Rhodium-catalyzed intramolecular hydroacylation of 1,2-disubstituted alkenes for the synthesis of 2-substituted indanones

Article abstract of DOI:10.1016/j.tet.2018.11.057

The intramolecular hydroacylation of 1,2-disubstituted alkenes was considered to be a challenging task due to the side reactions resulted from the lack of additional substituent at 1-position and the low activity caused by the steric hindrance of substituent at 2-position, and an asymmetric version has not been considered possible due to problems associated with the racemization of the products. We have partially solved these problems. Catalyzed by an activated diphosphine-Rh complex and reacted in a selected dihalogenated solvent, the intramolecular hydroacylation of o-(2-arylvinyl)benzaldehydes provided the corresponding 2-aryl-1-indanones in high yields, and its asymmetric variant using o-(2-alkylvinyl)benzaldehydes afforded chiral 2-alkyl-1-indanones in high yields and with moderate enantioselectivities.

Full text of DOI:10.1016/j.tet.2018.11.057

Tetrahedron xxx (xxxx) xxx
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Tetrahedron
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Rhodium-catalyzed intramolecular hydroacylation of 1,2-
disubstituted alkenes for the synthesis of 2-substituted indanones
,
Jing Yuan a, Chong Liu a, Yan Chen a, Zhenfeng Zhang b **, Deyue Yan a,
, b, *
Wanbin Zhang a
a Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University,
Shanghai 200240, PR China
b School of Pharmacy, Shanghai Jiao Tong University, Shanghai 200240, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
The intramolecular hydroacylation of 1,2-disubstituted alkenes was considered to be a challenging task
due to the side reactions resulted from the lack of additional substituent at 1-position and the low ac-
tivity caused by the steric hindrance of substituent at 2-position, and an asymmetric version has not been
considered possible due to problems associated with the racemization of the products. We have partially
solved these problems. Catalyzed by an activated diphosphine-Rh complex and reacted in a selected
dihalogenated solvent, the intramolecular hydroacylation of o-(2-arylvinyl)benzaldehydes provided the
corresponding 2-aryl-1-indanones in high yields, and its asymmetric variant using o-(2-alkylvinyl)
benzaldehydes afforded chiral 2-alkyl-1-indanones in high yields and with moderate
enantioselectivities.
Received 9 October 2018
Received in revised form
23 November 2018
Accepted 26 November 2018
Available online xxx
Keywords:
Asymmetric catalysis
Intramolecular hydroacylation
Rhodium
© 2018 Elsevier Ltd. All rights reserved.
Alkenes
Indanones
1. Introduction
of 1,1,2-trisubstituted alkenes (C and D) [4]. The existing of the
additional 1-substituent again played a crucial role in the process of
Since the 1970's, the hydroacylation of alkenes has attracted
increasing attention as an efficient method for the preparation of
achiral and chiral ketones [1]. Due to the chelating alkenyl and
formyl groups, the intramolecular hydroacylation of alkenes nor-
mally showed high activity and selectivity. However, the cyclic in-
termediates in turn imposed a high structural demand in order to
ensure satisfactory outcomes, especially for the substrates bearing
a rigid backbone and a multi-substituted vinyl group. Therefore,
successful examples have mainly been reported using 1-
monosubstituted or 1,1-disubstituted terminal alkenes (Fig. 1, A
and B) [2,3]. The introduction of additional 1-substituent (R group
in B) avoided side reactions such as dimerization and produced a
intramolecular hydroacylation. As expected, the intramolecular
hydroacylation of 1,2-disubstituted alkenes is still a challenging
task due to the side reactions resulted from lack of additional
substituent at 1-position and the low activity caused by the steric
hindrance of substituent at 2-position, and an asymmetric version
has not been considered possible due to the problem associated
with the racemization of
a-stereocenter. So far, there have been
only sporadic reports with unsatisfactory yields and no enantio-
selectivity [2a,3b]. Catalyzed by a DPPE-Rh complex, the intra-
molecular hydroacylation of a 2-methyl- or 2-phenyl-substituted
alkene bearing an ethyl backbone (E) afforded the desired products
in moderate yields. However, significant amount of byproducts
were also produced, especially for the substrate bearing a rigid
phenyl backbone [3b]. Using a similar catalyst, the intramolecular
hydroacylation of a 2-COOEt-substituted alkene bearing a phenyl
backbone (F) showed significantly lower activity than that of the
corresponding 1-COOEt-substituted alkene [2a]. Therefore, an
efficient and feasible intramolecular hydroacylation of 1,2-
disubstituted alkenes, and an asymmetric version, are highly
desired.
stable
b-stereocenter with high enantioselectivities [2a,d,e].
Recently, there have reported two works focused on the substrates
* Corresponding author. Shanghai Key Laboratory for Molecular Engineering of
Chiral Drugs, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong
University, Shanghai 200240, PR China.
** Corresponding author.
E-mail addresses: zhenfeng@sjtu.edu.cn (Z. Zhang), wanbin@sjtu.edu.cn
(W. Zhang).
Herein, we report an efficient intramolecular hydroacylation of
https://doi.org/10.1016/j.tet.2018.11.057
0040-4020/© 2018 Elsevier Ltd. All rights reserved.
Please cite this article as: J. Yuan et al., Rhodium-catalyzed intramolecular hydroacylation of 1,2-disubstituted alkenes for the synthesis of 2-
substituted indanones, Tetrahedron, https://doi.org/10.1016/j.tet.2018.11.057

2
J. Yuan et al. / Tetrahedron xxx (xxxx) xxx
2. Result and discussion
2-Aryl-1-indanone, as an attractive skeleton and a versatile in-
termediate, has found many valuable applications in the synthesis
of pharmaceuticals, ligands and molecular motors [6]. Therefore,
the preparation of 2-aryl-1-indanones has received a lot of atten-
tion since the early 1950s [7e11]. Several routes for their synthesis
have been developed, including Friedel-Crafts cyclization of phe-
nylpropionic acids [7], cyclocarbonylation of acetylenes [8], cycli-
zation of acrylophenones [9],
a-arylation of indanones [10], and
many more [11]. However, the limited substrate scope and the low
regioselectivity make these methods impractical. According to the
retrosynthetic analysis, a disconnection between the carbonyl
group and sp3-carbon has not previously been considered. There-
fore, an intramolecular hydroacylation of o-(2-arylvinyl)benzalde-
hydes was designed in order to synthesize the target 2-aryl-1-
indanones.
The initial attempt using DPPE-Rh as catalyst and dichloro-
methane (DCM) as solvent, which have been previously employed
in intramolecular hydroacylation of other 1,2-disubstituted alkenes
[2a,3b], failed to transform the model substrate (E)-2-
styrylbenzaldehyde (1a) to the desired product 2-phenyl-2,3-
dihydro-1H-inden-1-one (2a) (Table 1, entry 1). Inspired by the
ability of diphosphine ligands bearing different bite angles to affect
the transformation of sterically hindered alkenes [12], several other
diphosphine ligands bearing different backbones were tested in
this reaction (entries 2e6). It was found that the highest yield was
Fig. 1. Substrates for the intramolecular hydroacylation.
2-aryl- and 2-alkyl-substituted alkenes for the synthesis of 2-
substituted 1-indanones, which have been our long-lasting
research goals during past ten years [5]. By using an activated
diphosphine-Rh catalyst and a selected dihalogenated solvent, the
intramolecular hydroacylation of o-(2-arylvinyl)benzaldehydes (G)
and an asymmetric variant using o-(2-alkylvinyl)benzaldehydes
(H) were developed. This is the first time the aforementioned
problems concerning this type of substrates have been addressed.
In addition, the experimental results of these substrates have pro-
vided new insights into the reaction mechanism.
Table 1
Optimization of reaction conditions.
entrya
ligand
solvent
temp (ꢀC)
conv to 2a/2a' (%)b
1
2
3
4
5
6
7
8
DPPE
DPPP
DPPB
DPPM
DPPF
BINAP
DPPB
DPPB
DPPB
DPPB
DPPB
DPPB
DPPB
DPPB
DPPB
DPPB
DPPB
DPPB
DPPB
DPPB
DCM
DCM
DCM
DCM
DCM
DCM
THF
acetone
MeCN
toluene
dioxane
DCE
DCP
DME
DCE
DCE
DCE
30
30
30
30
30
30
60
50
65
105
100
80
75
80
80
80
80
65
80
80
nr
15/13
20/8
14/5
15/7
13/12
nr
nr
nr
nr
59/7
87/7
50/5
15/6
99/0
98/0
73/0
60/0
99/0
90/0
9
10
11
12
13
14
15c
16c,d
17c,e
18c
19c,f
20c,g
DCE
DCE
DCE
a
Conditions: 1 (0.1 mmol), catalyst (5 mol %), solvent (1 mL), 80 ꢀC, 12 h, unless otherwise noted.
b
c
d
e
f
The conversions of 1a to 2a/2a' were calculated from 1H NMR spectra.
Removing the dissolved hydrogen gas.
