Facile synthesis of densely substituted chroman derivatives through Bronsted acid ionic liquid catalyzed three-component reactions of aromatic aldehydes, 1,1-diarylethylenes and nucleophiles

Article abstract of DOI:10.1016/j.tet.2015.11.049

By using a sulfone-containing Bronsted acid ionic liquid as catalyst, various densely substituted chroman derivatives were synthesized through hitherto unreported three-component reactions of aromatic aldehydes, 1,1-diarylethylenes and nucleophiles. The r

Full text of DOI:10.1016/j.tet.2015.11.049

Tetrahedron xxx (2015) 1e10
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Facile synthesis of densely substituted chroman derivatives through
Brønsted acid ionic liquid catalyzed three-component reactions of
aromatic aldehydes, 1,1-diarylethylenes and nucleophiles
,
a
,
b,
Amir Taheri b, Bingbing Lai b, Jing Yang a , Juan Zhang , Yanlong Gu
*
*
*
a Henan University of Traditional Chinese Medicine, Zhengzhou 450008, China
b Huazhong University of Science and Technology (HUST), 1037 Luoyu Road, Hongshan District, Wuhan 430074, China
a r t i c l e i n f o
a b s t r a c t
Article history:
By using a sulfone-containing Brønsted acid ionic liquid as catalyst, various densely substituted chroman
derivatives were synthesized through hitherto unreported three-component reactions of aromatic al-
dehydes, 1,1-diarylethylenes and nucleophiles. The representative reactions involve (i) condensation of
benzaldehyde, 2-naphthol and 1,1-diphenylethylene and (ii) selective assembly of salicylaldehyde, indole
and 1,1-diphenylethylene. The reactions were performed under solvent-free conditions, and the only by-
product was water. The Brønsted acid ionic liquid could be recovered and reused without significant loss
of its activity.
Received 11 October 2015
Received in revised form 17 November 2015
Accepted 23 November 2015
Available online xxx
Keywords:
Multicomponent reaction
Ionic liquid
Ó 2015 Elsevier Ltd. All rights reserved.
Chroman synthesis
Acid catalyst
1. Introduction
natural products such as vitamin E and flavonoids.6 The significance
of these heterocyclic motifs has led to a demand for efficient syn-
Multicomponent reactions (MCRs) are powerful tools in modern
drug discovery and allow fast, automated and high throughput
synthesis of diverse structural scaffolds required in the search of
novel therapeutic and pharmacologically active molecules.1 Elec-
trophilic reaction of aldehyde with two different nucleophiles is
well known, which has been widely applied in organic synthesis
through the established MCRs.2 Although many successful exam-
ples have been reported, developing new MCRs based on this
strategy often encountered a notorious difficulty in controlling the
reaction selectivity. To address this issue, various approaches have
been developed to prevent the side reaction, condensation reaction
of aldehyde with the same nucleophile.3 An elegant one is to use
bifunctional aldehyde or nucleophile as substrate, which has mul-
tiple reactive sites enabling further intramolecular reaction.4 With
this strategy, the assembly reaction will occur in favor of forming
a stable product, which is generally associated with multiple in-
teractions of two different substrates. Therefore, the reaction se-
lectivity of MCRs is maximized.5
thetic methods. Metal complexes or acids catalyzed addition or
cyclization reactions of phenols and dienes were often used to
synthesize chromans.7
A sequential ring-closing metathesis-
transfer hydrogenation sequence has been used to synthesize
chromanes.8 Recently, intramolecular oxo-Michael addition re-
action was also employed to construct this scaffold.9 Although
there are myriad methods known to accomplish the synthesis of
these privileged molecules and their derivatives, sustained efforts
have been paid to developing efficient synthetic methods under
user-friendly conditions.
Recently, styrene derivatives were used as p-type nucleophiles
in many organic transformations.10 Particularly, in electrophilic
reaction of aldehyde, 1,1-diphenylethylene has been demonstrated
to be a very active nucleophile.11 We have recently investigated
three-component reactions of aldehyde with two different nucle-
ophiles.12 However, to the best of our knowledge, in this type of
MCRs, the styrenyl system-based
p-type nucleophiles have been
rarely reported.13 Considering the fact that 1,1-diphenylethylene
contains a CeC double bond, which is quite reactive upon addi-
tion of hydroxyl group,14 it is not unreasonable to expect that this
type of compound can act as a bifunctional nucleophile in estab-
lishing some three-component reaction of aldehyde. Out of these
considerations, we started some time ago, a research program on
this topic.
Chromans (dihydrobenzopyrans) are important and ubiquitous
structural motifs found in a variety of important biologically active
* Corresponding authors. Fax: þ86 (0)27 87 54 45 32 (Y.G.); e-mail addresses:
candyyjing@163.com (J. Yang), zj19820305@163.com (J. Zhang), klgyl@hust.edu.cn
(Y. Gu).
http://dx.doi.org/10.1016/j.tet.2015.11.049
0040-4020/Ó 2015 Elsevier Ltd. All rights reserved.
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A. Taheri et al. / Tetrahedron xxx (2015) 1e10
Brønsted acid ionic liquids have been widely used in synthesis
great delight, the three-component reaction proceeded very well
over ionic liquid 1a, and 93% of yield was obtained under the
identical conditions (entry 7). A conventional SO3H-functionalized
Brønsted acid ionic liquid, Forbes’s ionic liquid 1b, was also ex-
amined, however, the yield obtained is inferior as compared with
1a (entry 8). These results give us impetus to investigate the effects
of other parameters on the performance of the model three-
component reaction, such as temperature, reaction time and cata-
lyst amount (entries 9 to 11). Finally, the optimal conditions were
confirmed as follows: 80 ꢀC, 30 min and 5 mol % of ionic liquid 1a. It
should be noted that, at the end of the reaction, the formed product
could be easily isolated with ionic liquid catalyst by means of ex-
traction using dichloromethane. The recovered ionic liquid 1a could
be reused in the next run after 20 min of treatment under vacuum
conditions at 80 ꢀC (20 mmHg). Its catalytic activity in the model
reaction keeps unchanged in at least six runs.
To extend the scope of the reaction, other substrates were
submitted to the condensation under the conditions of entry 7. The
relevant results are reported in Fig. 1. First, various benzaldehydes
were examined by using 2-naphthol and 1,1-diphenylethylene as
counter substrates. In all cases, good to excellent yields were ob-
tained, whatever the nature of the substituent present on the al-
dehyde (electron-donating or electron-withdrawing). An aliphatic
aldehyde, 3-phenylpropanal, was also used, and the result obtained
was as competent as in the case of the aromatic aldehyde. Some
other phenols, such as 6-bromo-2-naphthol, trimethylhy-
droquinone and sesamol, were also submitted to the condensation.
And all these phenols afforded the corresponding adducts in good
yields under the conditions of entry 7. Proceeding on the same line,
we finally extended our strategy to more complex substrates in
order to determine the scope of our methodology. Remarkably, as
and catalysis.15 Particularly, these ILs have also been proved to be
effective for promoting many MCRs.16 Herein, we report for the
first time the use of 1,1-diphenylethylene as a bifunctional nu-
cleophile in establishing three-component reactions. The aim of
this work is to show that a combination of styrenyl system-based
p
-type nucleophile with aldehyde may provide a promising sce-
nario where three-component assembly occurs selectively, pro-
viding various densely substituted chroman derivatives in an
expedient way. The use of a Brønsted acid ionic liquid is the key to
make MCRs possible.
2. Results and discussion
Initially, three-component reaction of benzaldehyde 2a, 2-
naphthol 3a and 1,1-diphenylethylene 4a was investigated, and
the results are listed in Table 1. The reaction was performed under
solvent-free conditions at 80 ꢀC. The expected product was chro-
man 5a. In the presence of strong Brønsted acids, such as tolue-
nesulfonic acid and triflic acid, the three-component reaction
proceeded, but 5a was obtained only in moderate yields after
30 min of reaction (entries 1 and 2). Trifluoroacetic acid was proved
to be ineffective for this reaction (entry 3). The performance of
Lewis acids, such as Sc(OTf)3, Fe(OTf)3 and ZnCl2, was also exam-
ined in the three-component reactions, and the yield reached only
to 30% in the best case (entries 4 to 6). Although the yields are not
satisfactory, these preliminary results demonstrated that synthesis
of chroman through 1,1-diphenylethylene-participated three-
component reaction of aldehyde and a OH-containing counter
nucleophile is indeed possible. In order to find a suitable catalyst for
this three-component reaction, we then turned to a sulfonyl-
containing Brønsted acid ionic liquid 1a, which has displayed re-
markable catalytic activity in various organic reactions.17 To our
shown
in
Fig.
1,
4-hydroxycoumarin
2-hydroxy-1,4-
naphthoquinone, 4-hydroxy-6-methyl-2-pyrone and dimedone
also selectively reacted with 2-naphthol and 1,1-diphenylethylene,
affording a diverse array of valuable and complex chroman de-
rivatives. Di(4-chlorophenyl)ethylene can also be used in this
three-component reaction. However, attempts to use simple sty-
rene and its substituted counterparts, such as 4-methylstyrene and
Table 1
Three-component reaction of benzaldehyde 2a, 2-naphthol 3a and 1,1-
diphenylethylene 4aa
a
-methylstyrene, failed to afford the desired product. It may result
from the poor nucleophilicities of these styrenes.13
Ph-p-Me
Ph-p-Br
Ph-p-CF
3
Br
Ph
Ph
Ph
Ph
Ph
Ph
O
O
O
Ph
Ph
O
5b 91%
5c 91%
5d 90%
5e 80%
Ph
Cl
Cl
O N
2
Br
Cl
F
Entry
Catalyst
Yield (%)
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
5i 78%
1
2
3
4
5
6
7
8
PTSA
TfOH
CF3CO2H
Sc(OTf)3
Fe(OTf)3
ZnCl2
1a
1b
1a
1a
1a
54
45
Trace
30
15
Trace
93
60
61
49
O
O
O
O
5f 85%
5h 79%
Ph
5g 79%
Br
Ph
O
Ph
O
O
Ph
HO
O
O
O
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
O
O
9b
10c
11d
12f
5j 91%
5k 87%
Ph
5m 77%
Ph
5l 84%
Ph
73
92
O
O
O
O
Ph
1a
O
Ph-p-Cl
Ph-p-Cl
a
Ph
Ph
Ph
Ph
Ph
Ph
O
Reaction conditions: 2a, 0.5 mmol; 3a, 0.5 mmol, 4a, 0.5 mmol; catalyst,
O
O
O
0.025 mmol; 80 ꢀC, 30 min.
b
1a, 0.0125 mmol.
