Reactions of 3-arylpropenenitriles with arenes under superelectrophilic activation conditions: Hydroarylation of the carbon-carbon double bond followed by cyclization into 3-arylindanones

Article abstract of DOI:10.1016/j.tet.2020.131264

Reactions of 3-arylpropenenitriles [ArCH[dbnd]CHCN] with arenes [Ar'H] under the superelectrophilic activation conditions with Br?nsted superacid TfOH (CF₃SO₃H) or strong Lewis acid AlBr₃ result, first, in the formation of products of hydroarylation of the carbon-carbon double bond, 3,3-diarylpropanenitriles [Ar(Ar’)CHCH₂CN]. Reactions may go further in TfOH leading to 3-arylindanones, as products of intramolecular aromatic acylation by the electrophilically activated nitrile group. Intermediate cationic species, derived at the protonation of the starting 3-arylpropenenitriles onto the carbon of C[dbnd]C bond and the nitrile nitrogen, have been studied by DFT calculation. A plausible reaction mechanism including the formation of highly reactive dications [(Ar)HC⁺–CH₂C⁺ = NH] has been proposed. The obtained 3,3-diarylpropanenitriles have been transformed into pharmaceutically valuable 5-(2,2-diarylethyl)-1H-tetrazoles [Ar(Ar’)CHCH₂Tetr] and 3-diarylpropylamines [Ar(Ar’)CH(CH₂)₂NH₂] by the reactions with NaN₃ and LiAlH₄ correspondingly.

Full text of DOI:10.1016/j.tet.2020.131264

Tetrahedron xxx (xxxx) xxx
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Reactions of 3-arylpropenenitriles with arenes under
superelectrophilic activation conditions: Hydroarylation of the
carbon-carbon double bond followed by cyclization into 3-
arylindanones
Yelizaveta Gorbunova a, Dmitriy N. Zakusilo b, Irina A. Boyarskaya a,
, b, *
Aleksander V. Vasilyev a
a Department of Organic Chemistry, Institute of Chemistry, Saint Petersburg State University, Universitetskaya nab., 7/9, Saint Petersburg, 199034, Russia
b Department of Chemistry, Saint Petersburg State Forest Technical University, Institutsky per., 5, Saint Petersburg, 194021, Russia
a r t i c l e i n f o
a b s t r a c t
Article history:
Reactions of 3-arylpropenenitriles [ArCH]CHCN] with arenes [Ar’H] under the superelectrophilic acti-
vation conditions with Brønsted superacid TfOH (CF3SO3H) or strong Lewis acid AlBr3 result, first, in the
formation of products of hydroarylation of the carbon-carbon double bond, 3,3-diarylpropanenitriles
[Ar(Ar’)CHCH2CN]. Reactions may go further in TfOH leading to 3-arylindanones, as products of intra-
molecular aromatic acylation by the electrophilically activated nitrile group. Intermediate cationic spe-
cies, derived at the protonation of the starting 3-arylpropenenitriles onto the carbon of C]C bond and
the nitrile nitrogen, have been studied by DFT calculation. A plausible reaction mechanism including the
formation of highly reactive dications [(Ar)HCþeCH2Cþ ¼ NH] has been proposed. The obtained 3,3-
diarylpropanenitriles have been transformed into pharmaceutically valuable 5-(2,2-diarylethyl)-1H-
tetrazoles [Ar(Ar’)CHCH2Tetr] and 3-diarylpropylamines [Ar(Ar’)CH(CH2)2NH2] by the reactions with
NaN3 and LiAlH4 correspondingly.
Received 6 February 2020
Received in revised form
29 April 2020
Accepted 6 May 2020
Available online xxx
Keywords:
Nitriles
Superelectrophilic activation
Indanones
3,3-Diarylpropylamines
Tetrazoles
© 2020 Elsevier Ltd. All rights reserved.
1. Introduction
However, up to the moment, this reaction for unsaturated ni-
triles, for instance, derivatives of acrylonitrile, has been unknown.
Nitriles play a very important role in organic synthesis. Many
current studies are focused on the development of synthesis of
organic nitriles [1e4] and investigation of their chemical proper-
ties. Nitriles take part in various reactions leading to practically
valuable compounds, such as pharmaceuticals, heterocycles,
monomers for polymerization, ligands for metal complexation, etc.
[5e16] One of the useful synthetic transformations of nitriles is
electrophilic aromatic acylation under the activation of nitrile
group by Brønsted or Lewis acids, which has been known since the
beginning of the 20-th century, as Houben-Hoesch reaction [17,18].
Later on, this acylation has been carried out in the Brønsted
superacid CF3SO3H (triflic acid, TfOH) [19e24].
Just recently, we have shown that 3-phenylpropenenitrile (cinna-
monitrile) in reaction with arenes in the superacid TfOH gave two
types of compounds, 3-aryl-3-phenyl propanenitriles, as products
of hydroarylation of the carbon-carbon double bond, and/or 3-
phenylindanones [25]. These indanones were formed as second-
ary reaction products under the electrophilic aromatic acylation by
the activated nitrile group in 3-aryl-3-phenylpropanenitriles.
Based on our preliminary data [25] and work on electrophilic
activation of organic compounds [26e28], we undertook a special
investigation on transformations of unsaturated nitriles under
electrophilic activation conditions. The main goal of this work was a
study of reactions of 3-arylpropenenitriles (3-arylacrylonitriles,
cinnamonitriles) with arenes under the action of Brønsted super-
acid TfOH (CF3SO3H) or strong Lewis acid aluminium halogenides
AlX3 (X ¼ Cl, Br); and a study on reaction plausible cationic in-
termediates, derived from nitriles, by DFT calculations.
* Corresponding author. Department of Organic Chemistry, Institute of Chemis-
try, Saint Petersburg State University, Universitetskaya nab., 7/9, Saint Petersburg,
199034, Russia.
E-mail addresses: aleksvasil@mail.ru, a.vasilyev@spbu.ru (A.V. Vasilyev).
https://doi.org/10.1016/j.tet.2020.131264
0040-4020/© 2020 Elsevier Ltd. All rights reserved.
Please cite this article as: Y. Gorbunova et al., Reactions of 3-arylpropenenitriles with arenes under superelectrophilic activation conditions:
Hydroarylation of the carbon-carbon double bond followed by cyclization into 3-arylindanones, Tetrahedron, https://doi.org/10.1016/
j.tet.2020.131264