Solvent (2 mL).
Catalyst (3 mol %).
2 h.
g
1 h.
Please cite this article as: J. Yuan et al., Rhodium-catalyzed intramolecular hydroacylation of 1,2-disubstituted alkenes for the synthesis of 2-
substituted indanones, Tetrahedron, https://doi.org/10.1016/j.tet.2018.11.057

J. Yuan et al. / Tetrahedron xxx (xxxx) xxx
3
obtained by using DPPB which possesses a long carbon chain
backbone (entry 3). Different solvents were screened at their
boiling temperature using the DPPB-Rh catalyst. No reaction
occurred when the reaction was conducted in tetrahydrofuran
(THF), acetone, acetonitrile (MeCN) or toluene, whereas solvents
with chelating ability, such as dioxane, 1,2-dichloroethane (DCE),
1,2-dichloropropane (DCP) and 1,2-dimethoxyethane (DME) gave
the desired product in high yields (entries 7e14). After primary
screening, DCE was selected as the suitable solvent to afford 87%
conversion of the desired product 2a and with 7% conversion of the
reduced byproduct 2a' (entry 12). After completely removing the
dissolved hydrogen gas [13] in the solvent during the catalyst
activation step, the desired product was obtained in quantitative
yield without any byproduct (entry 15). Reducing the reactant
concentration by half slightly decreased the reaction rate (entry
16), while reducing the catalyst loading or reaction temperature
obviously lowered the conversion (entries 17 and 18). To our
delight, the reaction can go to completion within two hours (entries
19 and 20). Using the activated DPPB-Rh catalyst and the selected
dihalogenated solvent DCE, we investigated the substrate scope of
the hydroacylation of o-(2-arylvinyl)benzaldehydes (Scheme 1). All
the substrates 1a-r gave their corresponding products 2a-r in
complete conversion and with satisfactory isolated yields, regard-
less of the electronic nature and position of the substituents.
Further studies on the asymmetric intramolecular hydro-
acylation of 1a using several chiral diphosphine ligands afforded
the desired product 2a but with poor enantioselectivity (Scheme
2); this is due to racemization. Therefore, a time-dependent
experiment was conducted. Using (R)-DTBM-SegPhos as the
ligand [14], the ee value of the product was determined to be 60%
after 0.5 h, which decreased to 45% after 3 h and 31% after 12 h. The
ee drops further even when the mixture is kept at room
Scheme 2. Screening of ligands in asymmetric intramolecular hydroacylation of 1,2-
disubstituted alkenes.
temperature. After purification by chromatography, only the
racemic product is obtained. We also attempted the intramolecular
hydroacylation of related substrates, such as (E)-2-(2,4,6-
trimethoxystyryl)benzaldehyde and (E)-2-(2,4-dimethoxystyryl)
benzaldehyde, but failed to obtain any products, probably due to
steric hindrance.
In order to reduce racemization, we changed the 2-aryl groups
to electron-donating 2-alkyl groups in the structure of substrates.
Their asymmetric intramolecular hydroacylations were studied for
the synthesis of chiral 2-alkyl-1-indanones, which are important
bioactive compounds [6d,15]. Under the similar conditions, the
asymmetric hydroacylation of (E)-2-(prop-1-en-1-yl)benzal-
dehyde 1s was tested using different diphosphine ligands (Scheme
2). Again, (R)-DTBM-SegPhos was proved to be the best choice. The
product 2-methyl-2,3-dihydro-1H-inden-1-one 2s was obtained in
full conversion and with an enantioselectivity of 67% ee (Table 2,
entry 1). Decreasing the reaction temperature to 60 ꢀC dramatically
Table 2
Optimization of reaction conditions.
entrya
t (h)
conv (%)b
ee (%)c
1
2
3
12
3
1
12
3
1
>99
>99
>99
>99
67
69
71
66
67
71
67
69
4d
5d
6d
7f
8f
72 (28)e
50 (50)e
>99
12
3
>99
a
Conditions: (E)-1s (0.1 mmol), catalyst (5 mol %), DCE (1 mL), 80 ꢀC, unless
otherwise noted.
b
The conversions of 1s to 2s were calculated from 1H NMR spectra.
The ee values were determined by HPLC using chiral columns.
(Z)-1s was used instead of (E)-1s.
The conversions of (Z)-1s to (E)-1s were listed in the parentheses.
c
d
e
f
Scheme 1. Hydroacylation of o-(2-arylvinyl)benzaldehydes.
Z/E mixture (1/1) of 1s was used instead of (E)-1s.
Please cite this article as: J. Yuan et al., Rhodium-catalyzed intramolecular hydroacylation of 1,2-disubstituted alkenes for the synthesis of 2-
substituted indanones, Tetrahedron, https://doi.org/10.1016/j.tet.2018.11.057

4
J. Yuan et al. / Tetrahedron xxx (xxxx) xxx
reduced the conversion to 50% after 24 h with only 32% ee. A time-
dependent experiment has also been conducted over 1, 3, and 12 h
(entries 1e6). It was found that the (E)-isomer was completely
consumed in 1 h to produce the product in 71% ee (entry 3). The
enantioselectivity gradually decreased to 69% over 3 h and 67% over
12 h (entries 2 and 1). This reaction mixture was kept stirring at
room temperature for another 12 h, and no further decrease in
enantioselectivity was observed. The reactivity of the (Z)-isomer is
comparatively lower (entries 4e6). To our surprise, the product
possessing the same configuration and ee value was obtained for
(Z)- and (E)-substrates. When the reaction of the (Z)-isomer was
detected after 1 h, 50% of the starting material was converted to the
product with 71% ee, and the remaining 50% of the (Z)-substrate
was converted to the corresponding (E)-isomer (entry 6). When the
reaction was conducted at room temperature, the (Z)-substrate
completely converted to the (E)-isomer without any hydroacylative
product. Finally, catalysis of the Z/E mixture of 1s with the rhodium
complex of (R)-DTBM-SegPhos gave 2s in quantitative conversion
with 69% ee after 3 h (entries 7 and 8). In addition to 1s, several
other Z/E mixtures of 2-(2-alkylvinyl)benzaldehydes have also been
tested in this reaction (Scheme 3). The ethyl- and propyl-
substituted product 2t and 2u were obtained with 37% and 59%
ee's, respectively. However, the ethyl-substituted product 2t re-
quires a high catalyst loading (10 mol %) for full conversion in 3 h.
By combining the above experimental results and previously
reported data [4,16], a relatively clear mechanism can be proposed
(Scheme 4). The real catalyst PP-Rhþ was produced from pre-
catalyst PP-Rhþ-nbd by H2 activation. According to thermody-
namics, (E)-1s is more stable and (Z)-1s will gradually transformed
to (E)-1s via an intermediate five-membered cyclic Rh-complex
Int-1 (left). With the assistance of the rhodium complex with chi-
ral diphosphine ligand, only (E)-1s can be converted to the corre-
sponding product 2s via an intermediate six-membered cyclic Rh-
complex Int-2 (right).
3. Conclusion
Using an activated diphosphine-Rh catalyst and a selected
dihalogenated solvent, an efficient intramolecular hydroacylation
of 1,2-disubstituted alkenes has been developed. The intra-
molecular hydroacylation of o-(2-arylvinyl)benzaldehydes pro-
vided the 2-aryl-1-indanones in high yields. An asymmetric variant
with moderate enantioselectivities has also been realized using o-
(2-alkylvinyl)benzaldehydes as the substrates. Furthermore, the
experimental results provided some new information for the un-
derstanding of reaction mechanism.
4. Experimental section
4.1. General information
All reactions were performed in a dry glassware or in a glove box
under an atmosphere of nitrogen. The workup was carried out in
air, unless otherwise noted. Column chromatography was per-
formed using silica gel. Solvents were dried and distilled before use
by standard procedures. Commercially available reagents were
used without further purification.
Melting points were measured with SGW X-4 micro melting
point apparatus. 1H NMR (400 MHz), 13C NMR (100 MHz) spectra
were recorded on a Varian MERCURY plus-400 spectrometer. HRMS
was performed on a Waters Micromass Q-TOF Premier mass
spectrometer at the Instrumental Analysis Center of Shanghai Jiao
Tong University. Optical rotations were measured on a Rudolph
Research Analytical Autopol VI automatic polarimeter using a
50 mm path-length cell at 589 nm. Enantioselectivity was
measured by high performance liquid chromatography (HPLC) us-
ing Daicel Chiralcel columns with hexane/isopropanol as eluent.
4.2. General procedure for the preparation of o-(2-arylvinyl)
benzaldehydes [17]
Scheme 3. Asymmetric hydroacylation of o-(2-alkylvinyl) benzaldehydes.