5n 76%
5o 81%
5q 69 %
5p 80 %
c
50 ꢀC.
d
15 min.
1a was reused in the fifth run.
Fig. 1. Scope of three-component reaction of aldehyde, phenol and 1,1-
diphenylethylene.
f
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A. Taheri et al. / Tetrahedron xxx (2015) 1e10
3
As 1,1-diphenylethylene was normally synthesized through
dehydration of 1,1-diphenylethanol under acidic condition, we then
studied the possibility of synthesizing 5a from the precursor of 1,1-
diphenylethylene. As shown in Scheme 1, with ionic liquid 1a cat-
alyst, benzaldehyde, 2-naphthol and 1,1-diphenylethanol 6a as-
sembled smoothly under solvent-free conditions, affording 5a in
90% yield. In a similar fashion, 4,40-dichloro-alpha-methylbenzhy-
drol 6b reacted smoothly with benzaldehyde and 2-naphthol under
typical reaction conditions to afford the respective chroman 5q in
89% of yield. This reaction offered a cost-effective alternative to
synthesize 5a-type chroman without using expensive olefins.
Based on these observations, we deduced that the three-
component reaction was most likely triggered by an acid-
catalyzed electrophilic alkylation of benzaldehyde with a nucleo-
phile. 2-Naphthol-initiated mechanism involves the formation of
cationic intermediate (I), which was then trapped by 1,1-
diphenylethylene to form (II). This species can be formed alterna-
tively through a 1,1-diphenylethylene-initiated mechanism, which
involves the formation of a cationic intermediate (IV). Formation of
the desired product 5a is a result of an intramolecular hydro-
alkoxylation of intermediate (II). Because the selectivity obtained in
the three-component reaction is quite remarkable, we deduced
that the last step, intramolecular cyclization, may play a pivotal role
in maximizing the reaction selectivity.19 It should be noted that
a mechanism involving the formation of an ortho-quinone methide
intermediate (III) and oxo DielseAlder may also afford 5a. Based on
CHO
OH
+
the observations with 4-methylstyrene and a-methylstyrene, and
2a
3a
1a (10 mol %)
R
+
considering the literature results on tandem Knoevenagel/oxo
DielseAlder reaction,20 we believe that the last one is hardly op-
erative in the model reaction (Fig. 2).
O
80 C, 30 minutes
OH
R
R
R
If the mechanism involving formation of intermediate (II) is
operative, salicylaldehyde may also be used as a bifunctional
counter reagent of 1,1-diphenylethylene in the presence of a suit-
able nucleophile. The formed product should contain also a skele-
ton of chroman. Out of these considerations, three-component
reaction of salicylaldehyde 9a, 1,1-diphenylethylene and 1-methyl-
2-phenylindole 10a was then studied. As shown in Fig. 3, the ex-
pected product 11a was obtained in 81% yield by using 1a as cat-
alyst after 30 min of reaction at 80 ꢀC. Other salicylaldehydes also
underwent the catalytic condensation reaction to give the chroman
derivatives in good to excellent yields. Results with other indoles,
such as 2-methylindole, 5-bromoindole, 2-phenylindole and 1-
ethyl-2-phenylindole largely paralleled those of 1-methyl-2-
phenylindole. Finally, it was shown that the same conditions
could be applied with success to other nucleophile, such as tri-
methoxybenzene 12a (Scheme 3). In these reactions, an intra-
molecular hydroalkoxylation may play an important role in
5a R = H, 90 %
6a R = H
5q R = Cl, 89 %
6b R = Cl
Scheme 1. Three-component reaction of benzaldehyde, 1,1-diphenylethanol and 2-
naphthol.
To gain insights into the model three-component reaction, some
control experiments were carried out to elucidate the mechanism.
Firstly, benzaldehyde was treated by 1,1-diphenylethylene in the
presence of ionic liquid 1a. Intriguingly, a skipped diene 7a was
obtained after 30 min.11a Increasing the amount of 1,1-
diphenylethylene to 2.0 equiv led to 88% yield (Scheme 2). It is
well-known that benzaldehdye can react with 2-naphthol under
acidic conditions to form 8a.18 Ionic liquid 1a was found to be an
effective catalyst for this reaction as well (Scheme 2). Heating of
a mixture composed of 1,1-diphenylethylene and 2-naphthol at
80 ꢀC in the presence of ionic liquid 1a led to only recovery of
starting materials.
OH
3a (2.0 equiv.)
4a (2.0 equiv.)
1a (5 mol %)
CHO
1a (5 mol %)
80 C, 30 minutes
80 C, 30 minutes
O
2a
7a 88 %
8a 94 %
Scheme 2. Treatment of benzaldehyde with 1,1-diphenylethylene or 2-naphthol in the presence of ionic liquid 1a.
H
O
HO
or
- H O
- H O
H
acid catalyst
OH
O
(I)
(III)
(IV)
OH
oxo Diels-Alder
intramolecular cyclization
OH
O
(II)
5a
Fig. 2. Proposed mechanism.
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4
A. Taheri et al. / Tetrahedron xxx (2015) 1e10
maximizing the reaction selectivity. These results manifested that
three-component of salicylaldehyde and 1,1-diphenylethylene is
indeed an effective way to construct chroman scaffold.
Products generated from all the above-mentioned reactions are
generally solid. Structures of some products have been un-
ambiguously confirmed by the X-ray structural analysis. The details
are shown in Fig. 5, Fig. S1 and Table S1 (crystal data).
3. Conclusion
N
CHO
1a (5 mol %)
Ph
Ph
+
+
Ph
80 oC, 30 minutes
N
A general method was developed for the synthesis of chroman
derivatives through three-component reaction of aldehyde and 1,1-
diarylethylene. As the reaction was established with the aid of
intramolecular hydroalkoxylation of CeC double bond, some
hydroxy-containing carbon-based nucleophiles or salicylaldehydes
could be used as suitable reaction partners of 1,1-diarylethylene. A
sulfonyl-containing Brønsted acid ionic liquid was proved to be an
effective catalyst for these reactions. This method is very efficient to
synthesize chroman derivatives, and the only by-product is water.
Simple and readily available substrates and high functional group
compatibility are the features obtained in these systems. Another
advantage of using ionic liquid as a catalyst for these trans-
formations is that the catalyst can be easily recovered after com-
pletion of the reaction and can be reused in subsequent reactions.
Although at the present stage, the product diversity in these re-
actions are limited owing to the failure of using other olefins, the
transformation itself is interesting, and these results have already
served as a starting point for further investigations, which are
currently on going in our laboratories.
OH
4a
9a
10a
O
Ph
11a 81%
NH
N
N
N
Ph
Ph
Ph
Ph
Ph
Ph
R
Ph
Ph
Ph
O
O
O
O
Ph
Ph
Ph
OEt
11c R = Cl, 63%
11f 81%
11b 79%
11e 76%
NH
11d R = Br, 61%
NH
Et
N
N
Br
Ph
Cl
Br
Ph
Ph
Ph
Ph
Ph
Ph
Ph
O
O
O
O
Ph
11i 83%
11j 76%
11g 79%
11h 75%
Fig. 3. Three-component reaction of salicylaldehyde, 1,1-diphenylethylene and indole.
OMe
OMe
R
CHO
OH
4. Experimental section
4.1. General
+
MeO
OMe
MeO
OMe
1a (5 mol %)
9a R = H
9b R = NO2
R
12a
80 oC, 30 minutes
O
All the chemical reagents were used as they were received. Ionic
liquid 1a was synthesized according to a reported method.14a Ionic
liquid 1b was synthesized based on a literature’s method.22 1H and
13C NMR spectra were recorded on a Bruker AV-400. Chemical
shifts are expressed in ppm relative to Me4Si in CDCl3. HRMS was
recorded on a Bruker micrOTOF-Q II instrument. IR spectra were
recorded on an FTIR Bruker (VERTEX 70) using liquid film tech-
nology. All reactions were conducted in a 10 mL of V-type flask
equipped with triangle magnetic stirring.
+
4a
13a R = H, 86%
13b R = NO2, 91 %
Scheme 3. Three-component reaction of salicylaldehyde, 1,1-diphenylethylene and
trimethoxybenzene.
During our investigations, we found that chroman synthesis
using a two-component reaction of salicylaldehdye and 1,1-
diphenylethylene is also possible. By using ionic liquid 1a as cata-
lyst, a densely substituted chroman 14a could be obtained in 95%
yield (Fig. 4). The reaction might proceed through a tandem path-
way involving (i) electrophilic alkylation of aldehyde that gener-
ated a skipped diene, and (ii) an intramolecular hydroalkoxylation
of the diene intermediate, which afforded 14a as the final product.
4.2. A typical procedure for the multi component reactions
1a (11.8 mg, 0.025 mmol) was mixed with 1,1-diphenylethylene
4a (90.0 mg, 0.5 mmol) and 2-naphthol 3a (72.0 mg, 0.5 mmol) and
benzaldehyde 2a (53.0 mg, 0.5 mmol). The mixture was stirred for
30 min at 80 ꢀC. After reaction, the temperature was lowered to
room temperature and the reaction mixture solidified rapidly. Then
the mixture was washed with dicholoromethane (3 mlꢁ3). The
organic phase was combined together, and dried with anhydrous
Na2SO4. Then it was subjected to a flash silica column chromatog-
raphy after removing volatile solvent by a rotary evaporator. A
mixed solution of ethyl acetate and petro ether as eluting solvent
(the ratio of ethyl acetate/petroether is 1/20v/v) was used as eluting
solvent. The desired product 5a was obtained in 93% of yield,
191.8 mg. Tests for substrate scopes were all performed according
to an analogous procedure. The recovered ionic liquid was treated
at 80 ꢀC under vacuum (20 mmHg) for 20 min, and then used in the
next run.
