H-*BEA Zeolite-Catalyzed Nucleophilic Substitution in Allyl Alcohols Using Sulfonamides, Amides, and Anilines

Article abstract of DOI:10.1002/ejoc.202000296

Herein, we report a novel zeolite-catalyzed nucleophilic substitution in allyl alcohols. The product yield was improved upon the addition of NaOTf (0.05 mol-percent) using the studied zeolites. The highest yields were observed using H-*BEA(Si/Al₂ = 40)/NaOTf. The scope of the reaction with respect to the nucleophile was examined using 1,3-diphenylprop-2-ene-1-ol as a model substrate under optimized reaction conditions. p-Substituted aryl sulfonamides bearing electron-rich or electron-deficient substituents, alkyl sulfonamides, and heteroaryl sulfonamides undergo the amidation reaction to produce their corresponding allyl sulfonamides in good yield. Amides and anilines exhibited low activity under the optimized conditions, however, performing the reaction at 90 °C produced the target product. The scope of the allyl alcohol was investigated using p-toluenesulfonamide as the nucleophile and the reaction proceeded with a variety of allylic alcohols. To probe the practical utility of the H-*BEA-catalyzed amidation reaction, a gram-scale reaction was performed using 1.01 g (4.8 mmol) of allyl alcohol, which afforded the target product in 88 percent yield.

Full text of DOI:10.1002/ejoc.202000296

European Journal of Organic Chemistry
Accepted Article
Accepted Article
Title: H-*BEA Zeolite-catalyzed Nucleophilic Substitution in Allyl
Alcohols Using Sulfonamides, Amides, and Anilines
Authors: Akimichi Ohtsuki, Shunsuke Aoki, Ryo Nishida, Sachiko
Morita, Takeshi Fujii, and Kazu Okumura
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To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.202000296
Link to VoR: https://doi.org/10.1002/ejoc.202000296
01/2020

10.1002/ejoc.202000296
European Journal of Organic Chemistry
FULL PAPER
H-*BEA Zeolite-catalyzed Nucleophilic Substitution in Allyl
Alcohols Using Sulfonamides, Amides, and Anilines
Akimichi Ohtsuki, *[a] Shunsuke Aoki, [a] Ryo Nishida, [a] Sachiko Morita, [a] Takeshi Fujii, [a] Kazu Okumura
[a]
*
Abstract: Herein, we report a novel zeolite-catalyzed nucleophilic
substitution in allyl alcohols. The product yield was improved upon
the addition of NaOTf (0.05 mol%) using the studied zeolites. The
highest yields were observed using H-*BEA(Si/Al2=40)/NaOTf. The
scope of the reaction with respect to the nucleophile was examined
using 1,3-diphenylprop-2-ene-1-ol as a model substrate under
optimized reaction conditions. p-Substituted aryl sulfonamides
bearing electron-rich or electron-deficient substituents, alkyl
sulfonamides, and heteroaryl sulfonamides undergo the amidation
reaction to produce their corresponding allyl sulfonamides in good
yield. Amides and anilines exhibited low activity under the optimized
conditions, however, performing the reaction at 90 °C produced the
target product. The scope of the allyl alcohol was investigated using
p-toluenesulfonamide as the nucleophile and the reaction proceeded
with a variety of allylic alcohols. To probe the practical utility of the
H-*BEA-catalyzed amidation reaction, a gram-scale reaction was
performed using 1.01 g (4.8 mmol) of allyl alcohol, which afforded
the target product in 88% yield.
catalyst in 2000. 4 In addition, many metals, including transition
metals, and non-transition metal complexes or salts such as Re,
5
8
13
Mo, 6 Bi, 7 Au, Ag, 8c Yb, 9 Fe, 10 Al, 11 Zn, 12 and V have
also been used as catalysts (Scheme 1a). Brønsted acids (such
15
as sulfonic acid, 14 carboxylic acids, and phosphotungstic acid
16), Lewis acids (such as I2 17), and chiral Brønsted acids 18 have
also been used as catalysts (Scheme 1b). There are also
reports that do not use an external catalyst system, but there are
many restrictions to their use, 19 such as the need for specialized
solvents or strong bases with low nucleophilicity (such as
bis(trimethylsilyl)amine). Moreover, solid, metal, and acid
catalysts supported on a carrier have also been developed
20
(Scheme 1c).
The problem with such reported solid catalyst
systems is that they are time consuming to make.