A two-neck round bottom is charged with Pd(OAc)2 (242.6 mg,
1.1 mmol) and K3PO4 (3.32 g, 15.6 mmol) under nitrogen atmo-
sphere. To this mixture was added N,N-dimethylformamide
(20 mL), substituted 2-bromobenzaldehyde (10.8 mmol) and
substituted styrene (21.6 mmol). After stirring at 85 ꢀC for 12 h, the
mixture was cooled to room temperature and poured into ice water
(40 mL). The mixture was filtered through a celite pad and extrac-
ted with EtOAc (40 mL ꢁ 3). The combined organic layers were
washed with brine, dried over Na2SO4 and concentrated. The res-
idue was purified on a silica gel column with petroleum ether
(abbreviate to PE) as eluent to afford the desired product with (E)-
configuration in 36e90% yield.
4.3. General procedure for the preparation of o-(2-alkylvinyl)
benzaldehydes [18]
A suspension of Wittig reagent (40.0 mmol, 1.5 eq) in THF
(50 mL) was cooled to 0 ꢀC and nBuLi (2.5 M in hexane, 17.3 mL,
43.3 mmol, 1.6 eq) was added dropwise to give a red solution. After
stirring for 0.5 h, the 2-bromobenzaldehyde (27.0 mmol) was added
in one portion and the mixture was warmed up to room
Scheme 4. Proposed mechanism for the asymmetric hydroacylation of 2-(prop-1-en-
1-yl)benzaldehyde.
Please cite this article as: J. Yuan et al., Rhodium-catalyzed intramolecular hydroacylation of 1,2-disubstituted alkenes for the synthesis of 2-
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J. Yuan et al. / Tetrahedron xxx (xxxx) xxx
5
temperature and stirred for 10 h. When the reaction was completed
(TLC monitoring), H2O was added to quench the reaction. The
mixture was extracted with EtOAc (30 mL ꢁ 3). The combined
organic phases were washed with water and brine, dried over
Na2SO4 and concentrated. The residue was purified on a silica gel
column with PE as eluent to afford the o-(2-alkylvinyl)bromo-
benzene in 50e76% yield.
The o-(2-alkylvinyl)bromobenzene (23.6 mmol) was dissolved
in THF (50 mL) and cooled to ꢂ78 ꢀC. A solution of nBuLi (2.5 M in
hexane, 10.4 mL, 26.0 mmol, 1.1 eq) was added dropwise and the
reaction temperature was maintained at ꢂ78 ꢀC. After stirring for
30 min at ꢂ78 ꢀC, anhydrous N,N-dimethylformamide (2.2 mL,
28.4 mmol, 1.2 eq) was added dropwise to give a clear solution.
When the reaction was completed (TLC monitoring), H2O was
added slowly to quench the reaction and the pH of the system was
adjusted to 11 with NH4Cl. The water phase was separated and
extracted with EtOAc (50 mL ꢁ 3). The combined organic layers
were washed with water and brine, dried over Na2SO4 and
concentrated. The residue was purified on a silica gel column with
PE as eluent to afford the desired product as a (E/Z)-mixture in
57e76% yield.
4.3.5. (E)-4-Fluoro-2-styrylbenzaldehyde (1e)
Yellow liquid, 0.8 g, 41% yield. 1H NMR (400 MHz, DMSO‑d6):
10.27 (s, 1H), 8.09 (d, J ¼ 16.4 Hz, 1H), 7.90 (t, J ¼ 7.2 Hz, 1H), 7.69
d
(d, J ¼ 10.8 Hz, 1H), 7.60 (d, J ¼ 7.2 Hz, 2H), 7.40e7.22 (m, 5H). 13C
NMR (100 MHz, DMSO‑d6):
d
192.04, 166.57 (164.06, J ¼ 251 Hz),
142.39 (142.30, J ¼ 9 Hz), 136.50, 134.96 (134.86, J ¼ 10 Hz), 134.57,
129.54 (129.51, J ¼ 3 Hz), 128.83, 128.63, 127.18, 122.91 (122.89,
J ¼ 2 Hz), 115.18 (114.96, J ¼ 8 Hz), 113.12 (112.89, J ¼ 23 Hz). HRMS
(ESI): m/z calculated for
227.0872.
C
15H12FO [MþH]þ: 227.0867, found
4.3.6. (E)-4-Chloro-2-styrylbenzaldehyde (1f)
Pale yellow solid, 1.2 g, 76% yield, Mp: 60e61 ꢀC. 1H NMR
(400 MHz, CDCl3):
d
10.25 (s, 1H), 7.98 (d, J ¼ 16.4 Hz, 1H), 7.76 (d,
J ¼ 8.0 Hz, 1H), 7.68 (s, 1H), 7.56 (d, J ¼ 7.6 Hz, 2H), 7.43e7.27 (m,
4H), 7.06 (d, J ¼ 16.0 Hz, 1H). 13C NMR (100 MHz, CDCl3):
d 191.31,
141.53, 140.26, 136.47, 135.15, 133.70, 131.24, 128.90, 128.78, 128.15,
127.77, 127.20, 123.32. HRMS (ESI): m/z calculated for C15H12ClO
[MþH]þ 243.0571, found 243.0580.
4.3.7. (E)-4-Methyl-2-styrylbenzaldehyde (1g)
Yellow liquid, 1.6 g, 78% yield. 1H NMR (400 MHz, CDCl3):
d 10.23
(s, 1H), 8.03 (d, J ¼ 16.0 Hz, 1H), 7.70 (d, J ¼ 7.6 Hz, 1H), 7.55 (d,
4.3.1. (E)-2-Styrylbenzaldehyde (1a)
J ¼ 7.2 Hz, 2H), 7.49 (s, 1H), 7.36 (t, J ¼ 7.2 Hz, 2H), 7.29 (d, J ¼ 6.8 Hz,
Colorless solid, 1.8 g, 90% yield, Mp: 43e46 ꢀC. 1H NMR
1H), 7.21 (d, J ¼ 8.0 Hz, 1H), 7.03 (d, J ¼ 16.0 Hz, 1H), 2.43 (s, 3H). 13
C
(400 MHz, CDCl3):
d
10.33 (s, 1H), 8.05 (d, J ¼ 16.4 Hz, 1H), 7.85 (d,
NMR (100 MHz, CDCl3):
d 192.25, 144.59, 139.85, 136.98, 133.55,
J ¼ 7.6 Hz, 1H), 7.73 (d, J ¼ 7.6 Hz, 1H), 7.58 (d, J ¼ 8.0 Hz, 3H),
132.69, 130.77, 128.73, 128.52, 128.20, 127.64, 126.94, 124.92, 21.86.
HRMS (ESI): m/z calculated for C16H15O [MþH]þ 223.1117, found
223.1127.
7.46e7.35 (m, 3H), 7.35e7.25 (m, 1H), 7.06 (d, J ¼ 16.0 Hz, 1H). 13
C
NMR (100 MHz, CDCl3):
d 192.80, 140.10, 137.03, 134.14, 133.86,
133.08, 132.45, 128.90, 128.45, 127.75, 127.32, 127.11, 124.91. HRMS
(ESI): m/z calculated for
C
15H13
O
[MþH]þ 209.0961, found
4.3.8. (E)-4-Methoxy-2-styrylbenzaldehyde (1h)
209.0976.
White solid, 0.6 g, 40% yield, Mp: 40e43 ꢀC. 1H NMR (400 MHz,
CDCl3):
d
10.17 (s, 1H), 8.07 (d, J ¼ 16.4 Hz, 1H), 7.79 (d, J ¼ 7.6 Hz,
4.3.2. (E)-2-Fluoro-6-styrylbenzaldehyde (1b)
1H), 7.57 (d, J ¼ 7.2 Hz, 2H), 7.39 (t, J ¼ 7.2 Hz, 2H), 7.32 (d, J ¼ 7.2 Hz,
1H), 7.17 (s, 1H), 7.05 (d, J ¼ 16.0 Hz,1H), 6.93 (d, J ¼ 8.4 Hz,1H), 3.92
Yellow liquid, 1.4 g, 73% yield. 1H NMR (400 MHz, CDCl3):
d 10.54
(s, 1H), 8.10 (d, J ¼ 16.0 Hz, 1H), 7.55 (d, J ¼ 7.2 Hz, 2H), 7.46 (s, 2H),
(s, 3H). 13C NMR (100 MHz, CDCl3):
d 191.20, 163.83, 142.35, 136.90,
7.37 (t, J ¼ 7.2 Hz, 2H), 7.30 (d, J ¼ 7.2 Hz, 1H), 7.05 (d, J ¼ 16.8 Hz,
135.19, 133.88, 128.85, 128.43, 127.11, 126.94, 125.00, 113.29, 112.01,
55.67. HRMS (ESI): m/z calculated for C16H15O2 [MþH]þ 239.1067,
found 239.1074.
2H). 13C NMR (100 MHz, CDCl3):
d
189.03 (188.92, J ¼ 11 Hz), 167.33
(164.77, J ¼ 256 Hz), 140.99, 136.77, 135.05 (134.94, J ¼ 11 Hz),
133.96, 128.70, 128.35, 127.11, 125.42 (125.40, J ¼ 2 Hz), 122.62
(122.59, J ¼ 3 Hz), 120.99 (120.93, J ¼ 6 Hz), 114.75 (114.53,
J ¼ 22 Hz). HRMS (ESI): m/z calculated for C15H12FO [MþH]þ
227.0867, found 227.0873.