In
a
similar fashion, other salicylaldehydes and 1,1-
diphenylethylenes were also applicable in this condensation. This
reaction offered another way to construct chroman scaffold with-
out using any counter nucleophile.
Ph
CHO
OH
1a (5 mol %)
Ph
Ph
Ph
14a 95 %
+
80 C, 30 minutes
4a
9a
O
Ph-p-Cl
Ph-p-Cl
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Cl
Br
O N
4.3. Spectroscopic data of ionic liquids and organic products
Ph-p-Cl
Ph-p-Cl
O
O
O
O
Ph
Ph
Ph
4.3.1. 4-n-Buthyl-4-(3-sulfopropyl)thiomorpholinium 1,1-dioxide tri-
14d 79%
14b 92%
14e 65%
14c 88%
fluoromethane sulfonate (1a). Gum-like brown oil, 1H NMR
(400 MHz, D2O, 25 ꢀC):
d
¼3.82 (t, J¼8.0 Hz, 4H), 3.51e3.43 (m, 6H),
Fig. 4. Chroman synthesis through reaction of salicylaldehydes and 1,1-
diphenylethylenes.
3.30 (t, J¼8.0 Hz, 2H), 2.76 (t, J¼8.0 Hz, 2H), 2.00e1.93 (m, 2H), 1.51
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A. Taheri et al. / Tetrahedron xxx (2015) 1e10
5
Fig. 5. Crystal structures with numbered atoms of some products.21 Displacements ORETP are drawn at the 50% probability level with the atom-numbering scheme.
(quintet, J¼8.0 Hz, 2H), 1.18 (sex, J¼8.0 Hz, 2H), 0.72 ppm (t,
126.1, 125.9, 125.4, 123.3, 120.1, 116.2 (CPh-Ar, CHPh-Ar), 81.8
J¼8.0 Hz, 3H); 13C NMR (100 MHz, D2O, 25 ꢀC):
d¼121.1, 117.9
(COCH2Ph2), 45.0 (CHCH2), 38.9 (CH2) ppm. IR (cmꢂ1): 3056, 3023,
2955, 2927, 1620, 1597, 1512, 1490, 1447, 1395, 1345, 1231, 1206,
1158, 1088, 1060, 1026. HRMS (TOF, ESI): m/z calcd for C31H24NaO,
[MþNa]þ 435.1725, found 435.1724.
(CH2SO2), 57.3 (CH2SO3H), 46.7, 44.9 (CH2Nþ), 22.9, 18.7, 17.3, 12.6
(CH2CH3).
4.3.2. 1,3,3-Triphenyl-2,3-dihydro-1H-benzo[f]chromene
(5a). White solid, mp¼111e113 ꢀC. 1H NMR (400 MHz, CDCl3, TMS,
4.3.3. 3,3-Diphenyl-1-(p-tolyl)-2,3-dihydro-1H-benzo[f]chromene
25 ꢀC):
d
¼7.66 (d, J¼8.8 Hz, 1H), 7.60 (d, J¼8.0 Hz, 1H), 7.52 (d,
(5b). White solid, mp¼155e157 ꢀC, 1H NMR (400 MHz, CDCl3, TMS,
J¼8.0 Hz, 2H), 7.41e7.37 (m, 3H), 7.21e7.10 (m, 5H), 7.07e7.01 (m,
6H), 6.96 (t, J¼8.0 Hz, 3H), 4.44 (dd, J¼9.6, 7.6 Hz, 1H), 3.28 (dd,
J¼14.4, 6.8 Hz, 1H), 2.69 ppm (dd, J¼14.4, 10.0 Hz, 1H); 13C NMR
25 ꢀC):
d
¼7.71e7.61 (m, 3H), 7.54e7.40 (m, 6H), 7.26e7.14 (m, 7H),
6.91e6.88 (m, 4H), 4.42e4.40 (m,1H), 3.34e3.27 (m,1H), 2.71e2.63
(m, 1H), 2.19 ppm (d, J¼4.0 Hz, 3H); 13C NMR (100 MHz, CDCl3,
(100 MHz, CDCl3, 25 ꢀC):
d¼153.4, 146.6, 145.4, 143.5, 132.8, 130.1,
25 ꢀC)
d 153.3, 145.5, 143.6, 143.3, 135.6, 132.8, 130.1, 129.6, 129.4,
129.5, 129.0, 128.8, 128.6, 128.4, 127.9, 127.5, 127.4, 126.7, 126.2,
129.0, 128.8, 128.5, 128.4, 128.4, 127.7, 127.4, 127.3, 126.7, 126.0,
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6
A. Taheri et al. / Tetrahedron xxx (2015) 1e10
125.7, 125.4, 123.2, 120.1, 116.4 (CPh-Ar, CHPh-Ar), 81.8 (COCH2Ph2),
45.2 (CHCH2), 38.4(CH2), 21.3 (CH3) ppm. IR (cmꢂ1): 3054, 3019,
2956, 2917, 2867, 2854, 1620, 1600, 1510, 1493, 1463, 1445, 1390,
1341, 1231, 1205, 1184, 1158, 1107, 1063. HRMS (TOF, ESI): m/z calcd
for C32H26NaO, [MþNa]þ 449.1881, found 449.1870.
1045, 1012. HRMS (TOF, ESI): m/z calcd for C31H22Cl2NaO, [MþNa]þ
503.0945, found 503.0930.
4.3.8. 1-(2-Chloro-5-nitro-phenyl)-3,3-diphenyl-2,3-dihydro-1H-
benzo[f]chromene (5g). White solid, mp¼210e212 ꢀC. 1H NMR
(600 MHz, CDCl3, TMS, 25 ꢀC):
d
¼7.84e7.82 (m, 2H), 7.81e7.79 (m,
4.3.4. 4-(4-Bromophenyl)-2,2-diphenyl-3,4-dihydro-2H-benzo[h]
1H), 7.76 (d, J¼12.0 Hz,1H), 7.56 (d, J¼6.0 Hz, 2H), 7.47 (d, J¼12.0 Hz,
1H), 7.31 (t, J¼6.0 Hz, 2H), 7.27e7.26 (m, 2H), 7.22 (d, J¼12.0 Hz,
2H), 7.15 (t, J¼6.0 Hz, 1H), 7.05 (t, J¼6.0 Hz, 2H), 6.98 (t, J¼6.0 Hz,
1H), 6.92e6.88 (m, 2H), 5.05 (t, J¼6.0 Hz, 1H), 3.28 (q, J¼6.0 Hz, 1H),
chromene (5c). White solid, mp¼108e110 ꢀC, 1H NMR (600 MHz,
CDCl3, TMS, 25 ꢀC):
d
¼7.81e7.76 (m, 1H), 7.72 (dd, Ja¼6.0 Hz,
Jb¼24.0 Hz, 2H), 7.53 (dd, Ja¼6.0 Hz, Jb¼12.0 Hz, 2H), 7.42e7.40 (m,
1H), 7.36 (dd, Ja¼6.0 Hz, Jb¼12.0 Hz, 2H), 7.27e7.23 (m, 2H),
7.22e7.20 (m, 2H), 7.18e7.13 (m, 5H), 7.10e7.07 (m, 1H), 6.81 (d,
J¼6.0 Hz, 2H), 4.45 (t, J¼6.0 Hz, 1H), 3.28 (dd, Ja¼6.0 Hz,
Jb¼12.0 Hz, 1H), 2.74e2.69 ppm (m, 1H); 13C NMR (100 MHz,
3.02 ppm (q, J¼6.0 Hz, 1H); 13C NMR (100 MHz, CDCl3):
¼153.3,
d
146.5, 144.1, 143.8, 143.4, 139.3, 130.3, 130.1, 128.9, 128.5, 128.2,
127.6, 127.2, 126.9, 126.6, 126.1, 125.7, 125.1, 124.7, 123.5, 123.0,
122.0, 119.8, 118.4 (CPh-Ar, CHPh-Ar), 81.1 (COCH2Ph2), 38.8 (CHCH2),
34.9 (CH2) ppm. IR (cmꢂ1): 3437, 3059, 3021, 2954, 2922, 2852,
1624, 1603, 1573, 1518, 1464, 1442, 1405, 1344, 1266, 1241, 1210,
1195, 1149, 1097, 1045, 1012. HRMS (TOF, ESI): m/z calcd for
CDCl3, 25 ꢀC):
d
¼153.2, 145.2, 144.6, 143.3, 132.3, 131.7, 129.5,
129.5, 128.6, 128.5, 128.2, 127.4, 127.2, 126.4, 125.9, 124.7, 123.2,
119.9 (CPh-Ar, CHPh-Ar), 81.4 (COCH2Ph2), 44.1 (CHCH2), 37.9(CH2)
ppm. IR (cmꢂ1): 3449, 3057, 2961, 2925, 1709, 1621, 1594, 1512,
1484, 1462, 1431, 1398, 1348, 1234, 1210, 1063, 1007. HRMS (TOF,
C
31H22ClNNaO3, [MþNa]þ 514.1186, found 514.1173.
ESI): m/z calcd for
513.0821.