Zeolites are microporous crystalline aluminosilicates
constructed from infinitely extending three-dimensional networks
of silicate (SiO4) and aluminate (AlO4) linked via oxygen bridges,
which exhibit structural stability and non-corrosive and non-toxic
properties as well as similar properties to those observed for
Brønsted acids. Solid catalysts, in which the metal complex is
supported on a zeolite or using the zeolite itself as a solid acid
catalyst, have been studied in many organic reactions. 21 The
advantage of using the zeolite itself as a solid acid catalyst is
that the isolation of the product is easier than when using a
transition metal catalyst. Consequently, reuse of the catalyst is
easy. Herein, we report a novel zeolite-catalyzed nucleophilic
substitution in allyl alcohols using sulfonamides, amides, and
amines (Scheme 1d). The catalyst system using our zeolite
reported here is advantageous in that a commercial product can
be directly used as a catalyst.
Introduction
Allyl amides and allyl amines are crucial structures and
synthetic building blocks found in natural products, medicines,
1
functional compounds, and other highly bioactive molecules.
Catalytic amidation, including the oxidative amidation and
amination of allyl alcohols, which produce water as the only
byproduct, are very important strategies used in green chemistry
and industrial chemistry. 2 Recently, there has been a continuous
development of these reaction protocols using various catalytic
systems. In general, sulfonamides were initially used as the
nucleophile in this type of reaction, and many methods to
efficiently release the hydroxyl group of an allyl alcohol have
been reported (Scheme 1). Metal-catalyzed amidation and
amination reactions of allyl alcohols have been studied over the
last 30 years. For example, Hayashi and Yanagi first reported
3
Pd-phosphine-catalyzed asymmetric allylic amination in 1989,
and Lu and co-workers reported the use of Pd(OAc)2 as a
[a]
Dr. Akimichi Ohtsuki, Mr. Shunsuke Aoki, Mr. Ryo Nishida, Ms.
Sachiko Morita, Mr. Takeshi Fujii, Prof. Dr. Kazu Okumura
Applied Chemistry
Kogakuin University
2665-1 Nakano-cho, Hachioji, Tokyo 192-0015, Japan
http://www.ns.kogakuin.ac.jp/~wwb1019/
Scheme 1. Strategies for the substitution of the hydroxy group in allyl
E-mail: kt13623@ns.kogakuin.ac.jp; okmr@cc.kogakuin.ac.jp
alcohols.
Supporting information for this article is given via a link at the end of
the document.
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10.1002/ejoc.202000296
European Journal of Organic Chemistry
FULL PAPER
Results and Discussion
6–8), the strongest effect upon adding NaOTf was observed
between 0 and 50 C, but not at 90 C. From these results, we
decided to use 50 C as the reaction temperature. We then
confirmed the effect of the solvent on the reaction (entries 2 and
9–11). In each case, the effect of NaOTf was observed except
for ethyl acetate and the optimum solvent was determined to be
1,4-dioxane. These surprising effects of small amount of NaOTf
are currently unclear. We are thinking that the partial protonation
of the nucleophiles under acidic conditions caused by zeolite
was inhibited by changing the acid-base equilibrium by triflate
anion. From the results, we decided to use the conditions in
entry 2-right as the standard conditions for the amidation
reaction.
Initially, we performed a typical amidation reaction using
1,3-diphenylprop-2-ene-1-ol (1a) and p-toluenesulfonamide (2a)
in 1,4-dioxane at 50 °C for 4 h in the presence of different zeolite
catalysts. The reaction occurred in all cases and Table 1 shows
the extent of the reaction observed for the four zeolite catalysts
studied (H-*BEA (Si/Al2=40), entry 3; H-FAU (Si/Al2=7), entry 5;
H-MOR (Si/Al2=18), entry 7; MFI (Si/Al2=40), entry 9). When the
reaction was carried out in the absence of the zeolite catalyst,
the reaction did not occur (entry 1). Furthermore, the yield was
greatly improved upon the addition of NaOTf (0.05 mol% for 1a)
when using any of the zeolite catalysts studied (entries 4, 6, 8,
and 10). In particular, the highest yield was observed when
using H-*BEA/NaOTf (96%, entry 4). However, almost no
reaction was observed when using NaOTf alone (entry 2). From
these results, we decided to use the H-*BEA/NaOTf catalyst
system.