2
Y. Gorbunova et al. / Tetrahedron xxx (xxxx) xxx
2. Result and discussion
protosolvation of methoxy groups in superacid) (entries 24, 25), in
TfOH at room temperature resulted only in the formation of nitriles
2. On the other hand, good -nucleophiles, xylenes (dime-
Protonation of the nitrile nitrogen in 3-arylpropenenitriles 1a-e
in Brønsted acids gives, first, N-protonated species Aa-e (Table 1).
Second protonation of the carbon atom of the C]C bond affords
N,C-diprotonated forms Ba-e. Quantum chemical calculations for
cations Aa-e and Ba-e by DFT method were carried out in order to
estimate their electronic, orbital and electrophilic properties.
Charge distribution, contribution of atomic orbital into LUMO and
global electrophilicity indices
that, Gibbs free energies ( G298, kJ/mol) of two steps of the pro-
tonation reactions were calculated (Table 1). Calculations of G298
p
thylbenzenes) (entries 8e10, 12, 14e17), and pseudocumene (1,2,4-
trimethylbenzene) (entries 18e22) afforded indanones 3 at room
temperature. Decreasing the reaction temperature to 0 ꢁC allowed
to get selectively nitriles 2 in reactions with xylenes (entries 7, 11,
13). Apart from that, heating of solution of 2a in TfOH at 80 ꢁC for
2.5 h led to the corresponding 3-phenylindanone 3r in the yield of
40%. All these data clearly prove that nitriles 2 are initial reaction
products, which are further cyclized into indanones 3. Moderate
yields of target compounds 2 and 3 in some cases may be caused by
oligomerization of nitriles involving transformations of cyano
group in Brønsted acids [37].
u [29,30] were calculated. Apart from
D
D
values of protonation reactions have shown that the first proton-
ation step with the formation of cations Aa-e is thermodynamically
favorable with
leading to species Ba-e is very much unfavourable (
72 kJ/mol). However, one may not exclude a generating of dications
Ba-e in Brønsted superacids, due to a solvation effect of low
nucleophilic superacidic media. Species Ba-e are rather strong
D
G298 -25 ÷ ꢀ14 kJ/mol. The second protonation
A plausible mechanism for the reaction of nitriles 1 with arenes
in TfOH is given in Scheme 1 at the top. First, interaction of N,C-
diprotonated species B with arene takes place at the electrophilic
center C3 of dication B leading to N-protonated form of propane-
nitrile C. Hydrolysis of the latter gives nitrile 2. Cation C having an
electrophilic center at C1 of the protonated cyano group undergos
cyclization into caion D, which is N-protonated form of the corre-
sponding imine, hydrolysis of which finally results indanone 3.
Additionally we carried out DFT calculations on values of Gibbs
DG298 27 ÷
electrophiles having high electrophilicity indices
3.7e4.7 eV, compared to monocations Aa-e with 2.3e2.6 eV. Such
u values
u
dications may be considered as superelectrophiles [31,32]. Species
Ba-e bear large positive charges both on carbon C1 (0.70e0.71 e)
and C3 (0.08e0.19 e) that reveals that both these carbons may act as
reactive electrophilic centers (Table 1). However, orbital factors are
higher for C3, the atomic orbital contributions of this carbon into
LUMO (20.2e29.6%) are much higher than ones for C1 (0.5e10.7%).
It means that charge and orbital factors coincide in electrophilicity
of carbon C3 in dications Ba-e, and this carbon should be the most
reactive center in these species.
We also calculated properties of N,N-diprotonated species Ia
(Table 1, entry 16). The formation of such dications was considered
by Ohwada and Shudo [19e21]. High positive value of
(88.7 kJ/mol) for the second N-protonation step may reveal that
formation of doubly nitrogen protonated species is rather unlikely.
Dication Ia has high electrophilicity indice
free energies (DG298, kJ/mol) for the reactions of cation Ba leading
to species Ca, Da and target compounds 2a, 3r and on electronic
and orbital characteristics for cation Ca (Scheme 1, at the bottom).
Negative values of
that these transformations are very favorable thermodynamically.
The reaction Ca/2a has small positive G298 value of 5.7 kJ/mol, it
means that this process is possible, also taking into account a large
negative G298 value at the first stage Ba/Ca. Transformation of
DG values for the reactions Ba/Ca/3r reveal
D
D
species C into D and finally in indanones 3 depends on nucleo-
philicity of aromatic rings. Concerning electronic and orbital char-
acteristics of cation Ca, this species has a large positive charge (0.72
e) on the carbon C1 and small contribution of C1 into LUMO (5.1%
only) that shows a charge control in reactivity of Ca (see Scheme 1,
at the bottom).
DG298
u (4.9 eV), and positive
charge (0.37 e) is mainly localized at carbon C1.
Thus, based on the data of DFT calculations (Table 1), and taking
into account the formation of similar dications at the protonation of
alkenes conjugated with electron-withdrawing substituents in
Brønsted superacids, that was proved by NMR study [33e36], one
could expect that nitriles 1a-e may give rise to highly reactive
dicationic species Ba-e in the superacid TfOH.
Apart from TfOH, strong Lewis acids, aluminium halides AlX3
(X ¼ Cl, Br) were tested for the activation of nitriles 1. Good results
were obtained with aluminium bromide AlBr3; it was found that
reactions of nitriles 1 with arenes under the action of AlBr3 at 80 ꢁC
or room temperature for 1e3 h afforded only compounds 2 in good
yields (Table 2). This selective formation of nitriles 2, even in the
Then, we tried to catch intermediate protonated species, derived
from nitriles 1 in TfOH, by 1H NMR study. However, upon dissolving
of nitrile 1a in TfOH in NMR tube at room temperature, the for-
mation of complex mixture was observed. In preparative experi-
ment, after stirring of solution of 1a in TfOH at room temperature
for 1 h, oligomeric material was obtained. 1H NMR study of solution
of 1a in sulfuric acid H2SO4 at room temperature revealed a
generating of N-protosolvated species, like structure Aa (see
Table 1). However, nitrile 1a in reaction with benzene in H2SO4 at
room temperature for 16 h gave a complex mixture of oligomeric
compounds, no products of interaction with benzene were
detected.
Ractions of nitriles 1a-e with various arenes (benzene, and its
methylated, halogenated and methoxylated derivatives) in triflic
acid TfOH are given in Table 1. The formation of two kinds of
compounds, products of hydroarylation of the carbon-carbon
double bond 2a-j and/or indanones 3a-q, was detected. Struc-
tures of compounds 2a, 3a, 3g, and 3n were confirmed by X-ray
analysis [25]. Reactions of 1a-e with relatively low nucleophilic
arenes, such as benzene (entries 1e5), toluene (entry 6), 1,2-
dichlorobenzene (entry 23), and methoxy benzenes (anisole and
case of such good p-donor as pseudocumene (entries 9e13), re-
veals that the electrophilic activation of the nitrile group by AlBr3 is
not enough to achieve cyclization of 2 into indanone 3, contrary to
Brønsted superacid TfOH. There are some features of this AlBr3-
promoted reaction. One of them is a demethylation of methoxy
group with the formation of phenolic compounds 2k and 2q (en-
tries 5, 13). Another one is an aryl group exchange leading to
compound 2a (entries 2, 4), that was also observed in reactions of
amides of 3-arylpropenoic acids under superelectrophilic activa-
tion conditions by ourselves [38]. The same reactions with
aluminium chloride AlCl3 proceeded more complex and gave the
target reaction products in low yields with large amounts of olig-
omeric materials. Hydroarylation of nitriles 1 under the action of
AlBr3 may proceed in a way of coordination of this Lewis acid with
nitrogen of cyano group and carbon-carbon bond analogously
protonation of nitriles 1 in Scheme 1.
To investigate this reaction deeper we carried out the cyclization
of nitriles 2g,m into indanones 3f,k in TfOH at room temperature
for 1.5e2.5 h (Scheme 2). It was found an unusual regioselectivity of
electrophilic substitution at the formation of indane core. Thus,
nitrile 2g gave “unusual” indanone 3f, as the major reaction prod-
uct, and just trace amount of the expected one 3f1 (Scheme 2, and
veratrole, which may have low
p-nucleophilicity due to a
Please cite this article as: Y. Gorbunova et al., Reactions of 3-arylpropenenitriles with arenes under superelectrophilic activation conditions:
Hydroarylation of the carbon-carbon double bond followed by cyclization into 3-arylindanones, Tetrahedron, https://doi.org/10.1016/
j.tet.2020.131264

Y. Gorbunova et al. / Tetrahedron xxx (xxxx) xxx
3
Table 1
Selected calculated (DFT) electronic characteristics of cations Aa-e, Ba-e and Ia derived at the protonation of nitriles 1a-e.
с
с
Entry
1
Species
EHOMO, eV
ELUMO, eV
u a
,
eV
q(C [1]),b
0.31
e
q(C [3]),b
e
k(C [1])LUMO
,
%
k(C [3])LUMO
23.0
,
%
DG298 of proto-nation
re-action, kJ/mol
ꢀ8.12
ꢀ1.38
1.7
2.5
ꢀ0.08
3.1
2
ꢀ8.73
ꢀ2.44
0.65
0.02
14.9
33.1
ꢀ17
3
4
ꢀ10.16
ꢀ7.89
ꢀ4.37
ꢀ1.30
4.6
1.6
0.70
0.31
0.19
3.2
3.0
29.6
25.5
72
ꢀ0.08
5
6
7
8
ꢀ8.44
ꢀ10.15
ꢀ8.06
ꢀ8.58
ꢀ2.38
ꢀ4.15
ꢀ1.49
ꢀ2.53
2.4
4.3
1.7
2.5
0.65
0.70
0.31
0.65
0.02
0.15
ꢀ0.09
0.02
14.3
6.2
32.5
24.3
22.4
30.6
ꢀ21
55
2.8
13.8
ꢀ15
9
ꢀ10.25
ꢀ8.03
ꢀ8.50
ꢀ9.95
ꢀ7.55
ꢀ4.39
ꢀ1.51
ꢀ2.54
ꢀ4.41
ꢀ1.19
4.6
1.7
2.6
4.7
1.5
0.70
0.31
0.65
0.70
0.31
0.16
10.7
2.8
20.2
22.2
30.6
22.2
27.2
71
10
11
12
13
ꢀ0.09
0.01
13.8
5.0
ꢀ14
0.17
72
ꢀ0.08
3.2
(continued on next page)
Please cite this article as: Y. Gorbunova et al., Reactions of 3-arylpropenenitriles with arenes under superelectrophilic activation conditions:
Hydroarylation of the carbon-carbon double bond followed by cyclization into 3-arylindanones, Tetrahedron, https://doi.org/10.1016/
j.tet.2020.131264

4
Y. Gorbunova et al. / Tetrahedron xxx (xxxx) xxx
Table 1 (continued )
с
с
Entry
Species
E
HOMO, eV
ELUMO, eV
u a
,
eV
q(C [1]),b
0.64
e
q(C [3]),b
0.02
e
k(C [1])LUMO
13.9
,
%
k(C [3])LUMO
32.7
,
%
DG298 of proto-nation
re-action, kJ/mol
14
ꢀ8.02
ꢀ2.27
2.3
ꢀ25
15
16
ꢀ9.81
ꢀ10.1
ꢀ3.71
ꢀ4.61
3.7
4.9
0.71
0.37
0.08
0.5
7.8
28.9
29.6
27
ꢀ0.45
88.7
a
Global electrophilicity index
Natural charges.
Contribution of atomic orbital into the molecular orbital.
u
¼ (EHOMO þ ELUMO)2/8(ELUMO - EHOMO).
b
c
entry 12 in Table 2). Exact structures of indanones 3 were deter-
mined by HeH NOESY correlations between aromatic protons and
methyl groups with H3 indane proton (Scheme 2, and see NOESY
spectra in SI). One of the possible ways of the formation of this
indanone 3f may be an ipso-substitution in the intermediate cation
superelectrophilic activation conditions, we were able to get
separately, step by step, nitriles 2 and, then, indanones 3. It should
be mentioned, that indanones are very important compounds due
to their biological activity properties [39e41].
To show a synthetical potential of the obtained nitriles 2 we
carried out transformations of the nitrile group leading to some
pharmaceutically relevant compounds, namely, tetrazoles and
amines. Thus, interaction of nitriles 2a-d with sodium azide affor-
ded the corresponding 5-(2,2-diarylethyl)-1H-tetrazoles 4a-c
(Scheme 3). Tetrazoles are very important class of organic com-
pounds having many practically valuable properties, especially
medicinal ones [34e47]. We have recently developed a synthesis of
structurally close 5-(2,2-diarylethyl)-2-methyl-2H-tetrazoles by
hydroarylation of C]C bond in 5-(2-arylethenyl)-2-methyl-2H-
tetrazoles under superelectrophilic activation conditions [48].
Reduction of the nitrile group in compounds 2a-c by LiAlH4
furnishes the corresponding 3,3-diarylpropylamines 5a-c in high
yields (Scheme 4), which are in a great demand due to a variety of
their biologically active properties [49e53].
C1 leading to s-complex E1, which is rearranged into another s-
complex F1, that finally gives compound 3f. The same reaction
pathways were observed in the formation of other indanones 3 in
reactions of nitriles 1 with pseudocumene: 3k (Scheme 2, and from
1b in entry 18, Table 2), 3m (from 1e in entry 18 in Table 2), 3o
(from 1a in entry 21, Table 2), 3q (from 1c in entry 22, Table 2); and
with ortho-xylene: 3b (from 1a in entry 8, Table 2), 3c (from 1c in
entry 9, Table 2). The formation of these “unusual” indanones may
point out an extremely high reactivity of electrophilic center on the
carbon of the protonated nitrile group in intermediate cations C
(see the reaction mechanism in Scheme 1). We also checked re-
actions of nitriles 1 with sterically hindered 1,3,5-trimethylbenzene
(mesitylene) under the action of TfOH or AlBr3. However, in this
case, oligomeric material was obtained that may reveal significant
sterical demands for this reaction.
Thus, in reactions of nitriles
1
with arenes under
Scheme 1. Plausible mechanism for reaction of nitriles 1 with arenes in the Brønsted superacid TfOH (at the top); DFT calculated values of Gibbs free energies (DG298, kJ/mol) for the
reactions of cation Ba leading to species Ca, Da and target compounds 2a, 3r and DFT calculated electronic and orbital characteristics for cation Ca (at the bottom).
Please cite this article as: Y. Gorbunova et al., Reactions of 3-arylpropenenitriles with arenes under superelectrophilic activation conditions:
Hydroarylation of the carbon-carbon double bond followed by cyclization into 3-arylindanones, Tetrahedron, https://doi.org/10.1016/
j.tet.2020.131264