C
31H23BrNaO, [MþNa]þ 513.0830, found
4.3.9. 1-(5-Bromo-2-fluorophenyl)-3,3-diphenyl-2,3-dihydro-1H-
benzo[f]chromene (5h). White solid, mp¼148e150 ꢀC. 1H NMR
(400 MHz, CDCl3, TMS, 25 ꢀC):
d
¼7.80e7.74 (m, 2H), 7.70 (d,
4.3.5. 3,3-Diphenyl-1-(4-(trifluoromethyl)phenyl)-2,3-dihydro-1H-
benzo[f]chromene (5d). White solid, mp¼129e131 ꢀC. 1H NMR
(400 MHz, CDCl3, TMS, 25 ꢀC): 1H NMR (400 MHz, CDCl3, TMS,
J¼8.0 Hz, 1H), 7.54 (d, J¼8.0 Hz, 2H), 7.46e7.39 (m, 2H), 7.32e7.24
(m, 4H), 7.17e7.08 (m, 7H), 6.91e6.85 (m, 1H), 4.86 (t, J¼8.0 Hz, 1H),
3.24 (q, J¼8.0 Hz, 1H), 2.92 ppm (q, J¼8.0 Hz, 1H); 13C NMR
25 ꢀC):
d
¼7.76e7.74 (m, 2H), 7.70 (d, J¼8.0 Hz, 1H), 7.55e7.53 (m,
(100 MHz, CDCl3, 25 ꢀC):
d
¼160.7, 158.3, 153.3, 148.9, 143.9, 143.8,
3H), 7.30e7.24 (m, 5H), 7.15e7.14 (m, 2H), 7.08 (d, J¼4.0 Hz, 5H),
134.2,133.9,132.7,132.1,131.5,131.0,130.6,129.8,129.8,129.6,129.5,
128.9, 128.7, 128.3, 128.2, 128.1, 127.5, 127.4, 126.4, 126.3, 125.8,
124.7, 123.6, 123.4, 122.1, 122.1, 119.9, 118.2, 117.0, 116.7, 116.0, 113.2
(CPh-Ar, CHPh-Ar), 81.3 (COCH2Ph2), 60.5 (CHCH2), 40.5 (CH2) ppm. IR
(cmꢂ1): 3441, 3066, 2959, 2928, 2854, 1620, 1598, 1511, 1475, 1442,
1397, 1345, 1318, 1264, 1230, 1158, 1102, 1086. HRMS (TOF, ESI): m/z
calcd for C31H22BrFNaO, [MþNa]þ 531.0736, found 531.0740.
6.89 (d, J¼8.0 Hz, 2H), 3.28e3.23 (m, 1H), 2.86 ppm (h, J¼4.0 Hz,
1H); 13C NMR (100 MHz, CDCl3, 25 ꢀC):
d¼153.1, 149.1, 149.0, 147.9,
144.0, 143.7, 136.6,136.5, 132.4,131.4, 131.1, 129.8,129.7, 129.4, 129.1,
129.0, 128.6, 128.3, 128.2, 127.5, 127.2, 127.1, 126.3, 126.1, 126.0,
124.6, 124.4, 123.3, 122.4, 121.2, 119.9, 118.1, 116.6, 114.5 (CPh-Ar
,
CHPh-Ar), 81.3 (COCH2Ph2), 60.5 (CHCH2), 43.3 (CH2), 37.8 (d,
J¼21.0 Hz, CF3) ppm. IR (cmꢂ1): 3451, 3060, 2962, 2926, 1623, 1596,
1513,1491,1464, 1433, 1401, 1347,1236,1211,1117,1085,1061. HRMS
(TOF, ESI): m/z calcd for C32H23F3NaO, [MþNa]þ 503.1599, found
503.1587.
4.3.10. 3,3-Diphenyl-1-(3-phenylpropyl)-2,3-dihydro-1H-benzo[f]
chromene (5i). Yellow viscous liquid. 1H NMR (400 MHz, CDCl3,
TMS, 25 ꢀC):
d
¼7.68 (m, 2H), 7.60 (q, J¼4.0 Hz, 2H), 7.50e7.49 (m,
8H), 7.26e7.19 (m, 9H), 4.11e4.08 (m, 1H), 3.22e3.16 (m, 2H), 2.20
4.3.6. 1-(2-Bromophenyl)-3,3-diphenyl-2,3-dihydro-1H-benzo[f]
(s, 2H), 1.49e1.46 (m, 2H), 1.25e1.20 ppm (m, 2H); 13C NMR
chromene (5e). White solid, mp¼138e140 ꢀC, 1H NMR (600 MHz,
(100 MHz, CDCl3, 25 ꢀC):
d¼151.8, 146.4, 144.1, 141.9, 132.2, 129.9,
CDCl3, TMS, 25 ꢀC):
d
¼7.80 (dd, Ja¼12.0 Hz, Jb¼18.0 Hz, 1H), 7.74 (d,
128.8, 128.6, 128.5, 128.4, 128.3, 127.3, 127.2, 126.6, 126.1, 125.8,
123.1, 119.9, 118.6 (CPh-Ar, CHPh-Ar), 81.4 (COCH2Ph2), 39.0 (CHCH2),
37.3 (CH2), 33.5 (CH2), 30.2 (CH2) ppm. IR (cmꢂ1): 3444, 3058, 3024,
2924, 2859, 1620, 1597, 1511, 1492, 1447, 1393, 1262, 1233, 1159,
1120, 1094, 1074, 1029. HRMS (TOF, ESI): m/z calcd for C33H28NaO,
[MþNa]þ 463.2038, found 463.2045.
J¼6.0 Hz, 1H), 7.70 (d, J¼6.0 Hz, 1H), 7.53e7.51 (m, 2H), 7.42e7.40
(m, 1H), 7.36e7.34 (m, 2H), 7.27e7.24 (m, 2H), 7.22e7.20 (m, 2H),
7.17e7.15 (m, 5H), 7.10e7.07 (m, 1H), 6.80 (d, J¼6.0 Hz, 2H), 4.44 (m,
1H), 3.28 (q, J¼6.0 Hz, 1H), 2.73e2.69 ppm (m, 1H); 13C NMR
(100 MHz, CDCl3, 25 ꢀC):
d¼153.4, 149.0, 145.3, 145.0, 142.8, 132.7,
132.1, 129.9, 129.4, 129.3, 128.6, 128.4, 128.2, 128.0, 127.7, 127.4,
127.2, 126.6, 125.7, 124.8, 123.1, 119.9, 118.2, 115.7 (CPh-Ar, CHPh-Ar),
81.8 (COCH2Ph2), 41.5 (CHCH2), 38.0 (CH2) ppm. IR (cmꢂ1): 1344,
3057, 2954, 2927, 2856, 1619, 1595, 1512, 1492, 1464, 1433, 1397,
1311, 1234, 1210, 1087, 1051, 1023. HRMS (TOF, ESI): m/z calcd for
4.3.11. 8-Bromo-1,3,3-triphenyl-2,3-dihydro-1H-benzo[f]chromene
(5j). White solid, mp¼175e177 ꢀC, 1H NMR (400 MHz, CDCl3, TMS,
25 ꢀC):
d
¼7.81 (d, J¼1.6 Hz, 1H), 7.62 (d, J¼12.0 Hz, 1H), 7.53 (d,
J¼4.0 Hz, 2H), 7.43e7.39 (m, 3H), 7.27 (t, J¼8.0 Hz, 2H), 7.23e7.21
C
31H23BrNaO, [MþNa]þ 513.0830, found 513.0841.
(m, 2H), 7.19e7.12 (m, 5H), 7.08e7.06 (m, 2H), 6.98 (d, J¼8.0 Hz, 2H),
4.43e4.38 (m, 1H), 3.35e3.30 (m, 1H), 2.71e2.65 ppm (m, 1H); 13
C
4.3.7. 4-(2,3-Dichlorophenyl)-2,2-diphenyl-3,4-dihydro-2H-benzo[h]
NMR (100 MHz, CDCl3, 25 ꢀC):
d¼153.4, 146.0, 144.9, 142.9, 131.1,
chromene (5f). White solid, mp¼124e126 ꢀC. 1H NMR (600 MHz,
131.1, 130.2, 128.8, 128.7, 128.6, 128.3, 128.2, 127.6, 127.4, 127.3,
126.82, 126.40, 126.2,125.74,121.0,116.8,116.3 (CPh-Ar, CHPh-Ar), 81.7
(COCH2Ph2), 44.7 (CHCH2), 38.6 (CH2) ppm. IR (cmꢂ1): 3058, 3025,
2924, 1615, 1590, 1493, 1447, 1388, 1342, 1262, 1232, 1208, 1159,
1118, 1068, 1029. HRMS (TOF, ESI): m/z calcd for C31H23BrNaO,
[MþNa]þ 513.0830, found 513.0841.
CDCl3, TMS, 25 ꢀC):
d
¼7.72 (dd, Ja¼6.0 Hz, Jb¼24.0 Hz, 2H), 7.58 (d,
J¼12.0 Hz, 2H), 7.40 (dd, Ja¼6.0 Hz, Jb¼18.0 Hz, 3H), 7.24e7.16 (m,
10H), 6.95 (d, J¼6.0 Hz, 1H), 6.90 (d, J¼6.0 Hz, 1H), 5.02 (t, J¼6.0 Hz,
1H), 3.44 (q, J¼6.0 Hz, 1H), 2.62 ppm (t, J¼12.0 Hz, 1H); 13C NMR
(100 MHz, CDCl3, 25 ꢀC):
d¼153.4, 145.5, 145.2, 144.9, 143.0, 142.7,
142.5, 139.2, 133.5, 132.9, 132.0, 131.0, 129.9, 129.7, 129.5, 129.4,
129.2, 128.8, 128.7, 128.5, 128.4, 128.2, 128.2, 128.1, 128.06, 127.7,
127.6, 127.5, 127.5, 127.3, 127.2, 126.4, 126.1, 125.7, 124.3,123.3, 119.9,
115.0 (CPh-Ar, CHPh-Ar), 81.7 (COCH2Ph2), 44.1 (CHCH2), 36.1 (CH2)
ppm. IR (cmꢂ1): 3435, 3061, 3021, 2955, 2902, 2851, 1622, 1600,
1571, 1518, 1465, 1443, 1415, 1344, 1266, 1241, 1210, 1195, 1149, 1097,
4.3.12. 6,6,8-Triphenyl-7,8-dihydro-6H-[1,3]dioxolo[4,5-g]chromene
(5k). White solid, mp¼141e143 ꢀC. 1H NMR (400 MHz, CDCl3, TMS,
25 ꢀC):
d
¼7.50e7.44 (m, 4H), 7.29e7.14 (m, 11H), 6.70e6.67 (m, 1H),
6.07e6.05 (m, 1H), 5.66 (d, J¼14.8 Hz, 2H), 3.79e3.77 (m, 1H),
3.07e3.04 (m, 1H), 2.56e2.53 ppm (m, 1H); 13C NMR (100 MHz,
Please cite this article in press as: Taheri, A.; et al., Tetrahedron (2015), http://dx.doi.org/10.1016/j.tet.2015.11.049

A. Taheri et al. / Tetrahedron xxx (2015) 1e10
7
CDCl3, 25 ꢀC):
128.5, 127.5, 127.4, 127.0, 126.5, 125.9, 117.2, 108.5, 101.0 (CPh-Ar
CHPh-Ar), 99.1 (CH2O2), 82.1 (COCH2Ph2), 42.4 (CHCH2), 40.5 (CH2)
ppm. IR (cmꢂ1): 3062, 3022, 2954, 2899, 2874, 1630, 1601, 1481,
1449,1426,1388,1336,1311,1243,1216,1183,1152,1097,1062,1032.