4.3.9. (E)-5-Methoxy-2-styrylbenzaldehyde (1i)
White solid, 1.0 g, 50% yield, Mp: 54e55 ꢀC. 1H NMR (400 MHz,
CDCl3):
d
10.37 (s, 1H), 7.89 (d, J ¼ 15.6 Hz, 1H), 7.64 (d, J ¼ 8.8 Hz,
1H), 7.54 (d, J ¼ 7.6 Hz, 2H), 7.42e7.33 (m, 3H), 7.30 (d, J ¼ 7.2 Hz,
1H), 7.15 (d, J ¼ 8.4 Hz, 1H), 6.95 (d, J ¼ 16.0 Hz, 1H), 3.89 (s, 3H). 13
C
4.3.3. (E)-5-Fluoro-2-styrylbenzaldehyde (1c)
NMR (100 MHz, CDCl3):
d 191.74, 159.19, 137.04, 133.87, 133.25,
Pale yellow solid, 1.3 g, 79% yield, Mp: 46e47 ꢀC. 1H NMR
132.76, 128.76, 128.72, 128.01, 126.69, 123.78, 121.16, 113.77, 55.56.
HRMS (ESI): m/z calculated for C16H15O2 [MþH]þ 239.1067, found
239.1068.
(400 MHz, CDCl3):
d
10.29 (s, 1H), 7.86 (d, J ¼ 16.0 Hz, 1H), 7.66 (t,
J ¼ 6.0 Hz, 1H), 7.53 (d, J ¼ 6.4 Hz, 3H), 7.38 (t, J ¼ 7.2 Hz, 2H), 7.30 (t,
J ¼ 8.0 Hz, 2H), 6.96 (d, J ¼ 16.4 Hz, 1H). 13C NMR (100 MHz, CDCl3):
d
190.93 (190.91, J ¼ 2 Hz), 163.42 (160.94, J ¼ 248 Hz), 136.75,
4.3.10. (E)-2-Styryl-1-naphthaldehyde (1j)
136.60 (136.57, J ¼ 3 Hz), 134.51, 134.46, 129.60 (129.53, J ¼ 7 Hz),
128.94, 128.58, 127.01, 123.43, 121.39 (121.17, J ¼ 22 Hz), 117.25
(117.03, J ¼ 22 Hz). HRMS (ESI): m/z calculated for C15H12FO [MþH]þ
227.0867, found 227.0871.
Yellow solid, 0.9 g, 42% yield, Mp: 94e97 ꢀC. 1H NMR (400 MHz,
CDCl3):
d
10.45 (s, 1H), 8.26 (d, J ¼ 7.2 Hz, 1H), 8.04 (d, J ¼ 8.4 Hz,
1H), 7.90 (d, J ¼ 7.6 Hz, 1H), 7.85 (d, J ¼ 8.4 Hz, 1H), 7.78 (d,
J ¼ 16.0 Hz, 1H), 7.71e7.52 (m, 4H), 7.51e7.33 (m, 3H), 6.74 (d,
J ¼ 16.4 Hz, 1H). 13C NMR (100 MHz, CDCl3):
d 192.55, 142.47, 140.61,
4.3.4. (E)-3-Fluoro-2-styrylbenzaldehyde (1d)
136.30, 135.82, 132.09, 132.00, 129.01, 128.90, 128.87, 128.66, 128.12,
Yellow liquid, 0.9 g, 47% yield. 1H NMR (400 MHz, CDCl3):
d
10.26
127.03, 127.01, 126.06, 123.31, 121.53. HRMS (ESI): m/z calculated for
(s, 1H), 7.71 (d, J ¼ 7.2 Hz, 1H), 7.62e7.55 (m, 3H), 7.43e7.30 (m, 5H),
C
16H15O2 [MþH]þ 259.1117, found 259.1124.
7.00 (d, J ¼ 16.8 Hz, 1H). 13C NMR (100 MHz, CDCl3):
d 191.51
(191.48, J ¼ 3 Hz), 162.11 (159.61, J ¼ 250 Hz), 139.46 (139.39,
J ¼ 7 Hz),136.70,135.66 (135.63, J ¼ 3 Hz),128.91 (128.81, J ¼ 10 Hz),
128.56, 128.43, 128.35 (128.26, J ¼ 9 Hz), 127.08, 126.56 (126.53,
J ¼ 3 Hz), 120.87 (120.64, J ¼ 23 Hz), 117.61. HRMS (ESI): m/z calcu-
lated for C15H12FO [MþH]þ 227.0867, found 227.0877.
4.3.11. (E)-2-(2-methylstyryl)benzaldehyde (1k)
Yellow solid, 1.0 g, 55% yield, Mp: 57e61 ꢀC. 1H NMR (400 MHz,
CDCl3):
1H), 7.72e7.61 (m, 2H), 7.56 (t, J ¼ 7.2 Hz, 1H), 7.40 (t, J ¼ 7.2 Hz, 1H),
7.24e7.13 (m, 4H), 2.41 (s, 3H). 13C NMR (100 MHz, CDCl3):
192.59,
d
10.29 (s, 1H), 7.88 (d, J ¼ 16.0 Hz, 1H), 7.81 (d, J ¼ 7.2 Hz,
d
Please cite this article as: J. Yuan et al., Rhodium-catalyzed intramolecular hydroacylation of 1,2-disubstituted alkenes for the synthesis of 2-
substituted indanones, Tetrahedron, https://doi.org/10.1016/j.tet.2018.11.057

6
J. Yuan et al. / Tetrahedron xxx (xxxx) xxx
140.36, 136.10, 135.95, 133.78, 133.03, 132.09, 131.92, 130.54, 128.24,
127.64, 127.45, 126.39, 126.08, 125.92, 19.98. HRMS (ESI): m/z
calculated for C16H15O [MþH]þ 223.1117, found 223.1126.
4.3.18. (E)-2-(2-(naphthalen-2-yl)vinyl)benzaldehyde (1r)
Yellow solid, 0.4 g, 36% yield, Mp: 100e102 ꢀC. 1H NMR
(400 MHz, CDCl3):
d
10.35 (s, 1H), 8.18 (d, J ¼ 16.4 Hz, 1H), 7.89 (s,
1H), 7.87e7.74 (m, 6H), 7.60 (d, J ¼ 7.6 Hz, 1H), 7.52e7.40 (m, 3H),
7.22 (d, J ¼ 16.8 Hz, 1H). 13C NMR (100 MHz, CDCl3):
d 192.93,
4.3.12. (E)-2-(3-methylstyryl)benzaldehyde (1l)
Yellow solid, 0.9 g, 48% yield, Mp: 42e44 ꢀC. 1H NMR (400 MHz,
140.05, 134.55, 134.17, 133.89, 133.72, 133.48, 133.05, 132.70, 128.61,
128.28, 127.87, 127.78, 127.57, 127.24, 126.57, 126.39, 125.19, 123.80.
HRMS (ESI): m/z calculated for C15H12FO [MþH]þ 259.1117, found
259.1126.
CDCl3):
d
10.26 (s, 1H), 7.98 (d, J ¼ 16.0 Hz, 1H), 7.78 (d, J ¼ 7.6 Hz,
1H), 7.65 (d, J ¼ 7.6 Hz,1H), 7.51 (t, J ¼ 7.6 Hz,1H), 7.42e7.27 (m, 3H),
7.23 (t, J ¼ 7.6 Hz, 1H), 7.08 (d, J ¼ 7.2 Hz, 1H), 6.97 (d, J ¼ 16.0 Hz,
1H), 2.34 (s, 3H). 13C NMR (100 MHz, CDCl3):
d 192.67, 140.06,
4.3.19. 2-(Prop-1-en-1-yl)benzaldehyde (1s) (E/Z ¼ 1/1) [19]
138.35, 136.85, 134.16, 133.74, 132.90, 132.26, 129.20, 128.70, 127.62,
Pale yellow liquid, 9.0 g, 76% yield. 1H NMR (400 MHz, CDCl3):
127.56, 127.15, 124.48, 124.29, 21.48. HRMS (ESI): m/z calculated for
16H15O [MþH]þ 223.1117, found 223.1121.