Y. Gorbunova et al. / Tetrahedron xxx (xxxx) xxx
5
Table 2
Reactions of nitriles 1a-e with arenes in TfOH leading to nitriles 2 and/or indanones 3.
Entry
Initial compounds
Arene
Reaction time, h
Reaction products, yield (%)
Nitrile
1
2
3
4
5
1a
1b
1c
1d
1e
1
2a, R ¼ H (78%)
2b, R ¼ Me (51%)
2c, R ¼ Cl (62%)
2d, R ¼ Br (53%)
2e, R ¼ MeO (39%)
0.5
0.5
2.5
0.5
6
1a
1
2b (46%)
7
1a
15 (at 0 ꢁC)
8
9
1a
1c
1
2
10
1d
3
11
1a
8 (at 0 ꢁC)
(continued on next page)
Please cite this article as: Y. Gorbunova et al., Reactions of 3-arylpropenenitriles with arenes under superelectrophilic activation conditions:
Hydroarylation of the carbon-carbon double bond followed by cyclization into 3-arylindanones, Tetrahedron, https://doi.org/10.1016/
j.tet.2020.131264

6
Y. Gorbunova et al. / Tetrahedron xxx (xxxx) xxx
Table 2 (continued )
Entry
Initial compounds
Arene
Reaction time, h
2
Reaction products, yield (%)
Nitrile
12
1a
13
1a
9 (at 0 ꢁC)
14
15
16
17
1a
1c
1d
1e
1
1.5
3
3g, R ¼ H (57%)
3h, R ¼ Cl (42%)
3i, R ¼ Br (47%)
3j, R ¼ MeO (25%)
2.5
18
19
20
1b
1d
1e
2.5
3
2
21
22
1a
1c
1
2
3n (43%) þ 3o (32%), R ¼ H
3p (48%) þ 3q (15%), R ¼ Cl
23
1a
2
Please cite this article as: Y. Gorbunova et al., Reactions of 3-arylpropenenitriles with arenes under superelectrophilic activation conditions:
Hydroarylation of the carbon-carbon double bond followed by cyclization into 3-arylindanones, Tetrahedron, https://doi.org/10.1016/
j.tet.2020.131264

Y. Gorbunova et al. / Tetrahedron xxx (xxxx) xxx
7
Table 2 (continued )
Entry
Initial compounds
Arene
Reaction time, h
2
Reaction products, yield (%)
Nitrile
24
25
1a
2e (45%)
1a
1
3. Conclusions
3.1.3. General procedure for the synthesis of 3-arylpropenenitriles
(1b-e) by Mizoroki-Heck reaction
We have developed a method for regioselective hydroarylation
of the carbon-carbon double bond in 3-arylpropenenitriles in their
reactions with arenes under the action of AlBr3, leading to the
formation of 3,3-diarylpropanenitriles. The latter may be further
electrophilically cyclized into the 3-arylindanones in TfOH. Syn-
thetical potential of the obtained 3,3-diarylpropanenitriles has
been demonstrated by their transformation into the corresponding
tetrazoles and amines, which have a significant pharmaceutical
value.
Solution of iodoarene (1e1.5 mmol) in 5 mL of DMF and solution
of acrylonitrile (1.5e2 mmol) in 5 mL of DMF were mixed and
magnetically stirred under the argon. The obtained solution was
heated to 125e127 ꢁC, then Pd(OAc)2 (0.07e0.09 mmol), P(Ph)3
(0.10e0.20 mmol), and K2CO3 (0.30e0.040 mmol) were added. The
reaction mixture was magnetically stirred at 125e127 ꢁC for 4e6 h
under the argon, then it was poured into water (100 mL). The re-
action product was extracted with EtOAc (3 ꢂ 100 mL). The com-
bined organic layers were washed with water (2 ꢂ 100 mL), a
saturated aqueous solution of NH4Cl (2 ꢂ 100 mL), and water again
(2 ꢂ 100 mL), and dried with Na2SO4. After evaporation of the
solvent under the reduced pressure, the reaction product was iso-
lated by thin-layer chromatography (eluent e petroleum ether:
ethyl acetate, 20: 1 vol). The target nitriles 1b-e were obtained as
mixtures of E-,Z-isomers.
3.1. Experimental part
3.1.1. General remarks
NMR spectra of solutions of compounds in CDCl3 were recorded
on Bruker AVANCE III 400 spectrometers at 25 ꢁC (at 400 and
100 MHz for 1H and 13C NMR spectra respectively). The residual
3.1.3.1. (E/Z)-3-(4-Methylphenyl)propenenitrile (1b). [57]. Yield of
(d
7.26 ppm) for 1H NMR spectra, the
50%. Colorless oil. Mixture of E-/Z-isomers 1Н NMR (400
МHz,
proton-solvent peak CDCl3
carbon signal of CDCl3 (
d
77.1 ppm) for 13C NMR spectra were used
CDCl3):
d
(E-isomer) 2.38 (s, 3H), 5.81(d, J ¼ 16.8 Hz, CH, 1H), 7.21 (d,
J ¼ 8 Hz, 2H),7.34 (d, J ¼ 8 Hz, 2H), 7.36(d, J ¼ 16.8 Hz, CH, 1H). 1Н
as references. HRMS was carried out at instruments Bruker maXis
HRMS-ESI-QTOF Mass Spectrometer. Preparative TLC was per-
formed on silica gel Kieselgel 60 F254 (0.04e0.063 mm). IR spectra
were registered for tablets with KBr on Shimadzu spectrometer.
NMR spectra in TfOH were referenced to the signal of CH2Cl2 added
NMR (400
М
Hz, CDCl3):
d
(Z-isomer) 2.39 (s, 3H), 5.37(d, J ¼ 12 Hz,
CH, 1H), 7.08(d, J ¼ 12 Hz, CH, 1H), 7.24 (d, J ¼ 8 Hz, 2H), 7.71 (d,
J ¼ 8 Hz, 2H).
as internal standard:
d
d
5.30 ppm for 1H NMR spectra, and
3.1.3.2. (E/Z)-3-(4-Chlorophenyl)propenenitrile (1c). [57]. Yield of
53.52 ppm for 13C NMR spectra respectively.
47%. Solid. Mixture of E-/Z-isomers 1Н NMR (400
МHz, CDCl3): d (E-
isomer) 5.85(d, J ¼ 16 Hz, CH, 1H), 7.33(d, J ¼ 16 Hz, CH, 1H),
7.30e7.36 (m, 2H), 7.52 (d, J ¼ 8 Hz, 2H). 1Н NMR (400
МHz, CDCl3):
3.1.2. DFT calculations
d
(Z-isomer) 5.46(d, J ¼ 12 Hz, CH, 1H), 7.02(d, J ¼ 12 Hz, CH, 1H),
All computations were carried out at the DFT/HF hybrid level of
theory using hybrid exchange functional M06 by using GAUSSIAN
2009 program packages [54]. The geometries optimization were
performed using the 6-311þG(2d,2p) basis set (standard 6e311
basis set added with polarization (d,p) and diffuse functions). Op-
timizations were performed on all degrees of freedom and solvent-
phase optimized structures were verified as true minima with no
imaginary frequencies. The Hessian matrix was calculated analyt-
ically for the optimized structures in order to prove the location of
correct minima and to estimate the thermodynamic parameters.
Solvent-phase calculations used the Polarizable Continuum Model
(PCM).
Synthesis of starting 3-arylpropenenitriles 1a-e. 3-
Phenylpropenenitrile (1a) was obtained by the reaction of cin-
namaldehyde with hydroxyl amine hydrochloride in DMSO ac-
cording to the literature procedure [55]. Other substituted nitriles
E-,Z-1b-e were obtained by Mizoroki-Heck reaction [56].
7.28e7.39 (m, 2H), 7.72 (d, J ¼ 8.4 Hz, 2H).
3.1.3.3. (E/Z)-3-(4-Bromophenyl)propenenitrile (1d). [57]. Yield of
61%. Solid. Mixture of E-/Z-isomers 1Н NMR (400
Hz, CDCl3): (E-
М
d
isomer) 5.88(d, J ¼ 16.8 Hz, CH, 1H), 7.31 (d, J ¼ 8 Hz, 2H),7.34(d,
J ¼ 16.8 Hz, CH, 1H), 7.55 (d, J ¼ 8 Hz, 2H). 1Н NMR (400
МHz,
CDCl3):
d
(Z-isomer) 5.54(d, J ¼ 12 Hz, CH, 1H), 7.07(d, J ¼ 12 Hz, CH,
1H), 7.58 (d, J ¼ 8.4 Hz, 2H), 7.67 (d, J ¼ 8.4 Hz, 2H).
3.1.3.4. (E/Z)-3-(4-Methoxyphenyl)propenenitrile
(1e)
[57].
Yield of 35%. Colorless oil. Mixture of E-/Z-isomers 1Н NMR (400
М МHz, CDCl3): d (E-isomer) 5.71(d,
Hz, CDCl3) 1Н NMR (400
J ¼ 16 Hz, CH, 1H), 6.91 (d, J ¼ 8.8 Hz, 2H) 7.28(d, J ¼ 16 Hz, CH, 1H),
7.39 (d, J ¼ 8.8 Hz, 2H). 1Н NMR (400
МHz, CDCl3): d (Z-isomer)
5.28(d, J ¼ 12 Hz, CH,1H), 6.94 (d, J ¼ 8 Hz, 2H),7.03(d, J ¼ 12 Hz, CH,
1H), 7.79 (d, J ¼ 8 Hz, 2H)
Please cite this article as: Y. Gorbunova et al., Reactions of 3-arylpropenenitriles with arenes under superelectrophilic activation conditions:
Hydroarylation of the carbon-carbon double bond followed by cyclization into 3-arylindanones, Tetrahedron, https://doi.org/10.1016/
j.tet.2020.131264