HRMS (TOF, ESI): m/z calcd for C28H22NaO3, [MþNa]þ 429.1467,
found 429.1473.
d
¼149.1, 147.2, 145.9, 144.8, 143.7, 141.8, 128.9, 128.8,
TMS, 25 ꢀC):
d
¼8.15 (dd, J¼7.5, 1.1 Hz, 1H), 7.84 (dd, J¼7.4, 1.1 Hz,
,
1H), 7.63 (m, 2H), 7.52 (d, J¼7.6 Hz, 2H), 7.45e7.42 (m, 2H), 7.35 (t,
J¼7.6 Hz, 2H), 7.28e7.24 (m, 5H), 7.21e7.16 (m, 4H), 4.01 (dd, J¼10.8,
6.8 Hz, 1H), 3.28 (dd, J¼14.8, 6.8 Hz, 1H), 2.53 ppm (dd, J¼14.8,
11.2 Hz, 1H). 13C NMR (100 MHz, CDCl3, 25 ꢀC):
d
¼183.3, 179.7 (C]
O), 155.5 (C¼COPh), 143.7, 143.4, 141.8, 134.1, 133.1, 132.3, 131.1,
129.1, 128.8, 128.5, 128.1, 127.7, 127.2, 126.6, 126.3, 126.3, 125.7, 125.4
(CPh-Ar, CHPh-Ar), 124.9 (C]C), 84.8 (COCH2Ph2), 42.9 (CHCH2), 36.9
(CH2) ppm. IR (cmꢂ1): 3046, 3060, 3025, 2927, 1678, 1654, 1616,
1595, 1577, 1492, 1449, 1364, 1332, 1300, 1264, 1202, 1153, 1093,
1059. HRMS (TOF, ESI): m/z calcd for C31H22NaO3, [MþNa]þ
465.1467, found 465.1475.
4.3.13. 5,7,8-Trimethyl-2,2,4-triphenylchroman-6-ol
(5l). White
solid, mp¼190e191 ꢀC. 1H NMR (400 MHz, CDCl3, TMS, 25 ꢀC):
d¼7.47 (d, J¼6.8 Hz, 2H), 7.42 (d, J¼7.2 Hz, 2H), 7.24 (t, J¼7.6 Hz, 2H),
7.19e7.13 (m, 5H), 7.11e7.08 (m, 2H), 7.01 (d, J¼7.6 Hz, 2H) 4.20 (s,
1H), 4.07 (d, J¼7.6 Hz, 1H), 3.23 (dd, J¼15.2, J¼6.4 Hz, 1H), 2.45 (s,
3H), 2.17 (s, 3H), 1.46 ppm (s, 3H). 13C NMR (100 MHz, CDCl3, 25 ꢀC):
4.3.18. 2,2-Bis(4-chlorophenyl)-4-phenyl-3,4-dihydro-2H-benzo[g]
d
¼146.8, 146.7, 146.2, 146.1, 128.6, 128.5, 128.1, 127.6, 127.0, 126.8,
chromene (5q). White solid, mp¼260e262 ꢀC. 1H NMR (400 MHz,
126.3, 125.8, 125.4, 123.0, 122.3, 120.5, 119.6 (CPh-Ar, CHPh-Ar), 80.8
(COCH2Ph2), 44.8 (CHCH2), 40.0 (CH2), 13.5, 12.5, 12.5 (CH3) ppm. IR
(cmꢂ1): 3570, 3084, 3056, 3021, 2955, 2930, 1599, 1490, 1445, 1381,
1330, 1289, 1256, 1206, 1180, 1103, 1089, 1006. HRMS (TOF, ESI): m/z
calcd for C30H28NaO2, [MþNa]þ 443.1987, found 443.1980.
CDCl3, TMS, 25 ꢀC):
d
¼7.73 (dd, J¼15.0, 8.6 Hz, 2H), 7.45 (d, J¼8.8 Hz,
2H), 7.37 (d, J¼8.8 Hz, 1H), 7.32e7.18 (m, 6H), 7.15e7.07 (m, 6H),
6.94 (d, J¼6.4 Hz, 2H), 4.48e4.44 (m, 1H), 3.24 (dd, J¼14.4, 7.2 Hz,
1H), 2.72 ppm (dd, J¼14.4, 9.2 Hz, 1H). 13C NMR (100 MHz, CDCl3,
25 ꢀC):
d
¼152.5, 145.6, 142.9, 141.6, 133.4, 133.2, 132.4, 129.9, 129.5,
128.8, 128.7, 128.4, 128.3, 127.7, 127.6, 127.2, 126.0, 125.8, 124.8,
123.3, 119.5, 115.6 (CPh-Ar, CHPh-Ar), 80.6 (COCH2Ph2), 44.2 (CHCH2),
38.2 (CH2) ppm. IR (cmꢂ1): 3458, 3054, 2969, 2929, 2873, 1621,
1597, 1512, 1489, 1462, 1433, 1395, 1346, 1266, 1232, 1210, 1158,
1126, 1090. HRMS (TOF, ESI): m/z calcd for C31H22Cl2NaO, [MþNa]þ
503.0945, found 503.0960.
4.3.14. 2,2,4-Triphenyl-3,4-dihydropyrano[3,2-c]chromen-5(2H)-one
(5m). White solid, mp¼204e206 ꢀC. 1H NMR (400 MHz, CDCl3,
TMS, 25 ꢀC):
d
¼8.14 (d, J¼7.6 Hz, 1H), 7.55e7.51 (m, 1H), 7.46 (d,
J¼8.0 Hz, 2H), 7.41e7.38 (m, 2H), 7.36e7.21 (m, 10H), 7.18e7.15 (m,
3H), 3.91 (dd, J¼10.6, 6.6 Hz, 1H), 3.26 (dd, J¼15.0, 10.6 Hz, 1H),
2.60 ppm (dd, J¼14.5, 11.0 Hz, 1H); 13C NMR (100 MHz, CDCl3,
25 ꢀC):
d
¼161.0 (COOPh), 160.3 (C¼COOPh), 152.9, 143.7, 143.0,
4.3.19. Penta-1,4-diene-1,1,3,5,5-pentaylpentabenzene
141.5, 132.0, 129.1, 128.6, 128.5, 128.1, 127.87, 127.1, 126.6, 125.6,
125.5, 124.1, 122.7, 116.7, 115.9 (CPh-Ar, CHPh-Ar), 104.8 (C]C), 85.1
(COCH2Ph2), 43.4 (CHCH2), 36.8 (CH2) ppm. IR (cmꢂ1): 3402, 3086,
3058, 3031, 2967, 2935, 2897, 1708, 1622, 1568, 1491, 1450, 1381,
1325, 1264, 1222, 1203, 1176, 1155, 1106, 1084. HRMS (TOF, ESI): m/z
calcd for C30H22NaO3, [MþNa]þ 453.1467, found 453.1478.
(7a).11a White solid, mp¼223e225 ꢀC, 1H NMR (400 MHz, CDCl3,
TMS, 25 ꢀC):
d
¼7.23e7.12 (m, 16H), 7.10e7.07 (m, 2H), 7.02 (t,
J¼8.0 Hz, 4H), 6.87 (d, J¼8.0 Hz, 3H), 6.17 (d, J¼8.0 Hz, 2H),
4.45 ppm (t, J¼12.0 Hz, 1H); 13C NMR (100 MHz, CDCl3, 25 ꢀC):
d
¼144.2 (C]CH), 139.5 (C]CH), 142.8, 141.7, 130.1, 129.7, 128.7,
128.2, 128.1, 127.8, 127.8, 127.8, 127.3, 127.0, 126.4 (CPh-Ar, CHPh-Ar),
45.0 (CH) ppm.
4.3.15. 7-Methyl-2,2,4-triphenyl-3,4-dihydropyrano[4,3-b]pyran-
5(2H)-one (5n). White solid, mp¼173e175 ꢀC. 1H NMR (400 MHz,
4.3.20. 14-Phenyl-14H-dibenzo[a,j]xanthenes (8a).18 White solid,
CDCl3, TMS, 25 ꢀC):
d
¼7.41 (d, J¼7.6 Hz, 2H), 7.36 (t, J¼7.6 Hz, 2H),
mp¼184e186 ꢀC, 1H NMR (400 MHz, CDCl3, TMS, 25 ꢀC):
¼8.78 (d,
d
7.29 (d, J¼7.6 Hz, 3H), 7.25e7.20 (m, 4H), 7.18e7.13 (m, 3H), 6.06 (s,
1H), 3.72 (dd, J¼10.8, 6.8 Hz, 1H), 3.14 (dd, J¼14.4, 6.4 Hz, 1H), 2.48
(dd, J¼14.4, 10.8 Hz, 1H), 2.19 ppm (s, 3H). 13C NMR (100 MHz,
J¼12.0 Hz, 2H), 7.80 (dd, Ja¼8.0 Hz, Jb¼12.0 Hz, 4H), 7.58e7.46 (m,
6H), 7.41e7.38 (m, 2H), 7.13 (t, J¼8.0 Hz, 2H), 6.98 (t, J¼4.0 Hz, 1H),
6.48 ppm (s, 1H); 13C NMR (100 MHz, CDCl3):
131.5,131.1,128.9,128.9,128.6,128.3,126.9,126.5,124.3,122.8,118.1,
117.4 (CPh-Ar, CHPh-Ar), 38.1 (CH) ppm.
d
¼148.8, 145.1 (CeO),
CDCl3, 25 ꢀC):
d
¼165.3 (COOPh), 162.9 (C¼COOPh), 161.3, 143.7,
143.0, 141.6, 129.0, 128.6, 128.4, 128.0, 127.8, 127.0, 126.5, 125.8,
125.6, 101.6 (CPh-Ar, CHPh-Ar), 100.4 (C]C), 84.6 (COCH2Ph2), 43.4
(CHCH2), 36.1(CH2), 20.0 (CH3) ppm. IR (cmꢂ1): 3397, 3082, 3057,
3028, 2969, 2944, 2891, 1705, 1650, 1586, 1493, 1446, 1400, 1322,
1295, 1242, 1214, 1152, 1091, 1061. HRMS (TOF, ESI): m/z calcd for
4.3.21. 3-(2,2-Diphenylchroman-4-yl)-1-methyl-2-phenyl-1H-indole
(11a). White solid, mp¼116e168 ꢀC. 1H NMR (400 MHz, CDCl3,
TMS, 25 ꢀC):
d
¼7.47e7.41 (m,5H), 7.36e7.31 (m, 3H), 7.28e7.23 (m,
C
27H22NaO3, [MþNa]þ 417.1467, found 417.1473.