Table 2. Optimizations of H-*BEA-zeolite and reaction conditions [a]
Table 1. The Zeolite-catalyzed allyl sulfoneamide formation from 1,3-
diphenylprop-2-ene-1-ol (1a) and p-toluenesulfonamide (2a) [a]
[a] Reaction conditions: 0.48 mmol of 1,3-diphenylprop-2-ene-1-ol (1a) and
0.96 mmol of p-toluenesulfonamide (2a), Zeolite 21 mg, NaOTf 0 or 0.05 mol%
(0 or 0.24 mol), 0.5 mL 1,4-dioxane, under N2 atmosphere. [b] This yield was
determined by 1H NMR.
The scope of the reaction with respect to the amide was
examined using 1,3-diphenylprop-2-ene-1-ol (1a) as a model
substrate under standard conditions (Table 3). In the case of p-
substituted aryl sulfonamides 2a and 2c–2f bearing either
electron-rich or electron-deficient substituents, the amidation
reaction proceeded to give their corresponding allyl
sulfonamides products (3aa–3ae) in good yield. Functional
groups such as methoxy (2c), chloro (2d) trifluoromethoxy (2e),
and nitro (2f) were retained under the standard reaction
conditions. Alkyl sulfonamide 2g and heteroaryl sulfonamide 2h
also participated in the reaction. p-Nitrophenylsulfonamide 2f
exhibited low activity toward allyl alcohol 1a under the standard
conditions. However, performing the reaction at 90 C gave the
desired allyl sulfonamide product (3af). This problem was easily
overcome by changing the reaction conditions. When p-
(aminoalkyl)benzene sulfonamide 2i was used as the
nucleophile, the reaction did not proceed under any of the
reaction conditions studied. The new optimized conditions (90
C, 4 h) were applied to the reactions using amides 2j–2m. In
[a] Reaction conditions: 0.48 mmol of 1,3-diphenylprop-2-ene-1-ol (1a) and
0.96 mmol of p-toluenesulfonamide (2a), Zeolite 21 mg, NaOTf 0 or 0.05 mol%
(0 or 0.24 mol), 0.5 mL 1,4-dioxane, under N2 atmosphere. [b] This yield was
determined by 1H NMR.
Table 2 lists the results obtained during the initial
screening study of the reaction conditions using H-*BEA as the
catalyst. Upon comparing the catalytic activity of H-*BEA using
different Si/Al2 ratios, the product yield was increased upon the
addition of NaOTf (entry 1–5). In particular, H-*BEA(Si/Al2=40)
and NaOTf (0.05 mol%) gave the highest yield (96%, entry 2).
When the reaction temperature was investigated (entries 2 and
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10.1002/ejoc.202000296
European Journal of Organic Chemistry
FULL PAPER
the case of the benzamide derivatives bearing electron-deficient
(p-fluorobenzamide (2j)) or electron-rich (p-methoxyamide (2k))
substituents, the amidation reaction proceeded to give their
corresponding allyl sulfonamide products (3aj–3al) in good yield.
In addition to benzamides, alkylbenzamides (butyramide (2m))
also participated in the reaction under the new optimized
conditions. Similarly, the scope of the reaction with respect to
the aniline was examined using 1,3-diphenylprop-2-ene-1-ol (1a)
as a model substrate (Table 4). The reaction did not proceed
under the standard conditions.
scope of the allyl alcohols used in the reaction was investigated
using p-toluenesulfonamide (2a) as the nucleophile (Table 5).
The catalytic amidation reactions of electron-deficient (1b) and
electron-rich (1c) substrates proceeded in high yield. However,
-methylated allyl alcohol 2d did not show any reactivity toward
allyl alcohol 1a under standard conditions and the reaction was
performed at 90 C for 4 h. The amidation of 4-phenyl-3-butene-
2-ol (1e) also afforded allyl sulfonamides 3ea and 3fa in 43%
and 4% yield, respectively under the standard conditions.
