MHz): δ 195.18, 154.14,
147.28, 133.40, 132.18, 131.62, 129.97, 129.56, 129.34, 128.99, 128.36,
128.13, 128.07, 124.69, 124.07. IR (KBr): ν 3558, 3060, 2957, 2925,
2853, 1712, 1602, 1485, 1443, 1351, 1262, 1064, 1028, 785 cm−1.
Anal. Found (calcd) for C21H13BrO: C, 69.83 (69.82); H, 3.63 (3.63).
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ASSOCIATED CONTENT
■
S
* Supporting Information
(7) (a) Seoane, A.; Casanova, N.; Quinones, N.; Mascarenas, J. L.;
̃
̃
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.organo-
met.7b00004.
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NMR spectra of products (PDF)
AUTHOR INFORMATION
■
Corresponding Authors
*E-mail (J. Wang): wjh@tju.edu.cn.
*E-mail (G. Liu): guiyanliu2013@163.com.
ORCID
Xiaobo Yu: 0000-0002-0168-1165
Notes
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Chem. 1996, 61, 6941−6946. (b) Li, B.-J.; Wang, H.-Y.; Zhu, Q.-L.;
The authors declare no competing financial interest.
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DOI: 10.1021/acs.organomet.7b00004
Organometallics XXXX, XXX, XXX−XXX

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DOI: 10.1021/acs.organomet.7b00004
Organometallics XXXX, XXX, XXX−XXX