4H), 7.17e7.08 (m, 7H), 7.01 (d, J¼8.0 Hz, 1H), 6.91 (t, J¼8.0 Hz, 1H),
6.84 (d, J¼8.0 Hz, 1H), 6.68e6.65 (m, 1H), 4.11e4.06 (m, 1H), 3.60 (s.
4.3.16. 7,7-Dimethyl-2,2,4-triphenyl-3,4,7,8-tetrahydro-2H-chro-
3H), 2.98e2.87 ppm (m, 2H); 13C NMR (100 MHz, CDCl3):
d¼154.0,
men-5(6H)-one (5o). White solid, mp¼65e67 ꢀC. 1H NMR
146.1, 143.4, 139.8, 137.8, 131.7, 130.5, 129.3, 128.6, 128.4, 128.4,
128.3, 127.5, 127.3, 126.9, 126.3, 125.8, 125.6, 125.2, 121.7, 120.9,
120.5, 119.2, 117.1, 114.3, 109.6 (CPh-Ar, CHPh-Ar), 82.2 (COCH2Ph2),
39.9 (CHCH2), 31.1 (NCH3), 31.3 (CH2) ppm. IR (cmꢂ1): 3058, 3026,
2961, 2925,1603,1578,1478,1447,1405,1368,1292,1231,1157,1101.
HRMS (TOF, ESI): m/z calcd for C36H29NNaO, [MþNa]þ 514.2147,
found 514.2155.
(400 MHz, CDCl3, TMS, 25 ꢀC):
d
¼7.41 (d, J¼8.0 Hz, 2H), 7.36e7.25
(m, 5H), 7.21e7.15 (m, 5H), 7.10 (d, J¼8.0 Hz, 3H), 3.61e3.57 (m, 1H),
3.07 (dd, J¼14.4, 6.4 Hz, 1H), 2.67 (d, J¼17.2 Hz, 1H), 2.52 (d,
J¼17.2 Hz, 1H), 2.38 (dd, J¼18.0, 11.0 Hz, 1H), 2.11 (quit, J¼16.4,
8.4 Hz, 3H), 1.18 (s, 3H), 1.04 ppm (s, 3H); 13C NMR (100 MHz, CDCl3,
25 ꢀC):
d
¼196.4 (C]O), 169.6 (C¼COOPh), 144.9, 144.3, 142.6, 128.8,
128.4, 128.3, 127.8, 127.6, 127.0, 125.98, 126.0, 125.5(CPh-Ar, CHPh-Ar),
114.2 (C]C), 84.1 (COCH2Ph2), 51.0 (CHCH2), 43.5, 43.3, 35.6, 32.0
(CH2), 29.2, 28.1 (CH3) ppm. IR (cmꢂ1): 3060, 3027, 2958, 2930,
1660, 1626, 1553, 1492, 1449, 1373, 1322, 1286, 1258, 1223, 1160,
1066. HRMS (TOF, ESI): m/z calcd for C29H28NaO2, [MþNa]þ
431.1987, found 431.1992.
4.3.22. 3-(2,2-Diphenylchroman-4-yl)-2-phenyl-1H-indole
(11b). Yellow solid, mp¼120e122 ꢀC. 1H NMR (400 MHz, CDCl3,
TMS, 25 ꢀC):
d
¼8.03 (s, 1H), 7.50 (d, J¼8.0 Hz, 2H), 7.40e7.39 (m,
4H), 7.34e7.32 (m, 3H), 7.30e7.25 (m, 2H), 7.21e7.09 (m, 8H),
7.03e7.01 (m, 1H), 6.90e6.86 (m, 1H), 6.75 (d, J¼8.0 Hz, 1H), 6.63 (t,
J¼8.0 Hz, 1H), 4.36 (dd, Ja¼4.0 Hz, Jb¼12.0 Hz, 1H), 3.10e2.97 ppm
4.3.17. 2,2,4-Triphenyl-3,4-dihydro-2H-benzo[g]chromene-5,10-
(m, 2H); 13C NMR (100 MHz, CDCl3, 25 ꢀC):
d
¼154.0, 145.9, 143.7,
dione (5p). White solid, mp¼79e81 ꢀC. 1H NMR (400 MHz, CDCl3,
136.6,136.5,132.7, 129.3,128.9,128.5,128.3,128.1, 127.7, 127.5, 127.1,
Please cite this article in press as: Taheri, A.; et al., Tetrahedron (2015), http://dx.doi.org/10.1016/j.tet.2015.11.049

8
A. Taheri et al. / Tetrahedron xxx (2015) 1e10
126.3, 125.9, 122.3, 121.2, 120.6, 119.6, 117.1, 114.1, 111.1 (CPh-Ar, CHPh-
Ar), 82.3 (COCH2Ph2), 39.5 (CHCH2), 30.8 (CH2) ppm. IR (cmꢂ1): 3411,
3057, 3027, 2929, 1712, 1669, 1604, 1581, 1486, 1450, 1303, 1232,
1303, 1232, 1156, 1111, 1059, 1014. HRMS (TOF, ESI): m/z calcd for
1089, 1062. HRMS (TOF, ESI): m/z calcd for C40H31NNaO, [MþNa]þ
564.2303, found 564.2312.
4.3.27. 3-(8-Bromo-5-chloro-2,2-diphenylchroman-4-yl)-1-methyl-
C
35H27NNaO, [MþNa]þ 500.1990, found 500.1988.
2-phenyl-1H-indole (11g). White solid, mp¼125e127 ꢀC. 1H NMR
(400 MHz, CDCl3, TMS, 25 ꢀC):
J¼20.0 Hz, 6H), 7.32e7.24 (m, 5H), 7.18e7.07 (m, 5H), 7.01e6.92 (m,
2H), 6.78 (s, 1H), 4.11 (q, J¼4.0 Hz, 1H), 3.57 (s, 3H), 3.06e3.01 (m,
1H), 2.94e2.87 ppm (m, 1H); 13C NMR (100 MHz, CDCl3, 25 ꢀC):
d
¼7.58e7.56 (m, 2H), 7.41 (d,
4.3.23. Chloro-2,2-diphenylchroman-4-yl)-1-methyl-2-phenyl-1H-
indole (11c). White solid, mp¼214e216 ꢀC. 1H NMR (400 MHz,
CDCl3, TMS, 25 ꢀC):
7.28e7.18 (m, 6H), 7.11e7.10 (m, 5H), 7.03 (d, J¼8.0 Hz, 1H), 6.95
(t, J¼8.0 Hz, 1H), 6.80 (s, 1H), 4.06e4.01 (m, 1H), 3.62 (s, 3H),
2.93e2.89 ppm (m, 2H); 13C NMR (100 MHz, CDCl3, 25 ꢀC):
d
¼7.44e7.42 (m, 5H), 7.37e7.33 (m, 3H),
d¼149.2, 145.4, 142.8, 140.1, 137.9, 131.4, 130.8, 130.5, 128.9, 128.7,
128.6, 128.5, 128.2, 127.5, 127.4, 125.8, 125.7, 125.2, 125.2, 122.1,
120.5, 119.7, 112.8, 112.1, 109.9 (CPh-Ar, CHPh-Ar), 83.8 (COCH2Ph2),
39.1(CHCH2), 31.9 (NCH3), 31.0 (CH2) ppm. IR (cmꢂ1): 3448, 3059,
2937, 1705, 1603, 1560, 1492, 1468, 1442, 1400, 1363, 1337, 1278,
1251, 1221, 1175, 1156, 1094, 1062, 1022. HRMS (TOF, ESI): m/z calcd
for C36H27BrClNNaO, [MþNa]þ 626.0862, found 626.0877.
d
¼152.7, 145.6, 142.9, 139.8, 137.8, 131.4, 130.4, 128.8, 128.6,
128.5, 128.5, 128.3, 127.6, 127.4, 127.1, 127.1, 126.2, 125.7, 125.4,
125.3, 121.8, 120.5, 119.4, 118.6, 113.3, 109.6 (CPh-Ar, CHPh-Ar), 82.5
(COCH2Ph2), 39.5 (CHCH2), 31.4 (NCH3), 31.0 (CH2) ppm. IR
(cmꢂ1): 3053, 2964, 2933, 1599, 1575, 1469, 1445, 1401, 1362,
1335, 1281, 1253, 1229, 1175, 1157, 1116, 1089, 1059 ppm. HRMS
(TOF, ESI): m/z calcd for C36H28ClNNaO, [MþNa]þ 548.1757,
found 548.1766.