d
10.29 (s, 1H, E), 10.23 (s, 1H, Z), 7.90 (dd, J ¼ 8.0, 1.2 Hz, 1H, Z), 7.80
C
(d, J ¼ 8.0 Hz, 1H, E), 7.56 (td, J ¼ 8.0, 1.2 Hz, 1H, Z), 7.53e7.46 (m, 2H,
E), 7.42e7.33 (m, 1Hþ1H, E/Z), 7.29 (d, J ¼ 7.6 Hz, 1H, Z), 7.20 (dq,
J ¼ 15.6, 1.6 Hz, 1H, E), 6.83 (dq, J ¼ 11.2, 1.2 Hz, 1H, Z), 6.17 (dq,
J ¼ 15.6, 6.8 Hz, 1H, E), 6.04 (dq, J ¼ 15.6, 7.2 Hz, 1H, Z), 1.96 (dd,
J ¼ 6.8, 1.6 Hz, 3H, E), 1.69 (dd, J ¼ 7.2, 2.0 Hz, 3H, Z). 13C NMR
4.3.13. (E)-2-(4-methylstyryl)benzaldehyde (1m)
White solid, 1.5 g, 82% yield, Mp: 40e41 ꢀC. 1H NMR (400 MHz,
CDCl3):
d
10.24 (s, 1H), 7.95 (d, J ¼ 16.0 Hz, 1H), 7.75 (d, J ¼ 7.6 Hz,
1H), 7.63 (d, J ¼ 8.0 Hz, 1H), 7.48 (t, J ¼ 7.6 Hz, 1H), 7.41 (d, J ¼ 7.6 Hz,
(100 MHz, CDCl3):
d 192.60, 192.59, 141.04, 140.74, 133.78, 133.72,
2H), 7.33 (t, J ¼ 7.6 Hz, 1H), 7.13 (d, J ¼ 7.6 Hz, 2H), 6.96 (d,
133.64, 132.62, 132.12, 130.87, 130.56, 130.45, 128.77, 127.59, 127.34,
J ¼ 16.4 Hz, 1H), 2.32 (s, 3H). 13C NMR (100 MHz, CDCl3):
d 192.60,
127.14, 127.09, 126.42, 19.02, 14.49. HRMS (ESI): m/z calculated for
C
15H12FO [MþH]þ 147.0804, found 147.0809.
140.10, 138.30, 134.18, 133.91, 133.68, 132.81, 132.22, 129.52, 127.40,
127.01,126.97, 123.58, 21.36. HRMS (ESI): m/z calculated for C16H15
O
[MþH]þ 223.1117, found 223.1129.
4.3.20. 2-(But-1-en-1-yl)benzaldehyde (1t) (E/Z ¼ 1/0.7)
Pale yellow liquid, 1.5 g, 57% yield. 1H NMR (400 MHz, CDCl3):
4.3.14. (E)-2-(4-trifluorostyryl)benzaldehyde (1n)
d
10.30 (s, 1H, E), 10.25 (s, 0.7H, Z), 7.90 (d, J ¼ 3.6 Hz, 0.7H, Z), 7.81
White solid, 1.3 g, 53% yield, Mp: 39e42 ꢀC. 1H NMR (400 MHz,
(d, J ¼ 7.6 Hz, 1H, E), 7.60e7.47 (m, 2H þ 0.7H, E/Z), 7.42e7.32 (m,
0.7Hþ1H, E/Z), 7.27 (d, J ¼ 6.8 Hz, 1H, Z), 7.17 (d, J ¼ 15.6 Hz, 1H, E),
6.77 (d, J ¼ 11.6 Hz, 0.7H, Z), 6.26e6.14 (m, 1H, E), 5.97e5.86 (m,
0.7H, Z), 2.36e2.25 (m, 2H, E), 2.13e2.02 (m, 1.4H, Z), 1.13 (t,
J ¼ 7.6 Hz, 3H, E), 0.99 (t, J ¼ 7.6 Hz, 2.1H, Z). 13C NMR (100 MHz,
CDCl3):
d
10.24 (s, 1H), 8.17 (d, J ¼ 16.0 Hz, 1H), 7.81 (d, J ¼ 6.0 Hz,
1H), 7.71 (d, J ¼ 6.4 Hz, 1H), 7.60 (s, 5H), 7.47 (s, 1H), 7.04 (d,
J ¼ 16.4 Hz,1H). 13C NMR (100 MHz, CDCl3):
d 192.93,140.45,138.86,
133.83, 133.45, 132.06, 131.87, 130.25 (129.93, 129.61, 129.29,
J ¼ 32 Hz), 128.26, 128.17 (125.59, 122.88, 120.18, J ¼ 270 Hz),127.78,
127.18, 127.11, 125.76 (125.72, 125.68, 125.64, J ¼ 4 Hz). HRMS (ESI):
m/z calculated for C16H12F3O [MþH]þ 277.0835, found 277.0843.
CDCl3):
d 192.56, 141.16, 141.02, 139.05, 137.87, 133.75, 133.64,
133.29, 132.72, 130.79, 130.53, 128.70, 127.63, 127.35, 127.09, 124.89,
124.76, 26.53, 21.98, 14.07, 13.56. HRMS (ESI): m/z calculated for
C
15H12FO [MþH]þ 161.0961, found 161.0963.
4.3.15. (E)-2-(4-fluorostyryl)benzaldehyde (1o)
Yellow liquid, 1.0 g, 57% yield. 1H NMR (400 MHz, CDCl3):
d 10.26
4.3.21. 2-(Pent-1-en-1-yl)benzaldehyde (1u) (E/Z ¼ 1/1.3)
Pale yellow liquid, 2.7 g, 75% yield. 1H NMR (400 MHz, CDCl3):
(s, 1H), 7.97 (d, J ¼ 16.4 Hz, 1H), 7.80 (d, J ¼ 7.6 Hz, 1H), 7.67 (d,
J ¼ 8.0 Hz, 1H), 7.59e7.46 (m, 3H), 7.41 (d, J ¼ 7.6 Hz, 1H), 7.05 (t,
J ¼ 8.4 Hz, 2H), 6.98 (d, J ¼ 16.4 Hz, 1H). 13C NMR (100 MHz, CDCl3):
d
10.29 (s, 1H, E), 10.25 (s, 1.3H, Z), 7.86 (d, J ¼ 7.6 Hz, 1.3H, Z), 7.77 (d,
J ¼ 7.2 Hz, 1H, E), 7.54e7.44 (m, 2H þ 1.3H, E/Z), 7.38e7.28 (m,
1H þ 1.3H, E/Z), 7.23 (d, J ¼ 7.6 Hz,1.3H, Z), 7.15 (d, J ¼ 15.6 Hz,1H, E),
6.77 (d, J ¼ 11.2 Hz, 1H, Z), 6.17e6.08 (m, 1H, E), 5.94e5.85 (m, 1.3H,
Z), 2.23 (q, J ¼ 7.2 Hz, 2H, E), 2.01 (q, J ¼ 7.2 Hz, 2.6H, Z), 1.57e1.44
(m, 2H, E), 1.47e1.32 (m, 2.6H, Z), 0.94 (t, J ¼ 7.2 Hz, 3H, E), 0.82 (t,
d
192.76, 163.92 (161.45, J ¼ 247 Hz), 139.58, 133.71, 133.19 (133.16,
J ¼ 3 Hz), 132.85, 132.80, 132.47, 128.61 (128.53, J ¼ 8 Hz), 127.65,
126.99, 124.70 (124.68, J ¼ 2 Hz), 115.82 (115.61, J ¼ 21 Hz). HRMS
(ESI): m/z calculated for
C
15H12FO [MþH]þ 227.0867, found
J ¼ 7.2 Hz, 3.9H, Z). 13C NMR (100 MHz, CDCl3):
d 192.40, 141.06,
227.0880.
137.32, 136.15, 133.66, 133.56, 132.66, 130.70, 130.48, 128.55, 127.57,
127.25, 127.02, 125.94, 125.42, 35.43, 30.52, 22.66, 22.40, 13.76.
HRMS (ESI): m/z calculated for C15H12FO [MþH]þ 175.1117, found
175.1124.
4.3.16. (E)-2-(4-chlorostyryl)benzaldehyde (1p)
Deep yellow liquid, 1.4 g, 76% yield. 1H NMR (400 MHz, CDCl3):
d
10.25 (s, 1H), 8.03 (d, J ¼ 16.4 Hz, 1H), 7.80 (d, J ¼ 7.2 Hz, 1H), 7.68
(d, J ¼ 7.6 Hz, 1H), 7.55 (t, J ¼ 7.6 Hz, 1H), 7.50e7.37 (m, 3H), 7.31 (d,
4.4. General procedure for intramolecular hydroacylation
J ¼ 7.2 Hz, 2H), 6.97 (d, J ¼ 16.4 Hz, 1H). 13C NMR (100 MHz, CDCl3):
d
192.78, 139.33, 135.46, 133.80, 133.73, 132.99, 132.88, 132.30,
The Rh[(ndb)2]BF4 (0.025 mmol) and the ligand (0.025 mmol)
were placed in a dried Schlenk tube. The tube was purged with
nitrogen. Then, anhydrous and degassed DCE (1 mL) was intro-
duced in a glove box under an atmosphere of nitrogen. After stir-
ring at room temperature with hydrogen (pressurized to 1 atm) for
30 min, the reaction was stopped. Solvent was removed with an oil
pump. The (E)-o-(2-arylvinyl)benzaldehyde (0.5 mmol) was added
to the reaction mixture in a glove box under an atmosphere of ni-
trogen. The reaction was stirred at 80 ꢀC for 12 h. Then, the reaction
mixture was concentrated. The enantioselectivity of the product
was determined by HPLC using chiral columns. The yield was
calculated after purification on a silica gel column with freshly
distilled PE/Et2O (100/1) as eluent.