8
Y. Gorbunova et al. / Tetrahedron xxx (xxxx) xxx
Table 3
Reactions of nitriles 1a-e with arenes under the action of AlBr3 leading to compounds 2.
Entry
1
Initial compounds
Arene
Reaction conditions
Temperature, ꢁC
80
Reaction products, yield (%)
Nitrile
Time, h
1
1a
2
3
4
5
1b
1с
r.t.
75
80
r.t.
1
1
1
2
1d
1e
6
7
8
1a
1a
1a
80
80
80
1
1
1
Please cite this article as: Y. Gorbunova et al., Reactions of 3-arylpropenenitriles with arenes under superelectrophilic activation conditions:
Hydroarylation of the carbon-carbon double bond followed by cyclization into 3-arylindanones, Tetrahedron, https://doi.org/10.1016/
j.tet.2020.131264

Y. Gorbunova et al. / Tetrahedron xxx (xxxx) xxx
9
Table 3 (continued )
Entry
Initial compounds
Arene
Reaction conditions
Reaction products, yield (%)
Nitrile
Temperature, ꢁC
Time, h
9
1a
1b
1c
1d
80
r.t.
80
80
1
3
1
2
2l, R ¼ H (30%)
2m, R ¼ Me (69%)
2n, R ¼ Cl (57%)
2o, R ¼ Br (43%)
10
11
12
8
13
1e
r.t.
3
3.1.4. General procedure for the reaction of 3-arylpropenenitrile 1
with arenes in TfOH. Synthesis of nitriles 2 and indanones 3 (Table 2)
3-Arylpropenenitrile 1 (0.22e0.78 mmol) was added to mixture
of arene [benzene e 1 mL, other arenes e 1.2e1.7 equiv.)] in TfOH
(1e2 mL). Reaction mixture was magnetically stirred at 0 ꢁC or
room temperature for 0.5e15 h (see exact temperature and time
each experiment in Table 2). Then the mixture was quenched with
water (100 mL). Reaction products were extracted with EtOAc
Scheme 2. Cyclization of nitriles 2g,m into indanones 3f,k in TfOH.
Scheme 3. Synthesis of tetrazoles 4a-c from nitriles 2a-d.
Please cite this article as: Y. Gorbunova et al., Reactions of 3-arylpropenenitriles with arenes under superelectrophilic activation conditions:
Hydroarylation of the carbon-carbon double bond followed by cyclization into 3-arylindanones, Tetrahedron, https://doi.org/10.1016/
j.tet.2020.131264