4.3.28. 3-(2,2-Diphenylchroman-4-yl)-2-methyl-1H-indole
(11h). Yellow solid, mp¼88e90 ꢀC. 1H NMR (400 MHz, CDCl3, TMS,
25 ꢀC):
d
¼7.73 (s, 1H), 7.54 (dd, Ja¼8.0 Hz, Jb¼20. 0 Hz, 5H),
7.30e7.17 (m, 8H), 7.03 (t, J¼8.0 Hz, 1H), 6.89e6.81 (m, 2H),
4.3.24. 3-(7-Bromo-2,2-diphenylchroman-4-yl)-1-methyl-2-phenyl-
6.73e6.63 (m, 2H), 4.12e4.07 (m, 1H), 2.96e2.91 (m, 2H), 2.32 ppm
1H-indole (11d). White solid, mp¼210e212 ꢀC. 1H NMR (400 MHz,
(s, 3H); 13C NMR (100 MHz, CDCl3, TMS, 25 ꢀC):
d¼154.1, 146.0,
CDCl3, TMS, 25 ꢀC):
d
¼7.44e7.41 (m, 5H), 7.36e7.34 (m, 3H),
144.1,135.9,132.4,129.3,129.1,128.8,128.4,127.7,127.4,127.2,126.4,
125.9, 121.0, 120.6, 120.1, 119.1, 117.2, 112.8, 110.5 (CPh-Ar, CHPh-Ar),
82.2 (COCH2Ph2), 39.3 (CHCH2), 30.8 (CH2), 11.6 (CH3) ppm. IR
(cmꢂ1): 3407, 3057, 3027, 2925, 1706, 1581, 1484, 1448, 1231, 1110,
1060, 1019. HRMS (TOF, ESI): m/z calcd for C30H25NNaO, [MþNa]þ
438.1834, found 438.1850.
7.28e7.17 (m, 6H), 7.11 (t, J¼4.0 Hz, 3H), 7.07 (s, 2H), 7.03e6.94 (m,
2H), 6.79 (m,1H), 4.03 (q, J¼4.0 Hz,1H), 3.64 (s, 3H), 2.93e2.89 ppm
13
(m, 2H); C NMR (100 MHz, CDCl3, 25 ꢀC):
d¼152.6, 145.5, 142.9,
139.8, 137.8, 131.4, 130.4, 128.7, 128.6, 128.4, 128.2, 127.6, 127.4,
127.0, 127.0, 126.1, 125.6, 125.3, 125.3,121.8, 120.5, 119.4, 118.5, 113.3,
109.6 (CPh-Ar, CHPh-Ar), 82.5 (COCH2Ph2), 39.4 (CHCH2), 31.4 (NCH3),
30.9 (CH2) ppm. IR (cmꢂ1): 3438, 3054, 2924, 2852, 1601, 1470,
1445, 1402, 1364, 1337, 1281, 1254, 1231, 1176, 1158, 1117, 1088, 1060,
1015. HRMS (TOF, ESI): m/z calcd for C36H28BrNNaO, [MþNa]þ
592.1252, found 592.1260.
4.3.29. 5-Bromo-3-(2,2-diphenyl-chroman-4-yl)-1H-indole
(11i). White solid, mp¼145e146 ꢀC. 1H NMR (600 MHz, CDCl3,
TMS, 25 ꢀC):
d
¼8.04 (s,1H), 7.52 (dd, Ja¼6.0 Hz, Jb¼18.0 Hz, 4H), 7.40
(s, 1H), 7.35 (t, J¼6.0 Hz, 2H), 7.29 (t, J¼6.0 Hz, 2H), 7.26e7.20 (m,
4H), 7.17 (d, J¼3.6 Hz, 2H), 6.99 (d, J¼1.8 Hz, 1H), 6.81 (d, J¼6.0 Hz,
1H), 6.71 (quin, J¼6.0 Hz, 1H), 4.16 (dd, Ja¼6.0 Hz, Jb¼12.0 Hz, 1H),
4.3.25. 3-(8-Ethoxy-2,2-diphenylchroman-4-yl)-1-methyl-2-phenyl-
1H-indole (11e). White solid, mp¼165e167 ꢀC. 1H NMR (400 MHz,
3.11 (dd, Ja¼6.0 Hz, Jb¼18.0 Hz, 1H), 2.80 ppm (t, J¼12.0 Hz, 1H); 13
C
CDCl3, TMS, 25 ꢀC):
d
¼7.55 (d, J¼8.0 Hz, 2H), 7.43e7.39 (m, 5H),
NMR (100 MHz, CDCl3, 25 ꢀC):
d¼153.8, 145.7, 143.7, 135.2, 129.0,
7.33e7.21 (m, 5H), 7.19e7.14 (m, 2H), 7.08e7.03 (m, 4H), 6.90 (t,
J¼8.0 Hz, 1H), 6.75 (d, J¼8.0 Hz, 1H), 6.58 (t, J¼8.0 Hz, 1H), 6.45 (d,
J¼4.0 Hz, 1H), 4.23e4.17 (m, 2H), 4.09 (dd, Ja¼4.0 Hz, Jb¼12.0 Hz,
128.7, 128.3, 127.9, 127.4, 127.2, 126.3, 125.6, 125.1, 124.8, 123.6,
122.0, 120.5, 118.3, 117.3, 112.8 (CPh-Ar, CHPh-Ar), 82.0 (COCH2Ph2),
40.3 (CHCH2), 30.9 (CH2) ppm. IR (cmꢂ1): 3552, 3421, 3060, 2925,
1716, 1658, 1596, 1490, 1450, 1381, 1289, 1234, 1102, 1041. HRMS
(TOF, ESI): m/z calcd for C29H22BrNNaO, [MþNa]þ 502.0782, found
502.0790.
1H), 3.61 (s, 3H), 3.02e2.88 (m, 2H), 1.54 ppm (t, J¼8.0 Hz, 3H); 13
C
NMR (100 MHz, CDCl3, 25 ꢀC):
d¼148.1, 146.3, 143.8, 143.7, 139.6,
137.7, 131.6, 130.5, 128.6, 128.4, 128.3, 128.2, 127.0, 126.8, 126.2,
125.8, 125.6, 125.4, 121.7, 121.3, 120.9, 119.8, 119.2, 114.5, 111.8, 109.5
(CPh-Ar, CHPh-Ar), 81.9 (COCH2Ph2), 64.9 (OCH2), 39.4 (CHCH2), 31.3
(NCH3), 30.9 (CH2),15.3 (CH2CH3) ppm. IR (cmꢂ1): 3051, 3030, 2983,
2960, 2930, 2876, 1602, 1579, 1481, 1467, 1446, 1429, 1391, 1360,
1391, 1360, 1340, 1328, 1262, 1218, 1172, 1156, 1114, 1085, 1037.
HRMS (TOF, ESI): m/z calcd for C38H33NNaO2, [MþNa]þ 558.2409,
found 558.2411.
4.3.30. 3-(2,2-Diphenylchroman-4-yl)-1-ethyl-2-phenyl-1H-indole
(11j). White solid, mp¼164e166 ꢀC. 1H NMR (400 MHz, CDCl3,
TMS, 25 ꢀC):
d
¼7.45e7.36 (m, 8H), 7.25e7.22 (m, 4H), 7.14e7.04 (m,
8H), 6.91e6.84 (m, 2H), 6.66 (d, J¼4.0 Hz,1H), 4.04 (d, J¼8.0 Hz, 3H),
2.94e2.89 (m, 2H), 1.24e1.20 ppm (m, 3H); 13C NMR (100 MHz,
CDCl3, 25 ꢀC):
d
¼154.1, 143.4, 139.4, 136.7, 132.1, 130.6, 129.4, 128.7,
128.5, 128.3, 127.6, 127.3, 127.0, 126.4, 125.8, 125.3, 121.6, 121.1,
120.6, 119.2, 117.2, 114.6 (CPh-Ar, CHPh-Ar), 82.2 (COCH2Ph2), 40.0
(CHCH2), 38.9 (NCH2), 31.4 (CH2), 15.6 (CH2CH3) ppm. IR (cmꢂ1):
3415, 3053, 3026, 2973, 2632, 1603, 1579, 1481, 1449, 1368, 1346,
1266, 1231, 1210, 1155, 1103, 1062. HRMS (TOF, ESI): m/z calcd for
4.3.26. 3-(3,3-Diphenyl-2,3-dihydro-1H-benzo[f]chromen-1-yl)-1-
methyl-2-phenyl-1H-indole (11f). White solid, mp¼195e197 ꢀC. 1H
NMR (400 MHz, CDCl3, TMS, 25 ꢀC):
d
¼7.67e7.62 (m, 4H),
7.58e7.54 (m, 3H), 7.45 (d, J¼8.0 Hz, 2H), 7.41e7.38 (m, 1H),
7.34e7.23 (m, 5H), 7.21e7.17 (m, 2H), 7.10e7.00 (m, 5H), 6.98e6.93
(m, 1H), 6.74 (d, J¼8.0 Hz, 1H), 6.69 (t, J¼8.0 Hz, 1H), 4.49 (q,
C
37H31NNaO, [MþNa]þ 528.2303, found 528.2311.
J¼8.0 Hz, 1H), 3.60 (s, 3H), 3.19e3.14 (m, 1H), 2.97 ppm (t,
4.3.31. 2,2-Diphenyl-4-(2,4,6-trimethoxyphenyl)chroman
13
J¼12.0 Hz, 1H); C NMR (100 MHz, CDCl3, 25 ꢀC):
d
¼152.3, 146.0,
(13a). White solid, mp¼108e110 ꢀC. 1H NMR (400 MHz, CDCl3,
142.4, 137.7, 137.2, 133.2, 132.2, 130.5, 129.6, 129.1, 128.8, 128.6,
128.4, 128.2, 127.3, 127.1, 126.7, 125.8, 125.5, 125.2, 124.2, 122.8,
TMS, 25 ꢀC):
d
¼7.56e7.51 (m, 4H), 7.28e7.23 (m, 4H), 7.16e7.13 (m,
2H), 7.10e7.01 (m, 2H), 6.64e6.57 (m, 2H), 6.16 (d, J¼4.0 Hz, 1H),
6.07 (s, 1H), 4.61e4.57 (m, 1H), 3.73e3.69 (m, 6H), 3.34 (s, 3H),
3.02e2.94 (m, 1H), 2.85e2.80 ppm (m, 1H); 13C NMR (100 MHz,
121.5, 119.8, 119.1, 117.1, 116.9, 109.3 (CPh-Ar, CHPh-Ar), 81.8
(COCH2Ph2), 60.5 (CHCH2), 42.4 (NCH3), 31.1 (d, J¼7.0 Hz, CH2)
ppm. IR (cmꢂ1): 3053, 2953, 2929, 2833, 1623, 1599, 1543, 1512,
1489, 1465, 1444, 1395, 1357, 1335, 1268, 1232, 1209, 1155, 1124,
CDCl3, 25 ꢀC):
d
¼160.2, 160.0, 159.6, 153.8, 146.9, 144.2, 128.6, 128.3,
127.4, 127.2, 127.2, 127.0, 126.8, 126.5, 125.8, 120.2, 117.0, 112.5, 92.4,
Please cite this article in press as: Taheri, A.; et al., Tetrahedron (2015), http://dx.doi.org/10.1016/j.tet.2015.11.049

A. Taheri et al. / Tetrahedron xxx (2015) 1e10
9
90.9 (CPh-Ar, CHPh-Ar), 82.3 (COCH2Ph2), 56.3, 55.7, 55.4 (OCH3), 36.6
(CHCH2), 29.0 (CH2) ppm. IR (cmꢂ1): 3060, 3003, 2935, 2836, 1604,
1586,1489, 1449,1414,1337,1314,1259, 1230,1204,1147,1115,1059.