However, upon heating at 90 C for 4 h, the amidation reaction
Table 3. Substrate scope in the amidation of 1,3-diphenylprop-2-ene-1-ol (1a)
[a, b]
Table 4. Substrate scope in the amination of 1,3-diphenylprop-2-ene-1-ol (1a)
[a, b]
[a] Reaction conditions : 0.48 mmol of 1,3-diphenylprop-2-ene-1-ol (1a) and
0.96 mmol of anilines (2), H-*BEA 21 mg, NaOTf 0.05 mol% (0.24 mol), 0.5
mL 1,4-dioxane, under N2 atmosphere. [b] This yield was determined by 1H
NMR. [c] Solvent was changed to toluene (0.5 mL).
of 1e proceeded with allyl sulfonamides 3ea and 3fa to give their
corresponding products in 62% and 0%, respectively. The
amidation of 1-phenylbut-2-en-1-ol (1f) was preceded with allyl
sulfonamides 3ea and 3fa in 50%zs and 6% yield, respectively
under the standard conditions. When heated at 90 C for 4 h, the
amidation reaction of 1e proceeded with allyl sulfonamides 3ea
and 3fa in 64% and 0%, respectively. In addition, cyclic allylic
alcohol 1g, which had no aromatic ring in its structure, did not
show any reactivity under the standard conditions, but a 44%
yield of 3ga was obtained upon heating at 90 C for 16 h.
Similarly, diphenylmethanol (1h), which is not an allyl alcohol,
gave the target product (3ha) in low yield under standard
conditions, but in 67% yield upon heating at 90 C for 16 h.
Typically, alcohols can act as nucleophiles in the reaction
and produce dimeric ethers under acidic conditions. To examine
whether dimeric ether (4aa) was involved in the reaction
mechanism of this catalytic amidation, the reaction was
investigated using ether 4aa as a substrate instead of allyl
alcohol 1a (Scheme 2). Ether 4aa (0.24 mmol) and p-
toluenesulfonamide 2a (0.96 mmol) were reacted to produce a
93% NMR yield of allylamide under the standard conditions. This
result suggests the existence of a catalytic amidation reaction
[a] Reaction conditions: 0.48 mmol of 1,3-diphenylprop-2-ene-1-ol (1a) and
0.96 mmol of amides (2), Zeolite 21 mg, NaOTf 0.05 mol%(0.24 mol), 0.5 mL
1,4-dioxane, under N2 atmosphere. [b] This yield was determined by 1H NMR.
[c] Reaction temperature was 90 oC, reaction time was 16 h.
The new optimized conditions (90 C, 4 h) were applied to
the reactions using anilines 2n–2s. In the case of the p-
substituted electron-deficient anilines (2n, 2p, and 2q), the
amination reaction proceeded to give their corresponding allyl
amine products (3an, 3ap, and 3aq) in moderate or good yield.
Unfortunately, o-nitroaniline (2o) and electron-rich anilines 2r
and 2s were found to be much less reactive under these
conditions. However, this problem was easily overcome by
changing the reaction solvent. By performing the reaction in
toluene at 90 C for 16 h, the catalytic amination with o-
nitroaniline (2o) produced the target allyl amine product (3ao) in
good yield (73%). The optimized new conditions were applied to
anilines 2r and 2s and the corresponding allyl amine products
(3ar and 3as) were obtained in high yield. Subsequently, the
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10.1002/ejoc.202000296
European Journal of Organic Chemistry
FULL PAPER
mechanism involving ether 4aa after catalytic ether formation via
a protonated allyl alcohol intermediate from allyl alcohol 1a. 22
release of protons from the zeolite catalyst. We will conduct this
analysis in our future work.
To further probe the practical utility of the H-*BEA-
Table 5. Substrate scope in the amidation of allyalcohols (1) with p-
toluenesulfonamide (2a) [a, b]
catalyzed amidation reaction, a gram-scale reaction was
conducted using 1.01 g (4.8 mmol) of 1a to obtain allyl amide
3aa in 88% yield under the standard conditions (See
Experimental section).
The reaction between 1a and 2a was performed over H-
*BEA with varied Al concentration. The acid amount of these H-
*BEA was measured with temperature programmed desorption
of NH3 and the data was summarized in Table S2. The yield of
allyl amide 3aa was dependent on the Al concentration
(Al/(Si+Al)) of H-*BEA; the highest yield was obtained with the
use of H-*BEA with Al/(Si+Al)=0.012 (Si/Al2=40) as shown in
Figure S1. On further increase in the Al concentration, the yield
decreased. The tendency was rather unexpected because
Brønsted acid sites located at the external surface of H-*BEA
was supposed to be the active sites for reaction. Probably, the
adsorbed water, the amount of which is higher in with high-Al
zeolite, hindered the formation of allyl-cation intermediate in
Scheme 3.
Scheme 3. Proposal mechanism
[a] Reaction conditions : 0.48 mmol of allylalcohols (1) and 0.96 mmol of p-
toluenesulfonamide (2a), Zeolite 21 mg, NaOTf 0.05 mol% (0.24 mol), 0.5 mL
1,4-dioxane, under N2 atmosphere. [b] This yield was determined by 1H NMR.