10
Y. Gorbunova et al. / Tetrahedron xxx (xxxx) xxx
129.1(CarH), 129.4(CarH),132.1(CarH),140.3(Car), 140.7(Car); MS, m/z:
calcd. for С15Н12BrNNaþ [MþNa]þ 308.0045, found 308.0057.
3.1.5.3. 3-(2,4-Dimethylphenyl)-3-phenylpropanenitrile
(2g).
Obtained from nitrile 1a (38 mg, 0.29 mmol) in TfOH at 0 ꢁC for 8 h
(entry 11, Table 2) in yield of 15 mg, 22%; oilish compound; IR (KBr),
n
, сmꢀ1: 3028, 2922, 2852, 2250 (C^N), 1703, 1601, 1493; 1Н NMR
Scheme 4. Synthesis of amines 5a-c from nitriles 2a-c.
(400
4.52 (t, J ¼ 8Hz, 1H), 6.99(s, 1Н), 7.06(d, J ¼ 8Hz, 1Н), 7.12(d, J ¼ 8Hz,
1Н) 7.17e7.32(m 5Н) 13С NMR (100
Hz, CDCl3): 19.75(CH3),
М
Hz, CDCl3):
d
2.21 (s, 3H), 2.30 (s, 3H), 2.99 (d, J ¼ 8Hz, 2H),
(3 ꢂ 100 mL), the combined extracts were washed with water
(2 ꢂ 60 mL), saturated aqueous solution of NaHCO3 (100 mL), water
again (2 ꢂ 60 mL), and dried with Na2SO4. After evaporation of
solvent under reduced pressure, the obtained residue was sub-
jected to column or thin-layer chromatography on silica gel using
petroleum ether-benzene-dichloromethane mixtures (20 : 1 : 0.05,
vol.) or petroleum ether-ethyl acetate mixtures (20 : 1, vol.),
correspondingly, for eluation to get pure reaction products. Yields
of the products were determined after chromatographic isolation
(see Table 2).
М
d
21.0(CH3), 24.5(CH2), 43.2(CH), 118.7(C^N), 125.9(CarH),
127.1(CarH), 127.3(CarH), 127.8(CarH), 128.9(CarH), 132.0(CarH),
136.1(Car), 136.2(Car), 137.0(Car), 141.4(Car); MS, m/z: calcd. for
С
17Н17NNa [MþNa]þ 258.1259, found 258.1253.
3.1.5.4. 3-(2,5-Dimethylphenyl)-3-phenylpropanenitrile
(2h).
Obtained from nitrile 1a (42 mg, 0.33 mmol) in TfOH at 0 ꢁC for 9 h
(entry 13, Table 2) in yield of 10 mg, 15%; oilish compound; IR (KBr),
n
, сmꢀ1: 3027, 2921, 2851, 2249 (C^N), 1706, 1582, 1494; 1Н NMR
(400
4.52 (t,
7.29e7.33(m, 2Н) 13С NMR (100
24.4(CH2), 43.5(CH), 118.4(C^N), 126.7(CarH), 127.3(CarH),
127.9(CarH), 128.1(CarH), 128.9(CarH), 131.1(CarH), 133.2(Car),
135.9(Car), 138.9(Car), 141.2(Car); MS, m/z: calcd. for С17Н17NNaþ
[MþNa]þ 258.1259, found 258.1253.
М
Hz, CDCl3):
8Hz, 1H), 6.99e7.06(m, 3Н), 7.18e7.23(m, 3Н),
Hz, CDCl3): 19.4(CH3), 21.4(CH3),
d
2.20 (s, 3H), 2.34 (s, 3H), 3.00 (d, J ¼ 7.6 Hz, 2H),
3.1.5. General procedure for the reaction of 3-arylpropenenitrile 1
with arenes under the action of AlBr3. Synthesis of nitriles 2
(Table 3)
J
¼
М
d
3-Arylpropenenitrile 1 (0.4 mmol) was added to mixture of
AlBr3 (4 mmol, 10 equiv.) with arene (2e2.5 mL). Reaction mixture
was magnetically stirred at 80 ꢁC or room temperature for 1e3 h
(see exact temperature and time each experiment in Table 3). Then
the mixture was quenched with water (100 mL). Reaction products
were extracted with EtOAc (3 ꢂ 100 mL), the combined extracts
were washed with water (2 ꢂ 60 mL), saturated aqueous solution of
NaHCO3 (100 mL), water again (2 ꢂ 60 mL), and dried with Na2SO4.
After evaporation of solvent under reduced pressure, the obtained
residue was subjected to thin-layer chromatography on silica gel
using petroleum ether-benzene-ethyl acetate mixture (20 : 0.5 : 2,
vol.) for eluation to get pure reaction products. In some cases,
additional thin-layer chromatography purification was used using
eluation with petroleum ether-diethyl ether mixture (15 : 1, vol.)
Yields of the products were determined after chromatographic
isolation (see Table 3).
3.1.5.5. 3-(4-Hydroxyphenyl)-3-phenylpropanenitrile
Obtained from nitrile 1e (24 mg, 0.15 mmol) with AlBr3 at room
(2k)
[62].
temperature for 2 h (entry 5, Table 3) in yield of 18 mg, 53%; oilish
compound 1Н NMR (400
МHz, CDCl3):
d
3.00 (d, J ¼ 7.6 Hz, 2H), 4.33
(t, J ¼ 7.6 Hz, 1H), 4.91(s br.1Н, OH), 6.79(d, J ¼ 8.4 Hz, 2Н), 7.10(d,
J ¼ 8.4 Hz, 2Н), 7.21e7.27(m, 3Н), 7.32e7.35(m, 2Н) 13С NMR
(100МHz, CDCl3): d: 24.6 (CH2), 46.5 (CH),115.9 (CarH),118.9 (C^N),
127.5 (CarH),127.6 (CarH),128.9 (CarH),129.0 (CarH),133.6 (Car),141.6
(Car), 154.9 (Car); MS, m/z: calcd. for С15Н12NOꢀ [M ꢀ H]- 222.0919,
found 222. 0903.
3.1.5.6. 3-Phenyl-3-(2,4,5-trimethylphenyl)propanenitrile
Obtained from nitrile 1a (81 mg, 0.65 mmol) with AlBr3 at 80 ꢁC for
(2l).
Preparation and properties of 3,3-diphenylpropanenitrile (2а), 3-
(4-methylphenyl)-3-phenyl-propanenitrile
methoxyphenyl)-3-phenylpropanenitrile
(2b),
(2e),
[58]
[59]
3-(4-
3-(3,4-
1 h (entry 9, Table 3) in yield of 48 mg, 30%; oilish compound; IR
(KBr), n МHz, CDCl3): d 2.18 (s,
, сmꢀ1: 2248 (C^N) 1Н NMR (400
dimethylphenyl)-3-phenylpropanenitrile (2f),3-(3,4-dichlorophenyl)-
3-phenylpropanenitrile (2i), [60] 3-(3,4-dimethoxyphenyl)-3-
phenylpropanenitrile (2j) were previously reported by ourselves
[25].
3H), 2.21 (s, 3H), 2.25 (s, 3H), 2.99 (d, J ¼ 7.6Hz, 2H), 4.49 (t,
J ¼ 7.6Hz, 1H), 6.94(s, 1Н), 6.96(s, 1Н), 7.19(d, J ¼ 7.2Hz, 2Н), 7.24(d,
J ¼ 7.2Hz, 2Н), 7.30(d, J ¼ 7.6Hz, 2Н) 13С NMR (100
МHz, CDCl3):
d
19.2(CH3), 19.3(CH3), 19.7(CH3), 24.5(CH2), 43.2(CH), 118.8 (C^N),
127.2(CarH), 127.3(CarH), 127.8(CarH), 128.9(CarH), 132.6(CarH),
133.4(Car), 134.4(Car), 135.6(Car), 136.5(Car), 141.5(Car); MS, m/z:
calcd. for С18Н18NNaþ [MþNa]þ 272.1410, found 272.1403.
3.1.5.1. 3-(4-Chlorophenyl)-3-phenylpropanenitrile
Obtained from nitrile 1c (25 mg, 0.15 mmol) in TfOH at room
(2c)
[59].
temperature for 0.5 h (entry 3, Table 2) in yield of 23 mg, 62%; oilish
compound; IR (KBr),
CDCl3):
3.02 (d, J ¼ 8.0Hz, 2H), 4.36 (t, J ¼ 8.0Hz, 1H), 7.16e7.21(m,
4Н), 7.28e7.36 (m, 5Н) [13];С NMR (100 Hz, CDCl3): 24.3(CH2),
n МHz,
, сmꢀ1: 2250 (C^N) 1Н NMR (400
3.1.5.7. 3-(4-Methylphenyl)-3-(2,4,5-trimethylphenyl)propanenitrile
(2m). Obtained from nitrile 1b (29 mg, 0.2 mmol) with AlBr3 at
room temperature for 3 h (entry 10, Table 3) in yield of 42 mg, 69%;
d
М
d
n МHz,
, сmꢀ1: 2248 (C^N) 1Н NMR (400
46.7(CH), 118.2(C^N), 127.6(CarH), 127.8(CarH), 129.1(CarH),
129.2(CarH), 129.2(CarH),133.5(Car), 139.8(Car), 140.8(Car); MS, m/z:
calcd. for С15Н12СlNNaþ [Mþ Na]þ 264.0550, found 264.0549.
oilish compound; IR (KBr),
CDCl3): 2.18 (s, 3H), 2.21 (s, 3H), 2.24 (s, 3H), 2.31 (s, 3H), 2.97 (d,
J ¼ 8.0Hz, 2H), 4.46 (t, J ¼ 7.6Hz, 1H), 6.93(s, 1Н), 6.95(s, 1Н),
7.06e7.12(m, 4Н) 13С NMR (100
Hz, CDCl3): 19.2, 19.3, 19.7, 21.1,
d
М
d
3.1.5.2. 3-(4-Bromophenyl)-3-phenylpropanenitrile
Obtained from nitrile 1d (60 mg, 0.29 mmol) in TfOH at room
(2d)
[61].
24.5, 42.8, 118.9 (C^N), 127.3, 127.7, 129.6, 132.5, 133.4, 134.4, 135.5,
136.7, 136.9, 138.5; MS, m/z: calcd. for С19Н21NNaþ [M Na]þ
286.1566, found 286.1561.
temperature for 2.5 h (entry 4, Table 2) in yield of 44 mg, 53%; oilish
compound; IR (KBr),
CDCl3):
3.01 (d, J ¼ 7.6Hz, 2H), 4.35 (t, J ¼ 7.6Hz, 1H), 7.12 (d,
n МHz,
, сmꢀ1: 2245 (C^N),1490; 1Н NMR (400
d
3.1.5.8. 3-(4-Chlorophenyl)-3-(2,4,5-trimethylphenyl)propanenitrile
(2n). Obtained from nitrile 1c (30 mg, 0.18 mmol) with AlBr3 at
80 ꢁC for 1 h (entry 11, Table 3) in yield of 28 mg, 57%; oilish
J ¼ 8.0Hz, 2Н), 7.20e7.22(m, 2Н), 7.26e7.30(m, 1Н), 7.33e7.37(m,
2Н), 7.47(d, J ¼ 8.0Hz, 2Н) 13С NMR (100
МHz, CDCl3): d 24.2(CH2),
46.7(CH), 118.2(C^N), 121.5(Car), 127.5 (CarH), 127.7(CarH),
compound; IR (KBr), n МHz, CDCl3):
, сmꢀ1: (C^N) 1Н NMR (400
Please cite this article as: Y. Gorbunova et al., Reactions of 3-arylpropenenitriles with arenes under superelectrophilic activation conditions:
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j.tet.2020.131264