128.92, 128.15, 127.83, 127.04, 125.59. HRMS (ESI): m/z calculated
for C15H12FO [MþH]þ 243.0571, found 243.0578.
4.3.17. (E)-2-(4-methoxystyryl)benzaldehyde (1q)
Yellow solid, 0.7 g, 44% yield, Mp: 84e85 ꢀC. 1H NMR (400 MHz,
CDCl3):
d
10.32 (s, 1H), 7.91 (d, J ¼ 16.4 Hz, 1H), 7.83 (d, J ¼ 8.0 Hz,
1H), 7.71 (d, J ¼ 8.0 Hz, 1H), 7.57 (t, J ¼ 7.6 Hz, 1H), 7.51 (d, J ¼ 8.0 Hz,
2H), 7.41 (t, J ¼ 7.6 Hz, 1H), 7.02 (d, J ¼ 16.0 Hz, 1H), 6.92 (d,
J ¼ 8.0 Hz, 2H), 3.84 (s, 3H). 13C NMR (100 MHz, CDCl3):
d 192.88,
159.98, 140.50, 133.82, 133.78, 132.87, 132.34, 129.87, 128.43, 127.35,
127.09, 122.56, 114.35, 55.49. HRMS (ESI): m/z calculated for
C
15H12FO [MþH]þ 239.1067, found 239.1072.
Please cite this article as: J. Yuan et al., Rhodium-catalyzed intramolecular hydroacylation of 1,2-disubstituted alkenes for the synthesis of 2-
substituted indanones, Tetrahedron, https://doi.org/10.1016/j.tet.2018.11.057

J. Yuan et al. / Tetrahedron xxx (xxxx) xxx
7
4.4.1. 2-Phenyl-2,3-dihydro-1H-inden-1-one (2a)
4.4.7. 5-Methyl-2-phenyl-2,3-dihydro-1H-inden-1-one (2g)
Pale yellow solid, 89 mg, 80% yield. Mp: 78e81 ꢀC. 1H NMR
(400 MHz, CDCl3):
Yellow solid, 83 mg, 80% yield. Mp: 49e53 ꢀC. 1H NMR
(400 MHz, CDCl3):
d
7.80 (d, J ¼ 7.2 Hz, 1H), 7.63 (t, J ¼ 6.8 Hz, 1H),
d
7.70 (d, J ¼ 7.6 Hz, 1H), 7.35e7.26 (m, 3H),
7.52 (d, J ¼ 7.2 Hz, 1H), 7.41 (t, J ¼ 6.8 Hz, 1H), 7.34e7.12 (m, 5H),
7.27e7.20 (m, 2H), 7.17 (d, J ¼ 7.2 Hz, 2H), 3.92e3.82 (m, 1H), 3.63
3.90e3.84 (m, 1H), 3.67 (dd, J ¼ 16.8, 7.6 Hz, 1H), 3,26 (d, J ¼ 17.2 Hz,
(dd, J ¼ 17.6, 8.0 Hz, 1H), 3.23 (dd, J ¼ 17.2, 3.2 Hz, 1H), 2.47 (s, 3H).
1H). 13C NMR (100 MHz, CDCl3):
d
206.04, 153.77, 139.78, 136.30,
13C NMR (100 MHz, CDCl3):
d 205.50, 154.24, 146.27, 139.97, 133.96,
135.11, 128.91, 127.93, 127.82, 127.09, 126.53, 124.58, 53.47, 35.91.
HRMS (ESI): m/z calculated for C15H13O [MþH]þ 209.0961, found
209.0960. Determined by HPLC analysis using a Daicel Chiralcel IC-
3 column (25 cm ꢁ 0.46 cm), hexane/isopropanol ¼ 99/1, 1 mL/min,
254 nm, tR (major) ¼ 14.5 min, tR (minor) ¼ 22.4 min.
129.01, 128.79, 127.80, 126.92, 126.75, 124.33, 53.53, 35.73, 22.13.
HRMS (ESI): m/z calculated for C16H15O [MþH]þ 223.1117, found
223.1120.
4.4.8. 5-Methoxy-2-phenyl-2,3-dihydro-1H-inden-1-one (2h)
White solid, 96 mg, 81% yield. Mp: 90e93 ꢀC. 1H NMR (400 MHz,
4.4.2. 7-Fluoro-2-phenyl-2,3-dihydro-1H-inden-1-one (2b)
CDCl3):
d
7.74 (d, J ¼ 8.4 Hz,1H), 7.31 (t, J ¼ 7.2 Hz, 2H), 7.27e7.21 (m,
White solid, 91 mg, 81% yield. Mp: 86e89 ꢀC. 1H NMR (400 MHz,
1H), 7.18 (d, J ¼ 7.2 Hz, 2H), 6.95 (s, 2H), 3.91 (s, 3H), 3.90e3.85 (m,
CDCl3):
d
7.61 (q, J ¼ 6.8 Hz, 1H), 7.37e7.22 (m, 4H), 7.19 (d,
1H), 3.63 (dd, J ¼ 17.2, 8.0 Hz, 1H), 3.22 (d, J ¼ 17.2 Hz, 1H)). 13C NMR
J ¼ 7.2 Hz, 2H), 7.03 (t, J ¼ 8.4 Hz, 1H), 3.94e3.88 (m, 1H), 3.74e3.63
(100 MHz, CDCl3): d 204.28, 165.69, 156.85, 140.25, 129.56, 128.89,
(dd, J ¼ 17.2, 8.4 Hz, 1H), 3.28 (d, J ¼ 17.2 Hz,1H). 13C NMR (100 MHz,
127.89, 127.02, 126.28, 115.85, 109.62, 55.81, 53.66, 36.05. HRMS
(ESI): m/z calculated for
239.1061.
CDCl3):
d
202.13 (202.11, J ¼ 2 Hz), 160.81 (158.18, J ¼ 263 Hz),
C
16H15O2 [MþH]þ 239.1067, found
155.79 (155.76, J ¼ 3 Hz), 139.21, 137.08 (137.00, J ¼ 8 Hz), 128.99,
127.96, 127.31, 124.23 (124.10, J ¼ 13 Hz), 122.35 (122.31, J ¼ 4 Hz),
114.86 (114.67, J ¼ 19 Hz), 53.91, 35.75. HRMS (ESI): m/z calculated
for C15H12FO [MþH]þ 227.0867, found 227.0865.
4.4.9. 6-Methoxy-2-phenyl-2,3-dihydro-1H-inden-1-one (2i)
White solid, 96 mg, 81% yield. Mp: 137e140 ꢀC. 1H NMR
(400 MHz, CDCl3):
d
7.31 (d, J ¼ 8.0 Hz, 1H), 7.22 (t, J ¼ 7.2 Hz, 2H),
4.4.3. 6-Fluoro-2-phenyl-2,3-dihydro-1H-inden-1-one (2c)
7.15 (s, 3H), 7.08 (d, J ¼ 7.2 Hz, 2H), 3.84e3.77 (m, 1H), 3.74 (s, 3H),
Yellow solid, 105 mg, 93% yield. Mp: 94e96 ꢀC. 1H NMR
3.50 (dd, J ¼ 17.2, 8.0 Hz, 1H), 3.08 (d, J ¼ 17.2 Hz, 1H)). 13C NMR
(400 MHz, CDCl3):
d
7.53e7.46 (m, 1H), 7.45 (d, J ¼ 7.6 Hz, 1H),
(100 MHz, CDCl3): d 206.01, 159.77, 146.61, 139.91, 137.48, 128.90,
7.40e7.22 (m, 4H), 7.18 (d, J ¼ 7.2 Hz, 2H), 3.98e3.90 (m, 1H), 3.66
127.89, 127.21, 127.04, 124.55, 105.63, 55.70, 54.28, 35.30. HRMS
(ESI): m/z calculated for
239.1067.
(dd, J ¼ 15.6, 8.0 Hz,1H), 3.24 (d, J ¼ 17.2 Hz,1H). 13C NMR (100 MHz,
C
16H15O2 [MþH]þ 239.1067, found
CDCl3):
d
204.99 (204.97, J ¼ 2 Hz), 163.74 (161.27, J ¼ 247 Hz),
149.01 (148.99, J ¼ 2 Hz), 139.18, 137.96 (137.89, J ¼ 7 Hz), 128.88,
127.82, 127.76, 127.16, 122.85 (122.61, J ¼ 24 Hz), 120.35 (110.13,
J ¼ 22 Hz), 54.20, 35.19. HRMS (ESI): m/z calculated for C15H12FO
[MþH]þ 227.0867, found 227.0865.