[c] Reaction temperature was 90 oC, reaction time was 4 h. [d] Reaction
temperature was 90 oC, reaction time was 16 h.
Scheme 2. Catalytic amidation of dimeric ether (4aa)
Based on the above experimental results and previously
reported acid catalysts, we proposed a mechanism for the
reaction, as shown in Scheme 3. Initially, the proton released in
the catalytic cycle from the acid site of H-*BEA is coordinated to
the hydroxyl group of the allyl alcohol and water is then
eliminated to form an allyl-cation intermediate. A nucleophile
attacks on the allyl cation from the less sterically hindered side
followed by deprotonation gives the target allyl amide (Path A).
Similarly, the protonated allyl alcohol may react with a non-
protonated allyl alcohol to form a protonated dimeric ether. The
protonated dimeric ether can undergo nucleophilic attack at the
carbon atom followed by deprotonation to give the target allyl
amide product (Path B). Unfortunately, the mechanism of
increasing the catalyst activity by NaOTf is not clearly
understood, but we propose that NaOTf is involved in the
Conclusion
We developed
a
novel H-*BEA zeolite-catalyzed
nucleophilic substitution of allyl alcohols using a variety of
nitrogen nucleophiles. This catalytic system was activated upon
the addition of a very small amount of NaOTf and could be
applied to a wide range of nucleophiles. Furthermore, the
synthetic utility of this H-*BEA zeolite nucleophilic substitution
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10.1002/ejoc.202000296
European Journal of Organic Chemistry
FULL PAPER
protocol has been demonstrated using a gram-scale reaction.
Studies on the reaction mechanism, synthetic versatility,
application of this practical catalytic system to other acid catalyst
reactions, and the role of NaOTf in the catalytic system are now
in progress.
(TCI), methanesulfonamide 2g (TCI), 2-thiophenesulfonamide
2h (TCI) and 4-(2-aminoethyl)benzenesulfonamide 2i (Wako),
were purchased from the specified commercial suppliers and
used as received. All amides, 4-fluorobenzamide 2j (TCI), 4-
methoxybenzamide 2k (TCI), benzamide 2l (TCI) and
propylamide 2m (TCI), were purchased from the specified
commercial suppliers and used as received. All anilines, 4-
nitroaniline 2n (Wako), 2-nitroaniline 2o (TCI), 4-bromoaniline
2p (TCI), 4-chloroaniline 2q (TCI), 4-methoxyaniline 2r (TCI), 4-
methylaniline 2s (Wako) and 4-aminobenzonitrile 2t (Wako),
were purchased from the specified commercial suppliers and
used as received. Sodium trifluoromethansulfonate (TCI) was
purchased from the specified commercial suppliers and used as
received.
Experimental Section
Analytical thinlayer chromatography (TLC) was performed
1
on silica gel 60 F254 plates (Millipore). H (400 MHz) and 13C
(100 MHz) NMR spectra were recorded on a JEOL ECZ-400
spectrometer (JEOL) in CDCl3 or DMSO-d6 using
tetramethylsilane (TMS) as an internal reference standard. The
NMR chemical shifts are reffered singnals of CDCl3 (H 7.27
ppm) and DMSO-d6 (H 2.50 ppm) for 1H, and to the central line
of CDCl3 (C 77.16 ppm) and DMSO-d6 (39.52 ppm) for 13C.
NMR data have been reported as follows: chemical shifts () in
ppm , multiplicity (s = singlet, d = doublet, t = triplet, q = quartet
and m = multiplet), coupling constant (J) in Hz, and integration.
High resolution mass spectra (HRMS) were obtained on a JEOL
JMS-GC MATEII GCMS system. The Fourier transform Infrared
(FT-IR) spectra were recorded as KBr pallets on Spectrum One
(Perkin Elmer Precisely) by using potassium bromide disks and
monitored in 4000 - 1000 cm-1 region. The IR absorptions have
been reported in reciprocal centimeters with the following
relative intensities: s (strong), m (medium), or w (weak). Melting
points (Mp.) were measured on a Yanagimoto MP-S3 micro
melting point apparatus (Yanagimoto), differential thermal
analyzer and are uncorrected. Column chromatography was
performed with Silica Gel 60 (spherical, neutral) (63-210 m,
KANTO Chemical). Medium-pressure column chromatography
was carried out on a Biotage Flash Purification System Isolera
(Biotage), equipped with a 254 nm UV detector.