Y. Gorbunova et al. / Tetrahedron xxx (xxxx) xxx
11
d
2.15 (s, 3H), 2.21 (s, 3H), 2.25 (s, 3H), 2.96 (d, J ¼ 7.6Hz, 2H), 4.46 (t,
3.1.5.13. 3-(4-Bromophenyl)-6,7-dimethylindan-1-one (3d) [63].
Obtained from nitrile 1d (38 mg, 0.18 mmol) in TfOH at room
temperature for 3 h (entry 10, Table 2) in yield of 24 mg, 42%; oilish
J ¼ 7.6Hz, 1H), 6.92(s, 1Н), 6.94(s, 1Н), 7.13(d, J ¼ 8.4Hz, 2Н), 7.27 (d,
J ¼ 8.4Hz, 2Н) 13С NMR (100
МHz, CDCl3): d 19.2(CH3), 19.3(CH3),
19.7(CH3), 21.1(CH3), 24.5 (CH2), 42.8(CH), 118.9 (C^N), 127.3(CarH),
127.7(CarH), 129.6(CarH), 132.5(CarH), 133.4(Car), 134.4(Car),
135.5(Car), 136.7(Car), 136.9(Car), 138.5(Car); MS, m/z: calcd. for
compound; IR (KBr),
CDCl3):
n
, сmꢀ1: 1709 (C ¼ О) 1Н NMR (400
МHz,
d
2.32 (s, 3H), 2.65 (s, 3H), 2.60(dd, J ¼ 4.0, 19.0Hz, O]C-
CHA1H), 3.18(dd, J ¼ 19.0, 8.0Hz, O]C-CHA 1H), 4.41(dd, J ¼ 8.0,
4.0Hz, Ar-CH,1H), 6.93 (d, J ¼ 8.0Hz, 1H), 6.99 (d, J ¼ 8.0Hz, 2H), 7.31
С
18Н18ClNNaþ [M Na]þ 306,1020, found 306.1023.
(d, J ¼ 8.0Hz,1H), 7.41 (d, J ¼ 8.0Hz, 2H); 13С NMR (100
МHz, CDCl3):
d
13.8(CH3), 19.2(CH3),42.8(CH), 47.7(CH2), 120.7 (Car), 123.7(CarH),
3.1.5.9. 3-(4-Bromophenyl)-3-(2,4,5-trimethylphenyl)propanenitrile
(2o). Obtained from nitrile 1d (16 mg, 0.07 mmol) with AlBr3 at
80 ꢁC for 2 h (entry 12, Table 3) in yield of 10 mg, 43%; oilish
129.5(CarH), 132.0(CarH), 134.1 (Car), 136.4(CarH), 137.1 (Car), 137.2
(Car), 143.6 (Car), 156.1 (Car), 206.8 (C ¼ О); MS, m/z: calcd. for
n МHz,
, сmꢀ1: 2248 (C^N) 1Н NMR (400
С
17Н16BrOþ [MþH]þ315.0379, found 315.0371.
compound; IR (KBr),
CDCl3):
2.07 (s, 3H), 2.15 (s, 3H), 2.24 (s, 3H), 2.96 (d, J ¼ 8.0Hz,
d
2H), 4.44(t, J ¼ 7.6Hz 1H), 6.92(s, 1Н), 6.94(s, 1Н), 7.07(d, J ¼ 8.0Hz,
3.1.5.14. 3-(4-Bromophenyl)-5,6-dimethylindan-1-one
(3e).
2Н), 7.43(d, J ¼ 8.0Hz, 2Н) 13С NMR (100
МHz, CDCl3):
d
19.1(CH3),
Obtained from nitrile 1d (38 mg, 0.18 mmol) in TfOH at room
temperature for 3 h (entry 10, Table 2) in yield of 30 mg, 53%; oilish
19.3(CH3), 19.7(CH3), 24.3 (CH2), 42.7(CH), 118.5 (C^N), 121.3 (Car),
127.2(CarH), 129.6 (CarH), 132.1 (CarH), 132.7 (CarH), 133.3 (Car), 134.6
(Car), 135.9 (Car), 140.5 (Car); MS, m/z: calcd. for С18Н18BrNNaþ
[MþNa]þ 350.0515, found 350.0502.
compound; IR (KBr),
CDCl3):
n
, сmꢀ1: 1709 (C ¼ О) 1Н NMR (400
МHz,
d
2.28 (s, 3H), 2.32 (s, 3H), 2.58(dd, J ¼ 19.0, 3.6 Hz, O]C-
CHA1H), 3.18(dd, J ¼ 19.0, 8.0Hz, O]C-CHA 1H), 4.49(dd, J ¼ 8.0,
3.6Hz, Ar-CH, 1H), 6.98(s, 1Н), 6.99 (d, J ¼ 8.0Hz, 2H), 7.42 (d,
J ¼ 8.0Hz, 2H), 7.57(s, J ¼ 8.0Hz, 1Н) 13С NMR (100
МHz, CDCl3):
3.1.5.10. 3-(4-Methoxyphenyl)-3-(2,4,5-trimethylphenyl)propane-
nitrile (2p). Obtained from nitrile 1e (50 mg, 0.2 8 mmol) with
AlBr3 at room temperature for 3 h (entry 13, Table 3) in yield of
8 mg, 10%; oilish compound; IR (KBr),
(400 Hz, CDCl3): 2.17 (s, 3H), 2.20 (s, 3H), 2.24 (s, 3H), 2.95 (d,
d
19.9(CH3), 20.9(CH3),43.6(CH), 47.0(CH2), 120.8(Car), 123.9(CarH),
127.4(CarH), 129.7(CarH), 132.1(CarH), 135.1(Car), 137.3 (Car), 143.3
n
, сmꢀ1: 2248 (C^N) 1Н NMR
(Car), 145.7 (Car), 155.6 (Car), 205.4 (C ¼ О); MS, m/z: calcd. for
С
17Н16BrOþ [MþH]þ315.0379, found 315.0369.
М
d
J ¼ 7.6Hz, 2H), 3.77 (s, 3H, OCH3), 4.44 (t, J ¼ 7.6Hz, 1H), 6.83 (d,
J ¼ 8.4Hz 2Н), 6.93(s, 1Н), 6.94(s, 1Н), 7.10 (d, J ¼ 8.4 Hz, 2Н) 13С
3.1.5.15. 5,7-Dimethyl-3-phenylindan-1-one (3f). Obtained from
nitrile 1a (57 mg, 0.44 mmol) in TfOH at room temperature for 3 h
(entry 12, Table 2) in yield of 18 mg, 18%; oilish compound; IR (KBr),
NMR (100
МHz, CDCl3): d 1919.1(CH3), 19.3(CH3), 19.7(CH3),
24.7(CH2), 42.5(CH), 55.4(OCH3), 114.3(CarH), 118.9 (C^N),
127.2(CarH), 128.9(CarH), 132.6 (CarH), 133.4 (Сar), 133.5 (Сar), 134.4
(Сar), 135.6 (Сar), 136.7 (Сar), 158.7 (Сar); MS, m/z: calcd. for
n
, сmꢀ1: 3027, 2918, 2849, 1705 (C ¼ О), 1603, 1453; 1Н NMR (400
М
Hz, CDCl3):
d
2.31 (s, 3H), 2.65 (s, 3H), 2.65(dd, J ¼ 18.8, 4.0 Hz, O]
С
19Н21NNaOþ [MþNa]þ 302.1515, found 302.1516.
C-CHA,1H) 3.17 (dd, J ¼ 18.8, 8.4 Hz, O]CeCHB,1H), 4.44(dd, J ¼ 8.4,
4.0 Hz, Ph-CH,1H), 6.84 (s, 1H), 6.95 (s, 1H), 7.13(m, 2Н), 7.24(m, 1Н),
7.29e7.33(m, 2Н) 13С NMR (100
М
Hz, CDCl3):
d 18.2(CH3),
3.1.5.11. 3-(4-Hydroxyphenyl)-3-(2,4,5-trimethylphenyl)propane-
nitrile (2q). Obtained from nitrile 1e (50 mg, 0.28 mmol) with AlBr3
at room temperature for 3 h (entry 13, Table 3) in yield of 19 mg,
22.0(CH3),
43.9(CH),
47.6(CH2), 124.7(CarH), 126.9(CarH),
127.8(CarH), 128.9(CarH), 131.0(CarH), 131.9(Car), 138.6(Car),
n
, сmꢀ1: 2254 (C^N), 3395 (OH);
144.4(Car), 145.6(Car), 159.4(Car), 206.5 (C ¼ О); MS, m/z: calcd. for
25%; oilish compound; IR (KBr),
С
17Н17Oþ [MþH]þ 237.1274, found 237. 1274.
1Н NMR (400
М
Hz, CDCl3): 2.16 (s, 3H), 2.20 (s, 3H), 2.24 (s, 3H),
d
2.95(d, J ¼ 7.6Hz 2H), 4.42 (t, J ¼ 7.6Hz, 1H), 4.85(s, br. 1Н, OH),
6.75(d, J ¼ 8.4Hz, 2Н), 6.93(s, 1Н), 6.94(s, 1Н), 7.05 (d, J ¼ 8.4 Hz, 2Н)
3.1.5.16. 3-(4-Chlorophenyl)-4,7-dimethylindan-1-one (3h) [63].
Obtained from nitrile 1c (43 mg, 0.26 mmol) in TfOH at room
temperature for 1.5 h (entry 15, Table 2) in yield of 30 mg, 42%;
13С NMR (100
МHz, CDCl3): d 19.1(CH3), 19.3(CH3), 19.7(CH3), 24.7
(CH2), 42.4(CH), 115.7 (CarH), 118.9 (C^N), 127.1 (CarH), 129.1 (CarH),
132.6 (CarH), 133.4 (Сar), 134.6 (Сar), 134.4 (Сar), 135.5 (Сar), 136.7
(Сar), 154,7(Сar); MS, m/z: calcd. for С18Н19ClNNaOþ
[MþNa]þ288,1359, found 288.1370.
oilish compound; IR (KBr),
n
, сmꢀ1: 1706 (C ¼ О) 1Н NMR (400
МHz,
CDCl3):
d
1.96 (s, 3H), 2.66 (s, 3H), 2.50(dd, J ¼ 19.2,2.8Hz, O]C-CHA,
1H), 3.18(dd, J ¼ 19.2, 8.8Hz, O]C-CHA 1H), 4.49(dd, J ¼ 8.4, 2.4Hz,
Ar-CH, 1H), 6.95 (d, J ¼ 8.4 Hz, 2H), 7.10 (d, J ¼ 8.0 Hz, 1H), 7.22e7.24
Preparation and properties of 5,6-dimethyl-3-phenylindan-1-one
(3a), [63] 6,7-dimethyl-3-phenylindan-1-one (3b), [63] 4,7-dimethyl-
3-phenylindan-1-one (3g), [63] 4,6,7-trimethyl-3-phenylindan-1-one
(3n), 4,5,7-trimethyl-3-phenylindan-1-one (3o) were previously re-
ported by ourselves [25]. Spectral data of 3-phenylindan-1-one (3r)
corresponds to the literature data [63].
(m, 3H); 13С NMR (100
МHz, CDCl3): d 18.1(CH3),18.2(CH3),
42.7(CH), 48.9(CH2), 128.8 (CarH), 129.1 (CarH), 130.5 (CarH), 132.5
(Car), 133.7 (Car), 134.5 (Car), 136.0 (CarH), 136.1 (Car), 142.8 (Car),
155.7 (Car), 207.1 (C ¼ О); MS, m/z: calcd. for С17Н15ClNaOþ
[MþNa]þ 293.0704, found 293.0690.
3.1.5.12. 3-(4-Chlorophenyl)-6,7-dimethylindan-1-one (3c) [63].
Obtained from nitrile 1c (25 mg, 0.17 mmol) in TfOH at room
temperature for 2 h (entry 9, Table 2) in yield of 15 mg, 33%; oilish
3.1.5.17. 3-(4-Bromophenyl)-4,7-dimethylindan-1-one (3i) [64].
Obtained from nitrile 1d (32 mg, 0.15 mmol) in TfOH at room
temperature for 3 h (entry 15, Table 2) in yield of 22 mg, 47%; oilish
compound; IR (KBr),
CDCl3):
n
, сmꢀ1: 1704 (C ¼ О) 1Н NMR (400
М
Hz,
compound; IR (KBr),
CDCl3):
n
, сmꢀ1: 1707 (C ¼ О) 1Н NMR (400
МHz,
d
2.32 (s, 3H), 2.66 (s, 3H), 2.60(dd, J ¼ 19.0, 4.0Hz, O]C-
d
1.96 (s, 3H), 2.66 (s, 3H), 2.50(dd, J ¼ 19.2, 2.4Hz, O]C-
CHA 1H), 3.18(dd, J ¼ 19.0, 8.0Hz, O]C-CHA1H), 4.49(dd, J ¼ 8.4Hz,
Ar-CH,1H), 6.93 (d, J ¼ 8.0 Hz, 2H), 7.05 (d, J ¼ 8.0Hz, 1H), 7.26 (d,
CHA,1H), 3.18(dd, J ¼ 19.2, 8.4Hz, O]C-CHA 1H), 4.47(dd, J ¼ 8.4,
2.4Hz, Ar-CH 1H), 6.89 (d, J ¼ 8.4Hz, 2H.), 7.10 (d, J ¼ 7.6Hz, 1H), 7.23
J ¼ 8.0Hz, 2H), 7.31 (d, J ¼ 8.0Hz,2H); 13С NMR (100
М
Hz, CDCl3):
(d, J ¼ 7.6Hz,1H), 7.38 (d, J ¼ 8.4Hz, 2H); 13С NMR (100
МHz, CDCl3):
d
13.8(CH3), 19.8(CH3), 42.7(CH), 47.8(CH2), 123.7(CarH), 129.0
d 18.2(CH3), 42.8(CH), 47.9(CH2), 120.5 (Car), 129.2(CarH), 130.5
(CarH), 129.1(CarH), 132.7(Car), 134.1(Car), 136.4(CarH), 137.1(Car),
(CarH),132.0(CarH), 133.7 (Car), 134.5 (Car), 136.0(CarH), 136.1 (Car),
137.2(Car), 143.0(Car), 156.2(Car), 206.8 (C ¼ О); MS, m/z: calcd. for
143.3 (Car), 155.6(Car), 207.0 (C
С
¼
О); MS, m/z: calcd. for
С
17Н15ClNaOþ [MþNa]þ 293.0704, found 293.0693.
17Н15BrNaOþ [MþNa]þ337.0198, found 337.0207.
Please cite this article as: Y. Gorbunova et al., Reactions of 3-arylpropenenitriles with arenes under superelectrophilic activation conditions:
Hydroarylation of the carbon-carbon double bond followed by cyclization into 3-arylindanones, Tetrahedron, https://doi.org/10.1016/
j.tet.2020.131264