4.4.10. 2-Phenyl-2,3-dihydro-1H-cyclopenta[a]naphthalen-1-one
(2j)
Yellow solid, 115 mg, 90% yield. Mp: 60e61 ꢀC. 1H NMR
(400 MHz, CDCl3):
d
8.05 (d, J ¼ 8.0 Hz, 1H), 7.97 (d, J ¼ 8.0 Hz, 1H),
4.4.4. 4-Fluoro-2-phenyl-2,3-dihydro-1H-inden-1-one (2d)
7.85 (d, J ¼ 8.4 Hz, 1H), 7.78 (d, J ¼ 8.4 Hz, 1H), 7.74e7.60 (m, 2H),
Yellow solid, 96 mg, 85% yield. Mp: 34e36 ꢀC. 1H NMR
7.36e7.17 (m, 5H), 4.06e3.93 (m, 2H) 3.53 (d, J ¼ 16.0 Hz, 1H). 13
C
(400 MHz, CDCl3):
d
7.61 (d, J ¼ 7.2 Hz, 1H), 7.40 (q, J ¼ 7.2 Hz, 1H),
NMR (100 MHz, CDCl3): d 205.94, 155.23, 140.01, 136.85, 133.86,
7.36e7.21 (m, 4H), 7.18 (d, J ¼ 7.6 Hz, 2H), 3.95e3.85 (m, 1H), 3.69
130.33, 129.53, 129.09, 129.03, 129.00, 127.94, 127.32, 127.17, 124.63,
(dd, J ¼ 17.6, 8.4 Hz, 1H), 3.25 (dd, J ¼ 17.6, 2.8 Hz, 1H). 13C NMR
120.13, 53.37, 34.84. HRMS (ESI): m/z calculated for C19H15
O
(100 MHz, CDCl3):
d
204.66 (204.64, J ¼ 2 Hz), 161.64 (158.65,
[MþH]þ 259.1117, found 259.1128.
J ¼ 299 Hz), 139.55 (139.35, J ¼ 20 Hz), 139.06, 132.02, 129.83
(129.77, J ¼ 6 Hz), 128.95, 127.86, 127.26, 121.20 (121.00, J ¼ 20 Hz),
120.27 (120.23, J ¼ 4 Hz), 53.16, 31.35. HRMS (ESI): m/z calculated
for C15H12FO [MþH]þ 227.0867, found 227.0868.
4.4.11. 2-(o-Tolyl)-2,3-dihydro-1H-inden-1-one (2k)
White solid, 96 mg, 86% yield. Mp: 96e98 ꢀC. 1H NMR (400 MHz,
CDCl3):
d
7.84 (d, J ¼ 7.6 Hz, 1H), 7.65 (t, J ¼ 7.6 Hz, 1H), 7.51 (d,
J ¼ 7.6 Hz, 1H), 7.43 (t, J ¼ 7.6 Hz, 1H), 7.23e7.07 (m, 3H), 6.96 (d,
J ¼ 7.2 Hz, 1H), 4.15e4.06 (m, 1H), 3.70 (dd, J ¼ 17.2, 8.0 Hz, 1H), 3.15
(d, J ¼ 17.2 Hz, 1H), 2.35 (s, 3H). 13C NMR (100 MHz, CDCl3):
4.4.5. 5-Fluoro-2-phenyl-2,3-dihydro-1H-inden-1-one (2e)
White solid, 90 mg, 80% yield. Mp: 99e101 ꢀC. 1H NMR
(400 MHz, CDCl3):
d
7.82 (t, J ¼ 6.4 Hz, 1H), 7.33 (t, J ¼ 7.2 Hz, 2H),
d 206.84, 153.53, 138.66, 136.79, 136.76, 135.10, 130.84, 127.83,
7.29e7.22 (m, 1H), 7.22e7.08 (m, 4H), 3.95e3.88 (m, 1H), 3.67 (dd,
127.61, 127.17, 126.61, 126.53, 124.45, 51.01, 35.70, 20.24. HRMS
J ¼ 17.6, 8.4 Hz, 1H), 3.26 (d, J ¼ 17.6 Hz, 1H). 13C NMR (100 MHz,
(ESI): m/z calculated for C16H15O [MþH]þ 223.1117, found 223.1124.
CDCl3):
d
203.98, 168.65 (166.10, J ¼ 255 Hz), 156.55 (155.45,
J ¼ 10 Hz), 139.32, 132.59 (132.58, J ¼ 1 Hz), 128.87, 127.73, 127.13,
126.86 (126.75, J ¼ 11 Hz), 116.20 (115.97, J ¼ 23 Hz), 113.15 (112.93,
J ¼ 22 Hz), 53.54, 35.62. HRMS (ESI): m/z calculated for C15H12FO
[MþH]þ 227.0867, found 227.0872.
4.4.12. 2-(m-Tolyl)-2,3-dihydro-1H-inden-1-one (2l)
Yellow solid, 94 mg, 83% yield. Mp: 40e43 ꢀC. 1H NMR
(400 MHz, CDCl3):
d
7.81 (d, J ¼ 6.8 Hz, 1H), 7.62 (t, J ¼ 6.4 Hz, 1H),
7.51 (d, J ¼ 6.8 Hz, 1H), 7.41 (t, J ¼ 6.8 Hz, 1H), 7.27e7.14 (m, 1H), 7.05
(d, J ¼ 6.8 Hz, 1H), 7.01e6.92 (m, 2H), 3.93e3.76 (m, 1H), 3.66 (dd,
J ¼ 17.2, 8.0 Hz, 1H), 3.27 (d, J ¼ 17.2 Hz, 1H), 2.30 (s, 3H). 13C NMR
4.4.6. 5-Chloro-2-phenyl-2,3-dihydro-1H-inden-1-one (2f)
Pale yellow solid, 104 mg, 88% yield. Mp: 75e77 ꢀC. 1H NMR
(100 MHz, CDCl3): d 206.26, 153.86, 139.75, 138.55, 136.37, 135.08,
(400 MHz, CDCl3):
d
7.74 (d, J ¼ 8.0 Hz, 1H), 7.53 (s, 1H), 7.40 (d,
128.81, 128.70, 127.89, 127.79, 126.53, 124.95, 124.58, 53.46, 36.03,
21.52. HRMS (ESI): m/z calculated for C16H15O [MþH]þ 223.1117,
found 223.1124.
J ¼ 8.0 Hz, 1H), 7.36e7.22 (m, 3H), 7.17 (d, J ¼ 7.2 Hz, 2H), 3.95e3.86
(m, 1H), 3.67 (dd, J ¼ 17.6, 8.0 Hz, 1H), 3.25 (d, J ¼ 17.6 Hz, 1H). 13
C
NMR (100 MHz, CDCl3):
d 204.60, 155.23, 141.72, 139.33, 134.78,
129.04, 128.72, 127.89, 127.32, 126.77, 125.75, 53.56, 35.60. HRMS
(ESI): m/z calculated for C15H12ClO [MþH]þ 243.0571, found
243.0578.
4.4.13. 2-(p-Tolyl)-2,3-dihydro-1H-inden-1-one (2m)
White solid, 91 mg, 81% yield. Mp: 40e42 ꢀC. 1H NMR (400 MHz,
CDCl3):
d
7.80 (d, J ¼ 6.8 Hz, 1H), 7.63 (t, J ¼ 6.8 Hz, 1H), 7.51 (d,
Please cite this article as: J. Yuan et al., Rhodium-catalyzed intramolecular hydroacylation of 1,2-disubstituted alkenes for the synthesis of 2-
substituted indanones, Tetrahedron, https://doi.org/10.1016/j.tet.2018.11.057

8
J. Yuan et al. / Tetrahedron xxx (xxxx) xxx
J ¼ 7.2 Hz, 1H), 7.41 (t, J ¼ 7.2 Hz, 1H), 7.16e7.02 (m, 4H), 3.89e3.80
(m, 1H), 3.66 (dd, J ¼ 17.2, 8.4 Hz, 1H), 3.24 (d, J ¼ 17.2 Hz, 1H), 2.31
153.57, 136.41, 134.77, 127.43, 126.62, 124.04, 42.06, 35.03, 16.35.
HRMS (ESI): m/z calculated for C10H11O [MþH]þ 147.0804, found
(s, 3H). 13C NMR (100 MHz, CDCl3):
d
206.25, 153.77, 136.70, 136.67,
147.0809. [
a
]20 D ꢂ35 (c 0.8, CH2Cl2). 71% ee. Determined by HPLC
136.31, 135.02, 129.58, 127.77, 127.75, 126.50, 124.53, 53.13, 35.92,
21.13. HRMS (ESI): m/z calculated for C16H15O [MþH]þ 223.1117,
found 223.1133.
analysis using a Daicel Chiralcel IC-3 column (25 cm ꢁ 0.46 cm),
hexane/isopropanol ¼ 99/1,
0.5 mL/min, 254 nm, tR (mi-
nor) ¼ 13.2 min, tR (major) ¼ 14.1 min. The absolute configuration
was established by comparison of the optical rotation and HPLC
chart to the literature's results.