Synthesis of Ally Alcohols and Ethers
4-Fluoro-α-[(1E)-2-(4-fluorophenyl)ethenyl]-benzenemethan-
ol (1b)
23
Chang’s protocol used.
1,3-Bis(4-fluorophenyl)-(2E)-2-
propen-1-one (1.02 g, 4.18 mmol), dry-methanol (20 mL) and
dry THF (20 mL) were added to a 100 mL flask with stir bar
under N2 atmosphere, and the solution was stirred and cooled to
0
oC. Then, NaBH4 (1.04 g, 27.5 mmol) was added to the
reaction flask and the reaction mixture was warmed to room
temperature and stirred for 1 h. The reaction was monitored
o
using TLC. After reaction, the reaction flask was cooled to 0 C
and saturated aqueous solution of NH4Cl (200 mL) was slowly
added to quenching of NaBH4. The mixture was partitioned
between ethyl acetate and saturated aqueous solution of NH4Cl.
The organic layer was washed with saturated aqueous solution
of NH4Cl and water, dried (Na2SO4) and concentrated in vacuo.
The residue was purified by column chromatography on neutral
silica gel (20 - 30% ethyl acetate / hexane) to give a title
compound as colorless viscous oil (911 mg, 89%). Rf = 0.37
All commercial reagents and dry solvents were used
without futher purification. All reactions were carried out under
N2 atmosphere. 1,4-dioxane, ethyl acetate, toluene, methanol
and ethanol (for solvent) were purchased from KANTO Chemical
and used as received. Tetrahydrofuran (for solvent) was
purchased from WAKO Chemicals and used as received. All
zeolites were purchased from TOSOH Inc.. Ally alcohols, trans-1,
3-diphenyl-2-propen-1-ol 1a (TCI), 2-cyclohexen-1-ol 1g
(Aldrich) and benzhydrol 1h (TCI), were purchased from the
1
(40% ethyl acetate/hexane). H NMR (CDCl3, 400 MHz): 7.39-
7.32 (m, 4 H), 7.08-6.98 (m, 4 H), 6.62 (d, J = 16.0 Hz, 1 H),
6.26 (dd, J = 16.0, 6.40 Hz, 1 H), 5.34 (d, J = 6.40 Hz, 1 H), 2.34
(brs, 1 H). 13C NMR (CDCl3, 100 MHz): 163.8 (d, JC-F =13.4 Hz),
161.3 (d, JC-F = 12.5 Hz), 138.5 (d, JC-F = 2.8 Hz), 132.6 (d, JC-F
3.8 Hz), 131.1, 129.7, 128.3 (d, JC-F = 7.7 Hz), 128.2 (d, JC-F
8.6 Hz), 115.7 (d, JC-F = 8.6 Hz), 115.5 (d, JC-F = 7.7 Hz), 74.5.
=
=
specified commercial suppliers and used as received. 4-Fluoro-
4-Methyl-α-[(1E)-2-(4-methylphenyl)ethenyl]-benzenemetha-
nol (1c)
23
α-[(1E)-2-(4-fluorophenyl)ethenyl]-benzenemethanol 1b,
4-
Methyl-α-[(1E)-2-(4-methylphenyl)ethenyl]-benzenemethanol 1c,
24
25
24
α-[(1E)-1-methyl-2-phenylethenyl]-benzenemethanol 1d,
4-
Umeda’s protocol used.
The solution of 4-
phenyl-3-buten-2-ol 1e, 26 and α-1-propen-1-yl-benzenemethanol
1f
methylbenzaldehyde (1.01 g, 8.39 mmol) and 1-(4-
methylphenyl)ethanone (1.21 g, 9.02 mmol) in ethanol (20 mL)
was added to a 300 mL flask with stir bar, and the solution was
stirred and cooled to 0 oC. Then, H2O(10 mL) and KOH (521 mg,
9.30 mmol) were added to the reaction flask and the reaction
mixture was warmed to room temperature and stirred for
overnight. This reaction was monitored using TLC. After reaction,
H2O (200 mL) was added to the reaction flask, and the mixture
27
were prepared according to the literature procedures.