12
Y. Gorbunova et al. / Tetrahedron xxx (xxxx) xxx
3.1.5.18. 3-(4-Methoxyphenyl)-4,7-dimethylindan-1-one
(3j).
285.1041, found 285.1049.
Obtained from nitrile 1e (31 mg, 0.19 mmol) in TfOH at room
temperature for 2.5 h (entry 16, Table 2) in yield of 12 mg, 25%;
3.1.5.23. 3-(4-Chlorophenyl)-4,5,7-trimethylindan-1-one
Obtained from nitrile 1c (30 mg, 0.18 mmol) in TfOH at room
(3q).
oilish compound; IR (KBr),
CDCl3):
n
, сmꢀ1: 1704 (C ¼ О) 1Н NMR (400
М
Hz,
d
1.97 (s, 3H), 2.66 (s, 3H), 3.77 (s, 3H, ОCH3), 2.53(dd,
temperature for 2 h (entry 22, Table 2) in yield of 8 mg, 15%; oilish
J ¼ 19.2, 2.4Hz, O]C-CHA 1H), 3.17(dd, J ¼ 19.2, 8.4Hz, O]C-CHA
1H), 4.46(dd, J ¼ 8.4, 2.4Hz, Ar-CH 1H), 6.79 (d, J ¼ 8.4Hz, 2H), 6.93
compound 1Н NMR (400
МHz, CDCl3): d 1.89 (s, 3H), 2.27 (s, 3H),
2.48(dd, J ¼ 19.0, 2.0 Hz, O]C-CHA1H), 2.63 (s, 3H), 3.18(dd, J ¼ 19.0,
8.0 Hz, O]C-CHВ1H), 4.51(dd, J ¼ 8.0, 2.0 Hz, Ar-CH,1H), 6.93(d,
Har,J ¼ 8.4Hz, 2H), 7.02 (s, 1H, H-6), 7.22(d, HarJ ¼ 8.4Hz, 2Н) 13С
(d, J ¼ 8.4Hz, 2H), 7.08 (d, J ¼ 7.6Hz, 1H), 7.21 (d, J ¼ 7.6Hz, 1H); 13
С
NMR (100
МHz, CDCl3): d 18.2 (2CH3), 42.6(CH), 48.3(CH2),
55.4(ОCH3), 114.3 (CarH), 128.4 (CarH), 130.2 (CarH), 131.5(Car),
133.8(Car), 134.5 (Car), 135.9 (CarH), 136.3 (Car), 158.3 (Car), 207.9
(C ¼ О); MS, m/z: calcd. for С18Н19Oþ2 [Mþ Н]þ 267.1380, found
267.1369.
NMR (100 МHz, CDCl3): d 14.8(CH3), 18.1(CH3), 20.4(CH3), 42.8(CH),
48.3(CH2), 128.7(CarH), 129.1(CarH), 131.9(Car), 132.3(Car),
132.6(CarH), 135.7(Car), 143.4(Car), 144.5(Car), 155.9(Car), 206.7
(C ¼ О); MS, m/z: calcd. for С18Н18ClOþ [MþH]þ 285.1041, found
285.1043.
3.1.5.19. 3-(4-Methylphenyl)-4,5,7-trimethyl-indan-1-one
(3k).
Obtained from nitrile 1b (47 mg, 0.32 mmol) in TfOH at room
temperature for 2.5 h (entry 18, Table 2) in yield of 42 mg, 50%;
3.1.6. General procedure for the reaction of 3,3-diarylpropanenitrile
2 with NaN3. Synthesis of tetrazoles 4 (Scheme 3)
oilish compound; IR (KBr),
CDCl3):
n
, сmꢀ1: 1692 (C ¼ О) 1Н NMR (400
М
Hz,
Nitrile 2 (0.10e0.45 mmol) was added to mixture of NaN3
(0.32e1.27 mmol) and (CH3)2NH*HCl (0.68e2 mmol) in DMF
(5 mL). Reaction mixture was magnetically stirred at 127 ꢁC for
30e72 h. Then the mixture was quenched with aqueous solution of
hydrochloric acid (1.1N 100 mL). Reaction products were extracted
with EtOAc (4 ꢂ 100 mL). After evaporation of solvent under
reduced pressure, the obtained residue was subjected to thin-layer
chromatography on silica gel using petroleum ether-ethyl acetate
mixtures (20 : 1, vol.) for eluation of compounds 4b,c and petro-
leum ether-ethyl acetate-benzene mixtures (20 : 1 : 0.05, vol.) for
eluation of compounds 4a,d. Yields of the reaction products were
determined after chromatographic isolation.
d
1.91 (s, 3H), 2.27 (s, 3H), 2.29 (s, 3H), 2.52(dd, J ¼ 18.8,
2.0 Hz, O]C-CHA 1H), 2.64 (s, 3H), 3.17(dd, J ¼ 18.8, 8.4Hz, O]C-
CHВ 1H), 4.49(dd, J ¼ 8.4, 2.0 Hz, Ar-CH, 1H), 6.88 (d, J ¼ 8.0Hz, 2H),
6.99 (s, 1H, H-6), 7.05(d, J ¼ 8.0Hz, 2Н) 13С NMR (100
МHz, CDCl3):
d
14.7(CH3), 18.1(CH3), 20.3(CH3), 21.1(CH3),43.1(CH), 48.6(CH2),
127.3(CarH), 129.6(CarH), 132.1(Car), 132.3(CarH), 132.9(Car),
135.4(Car),136.0(Car),141.8(Car),144.2(Car),156.7(Car), 207.4 (C ¼ О);
MS, m/z: calcd. for С19Н20ONaþ [MþNa]þ287.1406, found 287.1405.
3.1.5.20. 3-(4-Bromophenyl)-4,6,7-trimethylind
аn-1-one
(3l).
Obtained from nitrile 1d (36 mg, 0.17 mmol) in TfOH at room
temperature for 3 h (entry 19, Table 2) in yield of 20 mg, 34%; oilish
compound; IR (KBr),
CDCl3):
n
, сmꢀ1: 1700 (C ¼ О) 1Н NMR (400
М
Hz,
3.1.6.1. 5-(2,2-Diphenylethyl)-1H-tetrazole (4
nitrile 2 (59 mg, 0.28 mmol) with NaN3 (44 mg, 0.67 mmol) and
(CH3)2NH*HCl (55 mg, 0.68 mmol) for 30 h in yield of 30 mg, 43%;
oilish compound; IR (KBr),
, сmꢀ1: 3100, 2853, 2710,2623, 1494; 1Н
NMR (400 Hz, CDCl3):
3.82 (d, J ¼ 8.4Hz, 2H), 4.70 (t, J ¼ 8.4Hz,
1H), 7.15e7.18 (m, 2H), 7.21e7.28 (m, 8H); 13С NMR (100
Hz,
а). Obtained from
d
1.93 (s, 3H), 2.30 (s, 3H), 2.62 (s, 3H), 2.50(dd, J ¼ 19.2,
а
2.0 Hz, O]C-CHA 1H), 3.19(dd, J ¼ 19.2, 8.0 Hz, O]C-CHВ1H),
4.41(dd, J ¼ 8,2Hz, Ar-CH,1H), 6.89 (d, J ¼ 8.4Hz, 2H), 7.15 (s, 1H, H-
n
5), 7.37(d, J ¼ 8.4Hz,2Н) 13С NMR (100
МHz, CDCl3):
d
13.4(CH3),
М
d
18.1(CH3), 19.1(CH3), 42.1(CH), 48.3(CH2), 120.4(Car), 129.2(CarH),
132.0(CarH), 133.0(Car), 134.4(Car), 134.5(Car), 137.6(Car), 138.0(CarH),
143.6(Car), 153.5(Car), 207.4 (C ¼ О); MS, m/z: calcd. for С18Н18BrOþ
[MþH]þ 329.0536, found 329.0530.
М
CDCl3): d 30.0(CH2), 49.6(CH), 127.2 (CarH), 127.7(CarH), 129.0(CarH),
142.3(Car), 155.5(C]N); MS, m/z: calcd. for С15Н15Nþ4 [MþH]þ
251.1291, found 251.1293.
3.1.5.21. 3-(4-Methoxyphenyl)-4,5,7-trimethylindan-1-one
(3m).
3.1.6.2. 5-(2-(4-Methylphenyl)-2-phenylethyl)-1H-tetrazole
(4b).
Obtained from nitrile 1e (25 mg, 0.16 mmol) in TfOH at room
temperature for 2 h (entry 20, Table 2) in yield of 19 mg, 43%; oilish
Obtained from nitrile 2b (100 mg, 0.45 mmol), with NaN3 (83 mg,
1.27 mmol) and (CH3)2NH*HCl (165 mg, 2.04 mmol) for 45 h in
compound; IR (KBr),
CDCl3):
n
, сmꢀ1: 1701 (C ¼ О) 1Н NMR (400
М
Hz,
yield of 89 mg, 75%; oilish compound; IR (KBr),
2921, 2852, 1557, 1456; 1Н NMR (400
Hz, CDCl3):
3.73 (d,J ¼ 8.0 Hz, 2H), 4.48 (t, J ¼ 8.0 Hz, 1H), 7.07e7.14 (m, 5H),
7.19e7.27 (m,4H); 13С NMR (100
Hz, CDCl3): 21.1(CH3),
n
, сmꢀ1: 3389, 3026,
2.28 (s, 3H),
d
1.91 (s, 3H), 2.27 (s, 3H), 2.50(dd, J ¼ 18.8, 2.0Hz, O]C-
М
d
CHA, 1H), 2.63 (s, 3H), 3.16(dd, J ¼ 18.8, 8.4Hz, O]C-CHВ,1H), 3.77(s,
OCH3, 3H), 4.48(dd, J ¼ 8.4, 2.0Hz, Ar-CH, 1H), 6.78(d, J ¼ 8.4Hz, 2H),
М
d
6.91 (d, J ¼ 8.4 Hz, 2H), 6.99 (s,1H, H-6); 13С NMR (100
М
Hz, CDCl3):
48.7(CH2),
30.2(CH2), 49.2(CH), 127.2(CarH), 127.6(CarH), 127.7(CarH),
129.0(CarH), 129.8 (CarH), 137.0(Car), 139.3(Car), 142.6(Car), 155.3(C]
N); MS, m/z: calcd. for С16Н16N4Naþ [MþNa]þ 287.1267 found
287.1264.
d
14.7(CH3),
18.1(CH3),
20.3(CH3),42.7(CH),
55.4(OCH3),114.3(CarH), 128.3(CarH), 132.1(Car), 132.3(CarH),
132.8(Car), 135.4(Car), 137.0(Car), 144.3 (Car), 156.8(Car), 158.2(Car),
207.5 (C ¼ О); MS, m/z: calcd. for С19Н20Oþ2 [MþH]þ 281.1536, found
281.1535.
3.1.6.3. 5-(2-(4-Chlorophenyl)-2-phenylethyl)-1H-tetrazole(4c).
Obtained from nitrile 2c (107 mg, 0.44 mmol) with NaN3 (55 mg,
0.84 mmol) and (CH3)2NH*HCl (149 mg, 1.84 mmol) for 68 h in
3.1.5.22. 3-(4-Chlorophenyl)-4,6,7-trimethylindan-1-one
(3p).
Obtained from nitrile 1c (30 mg, 0.18 mmol) in TfOH at room
yield of 92 mg, 73%; oilish compound; IR (KBr),
n
, сmꢀ1: 3028, 2853,
2737, 1562, 1492 сmꢀ1 1Н NMR (400
МHz, CDCl3): d 3.76 (d,
temperature for 2 h (entry 22, Table 2) in yield of 26 mg, 48%; oilish
compound 1Н NMR (400
М
Hz, CDCl3):
d
1.93 (s, 3H), 2.30 (s, 3H),
J ¼ 8.0Hz, 2H), 4.61(t, J ¼ 8.4Hz 1H), 7.15e7.26 (m, 9H); 13С NMR
2.50(dd, J ¼ 18.8, 2.0 Hz, O]C-CHA 1H), 2.62 (s, 3H), 3.19(dd,
J ¼ 18.8, 8.4Hz, O]C-CHВ 1H), 4.43(dd, J ¼ 8.4, 2.0Hz, Ar-CH,1H),
6.95 (d, J ¼ 8.4Hz, 2H), 7.15 (s, 1H, H-5), 7.22 (d, J ¼ 8.4 Hz, 2H);
(100 МHz, CDCl3): d 30.0(CH2), 49.0(CH), 127.5(CarH), 127.7(CarH),
129.0 (CarH), 129.1(CarH), 129.2 (CarH), 133.0(Car), 140.8(Car),
141.9(Car), 155.5(C]N); MS, m/z: calcd. for С15Н13 ClN4þ
[MþNa]þ307.0721, found 307.0713.
13С NMR (100
МHz, CDCl3):
d
13.4(CH3), 18.1(CH3),
19.1(CH3),42.0(CH), 48.4(CH2), 128.8(CarH), 129.1(CarH), 132.4(Car),
133.0(Car), 134.4(Car), 134.5(Car), 137.6(Car), 138.0(CarH), 143.1(Car),
153.6(Car), 207.4 (C ¼ О); MS, m/z: calcd. for С18Н18ClOþ [MþH]þ
3.1.6.4. 5-(2-(4-Bromophenyl)-2-phenylethyl)-1H-tetrazole(4d).
Obtained from nitrile 2d (30 mg, 0.10 mmol) with NaN3 (21 mg,
Please cite this article as: Y. Gorbunova et al., Reactions of 3-arylpropenenitriles with arenes under superelectrophilic activation conditions:
Hydroarylation of the carbon-carbon double bond followed by cyclization into 3-arylindanones, Tetrahedron, https://doi.org/10.1016/
j.tet.2020.131264