HRMS (TOF, ESI): m/z calcd for C30H28NaO4, [MþNa]þ 475.1885,
found 475.1890.
J¼14.0 Hz, J¼5.2 Hz, 1H), 2.33e2.26 ppm (m, 1H). 13C NMR
(100 MHz, CDCl3, 25 ꢀC):
d¼152.4, 145.6, 144.8, 142.4, 141.2, 129.4,
128.7, 128.5,128.5,128.4,128.3,127.9, 127.6, 127.5, 127.4, 127.2, 127.1,
126.6,126.3,125.7,125.5,118.8 (CPh-Ar, CHPh-Ar), 139.5 (C]CH),129.8
(C]CH), 82.0 (COCH2Ph2), 38.6 (CHCH2), 34.2 (CH2) ppm. IR
(cmꢂ1): 3063, 3030, 2978, 2930, 2859, 1599, 1577, 1484, 1445, 1299,
1275, 1230, 1186, 1123, 1065, 1018. HRMS (TOF, ESI): m/z calcd for
4.3.32. 8-Nitro-2,2-diphenyl-4-(2,4,6-trimethoxyphenyl)chroman
(13b). White solid, mp¼174e175 ꢀC. 1H NMR (400 MHz, CDCl3,
C
35H27ClNaO, [MþNa]þ 521.1648, found 521.1650.
TMS, 25 ꢀC):
d
¼7.98 (dd, Ja¼4.0 Hz, Jb¼8.0 Hz, 1H), 7.57 (d, J¼4.0 Hz,
1H), 7.49 (t, J¼8.0 Hz, 4H), 7.32 (q, J¼8.0 Hz, 4H), 7.25e7.22 (m, 2H),
7.14 (d, J¼8.0 Hz, 1H), 6.20 (d, J¼4.0 Hz, 1H), 6.08 (d, J¼1.6 Hz, 1H),
4.62 (dd, Ja¼8.0 Hz, Jb¼12.0 Hz, 1H), 3.80 (d, J¼12.0 Hz, 6H), 3.42 (s,
4.3.37. 4-[2,2-Bis-(4-chloro-phenyl)-vinyl]-2,2-bis-(4-chloro-phe-
nyl)-chroman (14e). White solid, mp¼88e90 ꢀC.1H NMR (400 MHz,
CDCl3, TMS, 25 ꢀC):
d
¼7.38 (d, J¼8.4 Hz, 2H), 7.30e7.23 (m, 6H), 7.16
3H), 2.92 ppm (m, 2H); 13C NMR (100 MHz, CDCl3, 25 ꢀC):
d¼160.6,
(t, J¼8.0 Hz, 4H), 7.11 (d, J¼8.0 Hz, 2H), 7.08e7.03 (m, 3H), 7.00 (d,
J¼8.8 Hz, 2H), 6.89 (t, J¼7.2 Hz, 1H), 6.12 (d, J¼9.6 Hz, 1H),
159.4, 159.3, 145.4, 142.9, 141.4, 128.7, 128.4, 127.5, 127.5, 126.3,
125.6, 123.8, 122.7, 117.4, 110.1, 92.0, 90.8 (CPh-Ar CHPh-Ar),
,
3.45e3.38 (m, 1H), 2.61 (dd, Ja¼5.2 Hz, Jb¼14.0 Hz, 1H), 2.27 ppm (t,
13
84.1(COCH2Ph2), 56.0, 55.4, 55.4 (OCH3), 36.0 (CHCH2), 29.0 (CH2)
ppm. IR (cmꢂ1): 3463, 3060, 3004, 2960, 2939, 2840, 1588, 1515,
1490,1451,1419,1340,1256,1203,1152,1119,1086,1058,1036,1012.
HRMS (TOF, ESI): m/z calcd for C30H27NNaO6, [MþNa]þ 520.1736,
found 520.1750.
J¼12.0 Hz, 1H); C NMR (100 MHz, CDCl3, 25 ꢀC):
d
¼153.1, 143.7,
142.4, 140.9, 137.5, 133.8, 133.7, 133.5, 133.4, 131.2, 130.7, 128.7,
128.6, 128.5, 128.3, 128.2, 127.6, 127.2, 124.0, 121.2, 117.4 (CPh-Ar
,
CHPh-Ar), 139.1 (C]CH), 129.1 (C]CH), 80.8 (COCH2Ph2),
38.5(CHCH2), 34.0 (CH2) ppm. IR (cmꢂ1): 3057, 2925, 1949, 1896,
1705, 1621, 1597, 1511, 1486, 1464, 1445, 1397, 1345, 1264, 1232,
1209, 1160, 1088, 1061. HRMS (TOF, ESI): m/z calcd for
4.3.33. 4-(2,2-Diphenyl-vinyl)-2,2-diphenyl-chroman (14a). White
solid, mp¼208e210 ꢀC. 1H NMR (400 MHz, CDCl3, TMS, 25 ꢀC):
C
35H24Cl4NaO, [MþNa]þ 623.0479, found 623.0460.
d
¼7.39e7.36 (m, 5H), 7.31e7.27 (m, 5H), 7.25e7.22 (m, 4H),
7.16e7.12 (m, 3H), 7.10e7.05 (m, 4H), 6.86 (t, J¼8.0 Hz, 1H), 6.14 (d,
J¼12.0 Hz, 1H), 3.60e3.53 (m, 1H), 2.80 (dd, Ja¼4.0 Hz, Jb¼8.0 Hz,
1H), 2.33 ppm (t, J¼12.0 Hz, 1H); 13C NMR (100 MHz, CDCl3, 25 ꢀC):
Acknowledgements
We gratefully acknowledge the financial support from the Key
Scientific and Technological Project of Henan Province (No.
102102310315) and Science and Technology Innovation Group of
Henan University of Traditional Chinese Medicine. The authors
thank for National Natural Science Foundation of China for the fi-
nancial support (21173089 and 21373093) and also for the Ana-
lytical and Testing Center of HUST. Chutian Scholar Program of the
Hubei Provincial Government and the Cooperative Innovation
Center of Hubei Province are also acknowledged. This work is also
supported by the Fundamental Research Funds for the Central
Universities of China (2014ZZGH019).
d
¼153.6, 146.0, 144.1, 142.7, 141.5, 129.4, 128.8, 128.6, 128.3, 128.3,
128.2, 127.8, 127.4, 127.3, 127.2, 127.0, 126.9, 126.3, 125.7, 124.8,
120.6, 117.3 (CPh-Ar, CHPh-Ar), 139.7 (C]CH), 130.8 (C]CH), 81.5
(COCH2Ph2), 38.8 (CHCH2), 34.0 (CH2) ppm. IR (cmꢂ1): 3438, 3057,
3020, 2959, 2921, 2851, 1598, 1577, 1484, 1444, 1297, 1272, 1231,
1120, 1059, 1016. HRMS (TOF, ESI): m/z calcd for C35H28NaO,
[MþNa]þ 487.2038, found 487.2045.
4.3.34. 7-Bromo-4-(2,2-diphenylvinyl)-2,2-diphenylchroman
(14b). White solid, mp¼231e233 ꢀC. 1H NMR (400 MHz, CDCl3,
TMS, 25 ꢀC):
d
¼7.39e7.35 (m, 5H), 7.30e7.22 (m,10H), 7.11e7.08 (m,
7H), 6.99 (d, J¼8.0 Hz, 1H), 6.09 (d, J¼8.0 Hz, 1H), 3.54 (t, J¼12.0 Hz,
Supplementary data
1H), 2.78 (dd, J¼4.0 Hz, J¼12.0 Hz,1H), 2.33e2.27 ppm (t, J¼12.0 Hz,
1H); 13C NMR (100 MHz, CDCl3, 25 ꢀC):
d
¼152.3, 145.6, 144.8, 142.3,
Supplementary data associated with this article can be found in
the online version, at http://dx.doi.org/10.1016/j.tet.2015.11.049.
141.2, 129.4, 128.7, 128.5, 128.5, 128.4, 128.3, 127.9, 127.6, 127.5,
127.4, 127.2, 127.1, 126.6, 126.3, 125.7, 125.5, 118.7 (CPh-Ar, CHPh-Ar),
139.5 (C]CH), 129.8(C]CH), 81.9 (COCH2Ph2), 38.6 (CHCH2), 34.2
(CH2) ppm. IR (cmꢂ1): 3059, 3025, 2968, 2920, 2865, 1598, 1456,
1439, 1288, 1270, 1235, 1185, 1124, 1066, 1011. HRMS (TOF, ESI): m/z
calcd for C35H27BrNaO, [MþNa]þ 565.1143, found 565.1150.
References and notes
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d
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(m, 4H), 7.30e7.28 (m, 5H), 7.27e7.25 (m, 3H), 7.14e7.05 (m, 6H),
6.09 (d, J¼9.6 Hz, 1H), 3.65e3.57 (m, 1H), 2.87 (dd, Ja¼5.2 Hz,
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d¼159.3, 145.9, 144.7, 141.7, 141.6, 140.9, 128.8, 128.6,
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83.4 (COCH2Ph2), 38.4 (CHCH2), 34.0 (CH2) ppm. IR (cmꢂ1): 3059,
3025, 2965, 1615, 1580, 1513, 1477, 1445, 1337, 1255, 1188, 1159,
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