[Oxybis(prop-1-ene-3,1,3-triyl)]tetrabenzene 4aa was prepared
using original procedure. All sulfonamides, p-toluenesulfonamide
2a
(TCI),
benzenesulfonamide
2c
2b
(Aldrich),
(TCI),
4-
4-
methoxybenzenesulfonamide
chlorobenzenesulfonamide 2d (TCI), 4-(trifluoromethoxy)
benzenesulfonamide 2e (TCI), 4-nitrobenzenesulfonamide 2f
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10.1002/ejoc.202000296
European Journal of Organic Chemistry
FULL PAPER
o
was partitioned between ethyl acetate and water. The organic
layer was washed with water, dried (Na2SO4) and concentrated
in vacuo to give 1,3-bis(4-methylphenyl)-(2E)-2-Propen-1-one
(1cc) as yellow viscose oil. This compound was used for the
subsequent reaction without further purification. Rf = 0.30 (30%
the reaction flask was stirred and cooled to 0 C. Then, NaBH4
(825 mg, 29.6 mmol) was added to the reaction flask and the
reaction mixture was warmed to room temperature and stirred
for 2 h. The reaction was monitored using TLC. After reaction,
o
the reaction flask was cooled to 0 C and saturated aqueous
1
ethyl acetate/hexane). H NMR (CDCl3, 400 MHz): 7.93 (d, J =
solution of NH4Cl (100 mL) was slowly added to quenching of
NaBH4. The mixture was partitioned between ethyl acetate and
saturated aqueous solution of NH4Cl. The organic layer was
washed with saturated aqueous solution of NH4Cl and water,
dried (Na2SO4) and concentrated in vacuo. The residue was
purified by column chromatography on neutral silica gel (0 - 20%
ethyl acetate / hexane) to give a title compound as white solid
(1.22 g, 55% (two steps)). Rf = 0.48 (40% ethyl acetate/hexane).
1H NMR (CDCl3, 400 MHz): 7.47-7.44 (m, 2 H), 7.41-7.30 (m, 7
H), 7.28-7.22 (m, 1 H), 6.80 (s, 1 H), 5.30-5.29 (m, 1 H), 2.11-
2.10 (m, 1 H), 1.76-1.76 (m, 3 H). 13C NMR (CDCl3, 100 MHz):
142.2, 139.7, 137.6, 129.2, 128.5, 128.3, 127.7, 126.7, 126.6,
126.1, 79.6, 14.2.
8.40 Hz, 2 H), 7.79 (d, J = 16.0 Hz, 1 H), 7.56-7.47 (m, 2 H),
7.30 (d, J = 8.00 Hz, 2 H), 7.23 (d, J = 8.00 Hz, 2 H), 2.44 (s, 3
H), 2.40 (s, 3 H). 13C NMR (CDCl3, 100 MHz): 190.3, 144.6,
143.6, 141.1, 135.9, 132.4, 129.8, 129.4, 128.8, 128.6, 121.2,
21.8, 21.7.
The residue (1,3-bis(4-methylphenyl)-(2E)-2-propen-1-one,
95% NMR purity) methanol (20 mL) and THF (20 mL) were
added to a 300 mL flask with stir bar under N2 atmosphere, and
o
the reaction flask was stirred and cooled to 0 C. Then, NaBH4
(412 mg, 10.9 mmol) was added to the reaction flask and the
reaction mixture was warmed to room temperature and stirred
for overnight. The reaction was monitored using TLC. After
reaction, the reaction flask was cooled to 0 oC and saturated
aqueous solution of NH4Cl (200 mL) was slowly added to
quenching of NaBH4. The mixture was partitioned between ethyl
acetate and saturated aqueous solution of NH4Cl. The organic
layer was washed with saturated aqueous solution of NH4Cl and
water, dried (Na2SO4) and concentrated in vacuo. The residue
was purified by column chromatography on neutral silica gel (10
- 20% ethyl acetate / hexane) to give a title compound as white
solid (1.62 g, 90% (two steps)). Rf = 0.47 (40% ethyl
acetate/hexane). 1H NMR (CDCl3, 400 MHz): 7.37-7.31 (m, 2 H),
7.24-7.21 (m, 2 H), 7.18-7.14 (m, 2 H), 6.67 (d, J = 16.0 Hz, 1 H),
6.37 (dd, J = 16.0, 6.60 Hz, 1 H), 5.35 (d, J = 6.60 Hz, 1 H), 2.46
(brs, 1 H), 2.41 (s, 3 H), 2.39 (s, 3 H). 13C NMR (CDCl3, 100
MHz): 140.1, 137.6, 137.5, 133.9, 130.8, 130.3, 129.3, 126.6,
126.4, 75.0, 21.3, 21.2.