Y. Gorbunova et al. / Tetrahedron xxx (xxxx) xxx
13
0.32 mmol) and (CH3)2NH*HCl (83 mg, 1.02 mmol) for 72 h in yield
of 18 mg, 53%; 18 mg, 53%; oilish compound; IR (KBr),
, сmꢀ1
3000, 2923, 2853, 1489 сmꢀ1 1Н NMR (400
Hz, CDCl3): 3.75 (d,
Appendix A. Supplementary data
n
:
М
d
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.tet.2020.131264.
J ¼ 8.0Hz, 2H), 4.59 (t, J ¼ 8.4Hz,1H), 7.11 (d, 2H J ¼ 8.4Hz), 7.19e7.26
(m, 6H), 7.35 (d, J ¼ 8.4Hz, 2H); 13С NMR (100
МHz, CDCl3):
d
29.9(CH2), 49.0(CH), 121.1(Car), 127.5(CarH), 127.7(CarH),
Supplementary data
129.2(CarH), 129.5 (CarH), 132.0(CarH), 141.4(Car), 141.8(Car),
155.5(C]N); MS, m/z: calcd. for С15Н14 BrNþ4 [MþH]þ 329.0396
found 329.0382.
Copies of 1H, 13C NMR spectra, data of DFT calculations.
References
3.1.7. General procedure for the reduction of 3,3-
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diarylpropanenitrile 2 by LiAlH4. Synthesis of amines 5 (Scheme 4)
Nitrile 2 (0.14e0.19 mmol) was added to mixture of LiAlH4
(0.097e0.5 mmol) with Et2O (5 mL). Reaction mixture was
magnetically stirred at 35 ꢁC for 1e4 h. Then the mixture was
quenched with water (50 mL). Reaction products were extracted
with CH2Cl2 (3 ꢂ 50 mL), the combined extracts were washed with
saturated aqueous solution of NaHCO3 (3 ꢂ 20 mL), water (20 mL),
and dried with Na2SO4. Yields of the products were determined
after column chromatographic isolation.
3.1.7.1. 3,3-Diphenylpropan-1-amine (5a) [38,65]. Obtained from
nitrile 2
4 h in yield of 35 mg, 86%; oilish compound 1Н NMR (400
CDCl3):
1.32(s,br, 2H, NH2), 2.20 (q, J ¼ 7.6Hz, 2H), 2.67 (t,
J ¼ 7.2Hz, 2H), 4.03 (t, J ¼ 7.6Hz, 1H), 7.15e7.19 (m, 2Н),
а
(40 mg, 0.19 mmol) with LiAlH4 (3.7 mg, 0.097 mmol) for
МHz,
d
7.24e7.30(m, 8Н) 13С NMR (100
МHz, CDCl3): d 39.2, 40.6, 48.8,
126.2, 127.9, 128.6, 144.8; MS, m/z: calcd. for С15Н18Nþ [MþН]þ
[14] F.F. Fleming, Z.Y. Zhang, Tetrahedron 61 (2005) 747e789.
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М
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Declaration of competing interest
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Acknowledgements
This work was supported by the Russian Foundation for Basic
Research (RFBR, grant no. 18-33-00171). Spectral studies were
performed at the Center for Magnetic Resonance, the Center for
Chemical Analysis and Materials Research of Saint Petersburg State
University, Saint Petersburg, Russia.
Please cite this article as: Y. Gorbunova et al., Reactions of 3-arylpropenenitriles with arenes under superelectrophilic activation conditions:
Hydroarylation of the carbon-carbon double bond followed by cyclization into 3-arylindanones, Tetrahedron, https://doi.org/10.1016/
j.tet.2020.131264

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Please cite this article as: Y. Gorbunova et al., Reactions of 3-arylpropenenitriles with arenes under superelectrophilic activation conditions:
Hydroarylation of the carbon-carbon double bond followed by cyclization into 3-arylindanones, Tetrahedron, https://doi.org/10.1016/
j.tet.2020.131264