4.4.14. 2-(4-(Trifluoromethyl)phenyl)-2,3-dihydro-1H-inden-1-one
(2n)
White solid, 123 mg, 89% yield. Mp: 76e77 ꢀC. 1H NMR
4.4.20. (R)-2-Ethyl-2,3-dihydro-1H-inden-1-one (2t)
Pale yellow liquid, 66 mg, 82% yield. 1H NMR (400 MHz, CDCl3):
(400 MHz, CDCl3):
d
7.82 (d, J ¼ 7.6 Hz, 1H), 7.68 (t, J ¼ 7.2 Hz, 1H),
7.62e7.50 (m, 3H), 7.45 (t, J ¼ 7.2 Hz, 1H), 7.32 (d, J ¼ 8.0 Hz, 2H),
d
7.74 (d, J ¼ 7.6 Hz, 1H), 7.57 (t, J ¼ 7.2 Hz, 1H), 7.45 (d, J ¼ 7.2 Hz,
3.99e3.91 (m, 1H), 3.73 (dd, J ¼ 17.2, 8.0 Hz, 1H), 3.30 (d, J ¼ 17.2 Hz,
1H), 7.35 (t, J ¼ 6.8 Hz, 1H), 3.31 (dd, J ¼ 16.8, 7.2 Hz, 1H), 2.82 (d,
J ¼ 17.2 Hz,1H), 2.67e2.54 (m, 1H), 2.06e1.88 (m,1H),1.63e1.44 (m,
1H). 13C NMR (100 MHz, CDCl3):
d 205.06, 153.44, 143.73, 136.02,
1H), 1.01 (t, J ¼ 6.8 Hz, 3H). 13C NMR (100 MHz, CDCl3):
d 209.15,
135.46, 129.87 (129.55, 129.23, 128.90, J ¼ 32 Hz), 128.41, 128.30
(125.59, 122.89, 120.23, J ¼ 270 Hz), 128.10, 126.61, 125.91 (125.87,
125.84, 125.80, J ¼ 4 Hz), 124.73, 53.21, 35.56. HRMS (ESI): m/z
calculated for C16H12F3O [MþH]þ 277.0835, found 277.0842.
153.94, 137.10, 134.72, 127.42, 126.67, 123.96, 48.90, 32.48, 24.61,
11.72. HRMS (ESI): m/z calculated for C11H13O [MþH]þ 161.0961,
found 161.0970. [
a
]20 D ꢂ22 (c 0.6, CH2Cl2). 37% ee. Determined by
HPLC analysis using
(25 cm ꢁ 0.46 cm),
a
Daicel Chiralcel IC-3 column
0.5 mL/min,
4.4.15. 2-(4-Fluorophenyl)-2,3-dihydro-1H-inden-1-one (2o)
White solid, 97 mg, 86% yield. Mp: 50e52 ꢀC. 1H NMR (400 MHz,
hexane/isopropanol ¼ 99/1,
254 nm, tR (minor) ¼ 10.7 min, tR (major) ¼ 11.6 min.
CDCl3):
d
7.81 (d, J ¼ 7.6 Hz, 1H), 7.66 (t, J ¼ 6.8 Hz, 1H), 7.53 (d,
J ¼ 7.2 Hz, 1H), 7.43 (t, J ¼ 6.8 Hz, 1H), 7.16 (s, 2H), 7.01 (t, J ¼ 7.6 Hz,
4.4.21. (R)-2-Propyl-2,3-dihydro-1H-inden-1-one (2u)
Pale yellow liquid, 75 mg, 86% yield. 1H NMR (400 MHz, CDCl3):
2H), 3.93e3.84 (m, 1H), 3.70 (dd, J ¼ 17.2, 8.0 Hz, 1H), 3.25 (d,
J ¼ 17.2 Hz, 1H). 13C NMR (100 MHz, CDCl3):
d 205.91, 163.23
d
7.75 (d, J ¼ 7.6 Hz, 1H), 7.57 (t, J ¼ 7.6 Hz, 1H), 7.45 (d, J ¼ 7.6 Hz,
(160.79, J ¼ 244 Hz),153.56,136.16,135.46 (135.43, J ¼ 3 Hz),135.30,
129.56 (129.48, J ¼ 8 Hz), 127.98, 126.58, 124.70, 115.91 (115.70,
J ¼ 21 Hz), 52.71, 35.96. HRMS (ESI): m/z calculated for C15H12FO
[MþH]þ 227.0867, found 227.0868.
1H), 7.36 (t, J ¼ 7.2 Hz, 1H), 3.32 (dd, J ¼ 17.2, 7.6 Hz, 1H), 2.81 (d,
J ¼ 17.2 Hz, 1H), 2.68e2.59 (m, 1H), 1.98e1.87 (m, 1H), 1.54e1.37 (m,
3H), 0.96 (t, J ¼ 6.4 Hz, 3H). 13C NMR (100 MHz, CDCl3):
d 209.22,
153.91, 137.02, 134.73, 127.44, 126.66, 124.01, 47.45, 33.78, 33.04,
20.80, 14.20. HRMS (ESI): m/z calculated for C12H15O [MþH]þ
4.4.16. 2-(4-Chlorophenyl)-2,3-dihydro-1H-inden-1-one (2p)
White solid, 108 mg, 86% yield. Mp: 64e65 ꢀC. 1H NMR
175.1117, found 175.1112. [
a
]20 D ꢂ28 (c 0.9, CH2Cl2). 59% ee.
Determined by HPLC analysis using a Daicel Chiralcel IC-3 column
0.5 mL/min,
(400 MHz, CDCl3):
d
7.80 (d, J ¼ 7.6 Hz, 1H), 7.65 (t, J ¼ 7.2 Hz, 1H),
(25 cm ꢁ 0.46 cm),
hexane/isopropanol ¼ 99/1,
7.53 (d, J ¼ 7.6 Hz, 1H), 7.42 (t, J ¼ 7.2 Hz, 1H), 7.28 (d, J ¼ 8.0 Hz, 2H),
7.12 (d, J ¼ 7.6 Hz, 2H), 3.89e3.81 (m, 1H), 3.68 (dd, J ¼ 17.2, 8.0 Hz,
254 nm, tR (minor) ¼ 9.6 min, tR (major) ¼ 10.4 min.
1H), 3.24 (d, J ¼ 17.6 Hz, 1H). 13C NMR (100 MHz, CDCl3):
d 205.45,
Acknowledgments
153.40, 138.06, 135.96, 135.22, 132.83, 129.24, 128.92, 127.87, 126.47,
124.55, 52.68, 35.61. HRMS (ESI): m/z calculated for C15H12ClO
[MþH]þ 243.0571, found 243.0581.
This work was partially supported by National Natural Science
Foundation of China (Nos. 21572131 and 21620102003), Shanghai
Municipal Education Commission (No. 201701070002E00030). We
thank the Instrumental Analysis Center of Shanghai Jiao Tong
University.
4.4.17. 2-(4-Methoxyphenyl)-2,3-dihydro-1H-inden-1-one (2q)
White solid, 99 mg, 83% yield. Mp: 64e66 ꢀC. 1H NMR (400 MHz,
CDCl3):
d
7.81 (d, J ¼ 7.2 Hz, 1H), 7.64 (t, J ¼ 6.8 Hz, 1H), 7.52 (d,
J ¼ 7.2 Hz, 1H), 7.42 (t, J ¼ 6.8 Hz, 1H), 7.11 (d, J ¼ 7.2 Hz, 2H), 6.86 (d,
J ¼ 8.0 Hz, 2H), 3.89e3.81 (m, 1H), 3.78 (s, 1H), 3.78 (dd, J ¼ 17.2,
7.6 Hz, 1H), 3.25 (d, J ¼ 17.6 Hz, 1H). 13C NMR (100 MHz, CDCl3):
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.tet.2018.11.057.
d
206.47, 158.72, 153.75, 136.35, 135.11, 131.83, 128.98, 127.83,
126.55, 124.63, 114.40, 55.42, 52.78, 36.04. HRMS (ESI): m/z calcu-
lated for C16H15O2 [MþH]þ 239.1067, found 239.1067.
References
4.4.18. 2-(Naphthalen-2-yl)-2,3-dihydro-1H-inden-1-one (2r)
Brown solid, 111 mg, 86% yield. Mp: 79e82 ꢀC. 1H NMR
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d
7.86 (d, J ¼ 7.2 Hz, 1H), 7.83e7.73 (m, 3H),
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d 209.61,
Please cite this article as: J. Yuan et al., Rhodium-catalyzed intramolecular hydroacylation of 1,2-disubstituted alkenes for the synthesis of 2-
substituted indanones, Tetrahedron, https://doi.org/10.1016/j.tet.2018.11.057

J. Yuan et al. / Tetrahedron xxx (xxxx) xxx
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Please cite this article as: J. Yuan et al., Rhodium-catalyzed intramolecular hydroacylation of 1,2-disubstituted alkenes for the synthesis of 2-
substituted indanones, Tetrahedron, https://doi.org/10.1016/j.tet.2018.11.057