4-phenyl-3-buten-2-ol (1e)
26
Onaka’s protocol used. 4-Phenyl-3-buten-2-one (1.18 g,
8.07 mmol) and dry-methanol (100 mL) were added to a 300 mL
flask with stir bar under N2 atmosphere, and the solution was
o
stirred and cooled to 0 C. Then, NaBH4 (372 mg, 9.84 mmol)
was added to the reaction flask and the reaction mixture was
warmed to room temperature and stirred for 1 h. The reaction
was monitored using TLC. After reaction, the reaction flask was
cooled to 0 oC and aqueous solution of HCl (0.2 M, 20 mL) was
slowly added to quenching of NaBH4 and water (80 mL) was
added. The mixture was partitioned between ethyl acetate and
water. The organic layer was washed with HCl aq (0.2 M) and
water, dried (Na2SO4) and concentrated in vacuo. The residue
was purified by column chromatography on neutral silica gel
(30% ethyl acetate / hexane) to give a title compound as
colorless oil (1.01 g, 85%). Rf = 0.34 (40% ethyl acetate/hexane).
1H NMR (CDCl3, 400 MHz): 7.40-7.23 (m, 5 H), 6.57 (d, J = 16.0
Hz, 1 H), 6.27 (dd, J = 16.0, 6.60 Hz, 1 H), 4.50-4.47 (m, 1 H),
2.31 (brs, 1 H), 1.39 (d, J = 6.40 Hz, 3 H). 13C NMR (CDCl3, 100
MHz): 136.8, 133.7, 129.4, 128.6, 127.7, 126.5, 68.9, 23.5.
-[(1E)-1-methyl-2-phenylethenyl]-benzenemethanol (1d)
25
The precursor was prepared using Yangr’s method.
Benzaldehyde (1.04 g, 9.80 mmol), 1-phenyl-1-propanone (1.40
g, 10.1 mmol), piperidine (2.0 mL, 1.72 g, 20.2 mmol), acetic
acid (2.0 mL, 2.1 g, 35.0 mmol) and ethanol (10 mL) were added
to 100 mL flask with stir bar and reflux condenser. The reaction
mixture was stirred at 85 oC for 13 h. This reaction was
monitored using TLC and 1H NMR. To this reaction mixture,
saturated aqueous solution of NH4Cl (100 mL) was slowly added
to quenching the reaction. The mixture was partitioned between
ethyl acetate and saturated aqueous solution of NH4Cl. The
organic layer was washed with water, dried (Na2SO4) and
concentrated in vacuo to give (E)-2-methyl-1,3-diphenylprop-2-
en-1-one as viscose yellow oil (NMR purity was 50%). This
compound was used for the subsequent reaction without further
purification. Rf = 0.30 (30% ethyl acetate/hexane).
-1-propen-1-yl-benzenemethanol (1f)
27
Nau’s protocol used. 2-Butenal (1.05 g, 14.9 mmol) and
dry THF (50 mL) were added to a 300 mL flask with stir bar
under N2 atmosphere, and the solution was stirred and cooled to
0 oC. The solution of phenylmagnesium bromide in diethyl ether
(3.0 M solution, 7 mL, 21 mmol) was slowly added to the
reaction flask and the reaction mixture was warmed to room
temperature and stirred for 1 h. This reaction was monitored
o
using TLC. After reaction, the reaction flask was cooled to 0 C
and saturated aqueous solution of NH4Cl (100 mL) was slowly
added to quenching of phenylmagunesium bromide. The mixture
was partitioned between ethyl acetate and saturated aqueous
solution of NH4Cl. The organic layer was washed with saturated
aqueous solution of NH4Cl and water, dried (Na2SO4) and
The residue ((E)-2-methyl-1,3-diphenylprop-2-en-1-one,
50% NMR purity), methanol (20 mL) and THF (20 mL) were
added to a 300 mL flask with stir bar under N2 atmosphere, and
This article is protected by copyright. All rights reserved.

10.1002/ejoc.202000296
European Journal of Organic Chemistry
FULL PAPER
concentrated in vacuo. The residue was purified by column
chromatography on neutral silica gel (0 – 30% ethyl acetate /
hexane) to give a title compound as colorless oil (1.83 g, 83%).
Rf = 0.65 (40% ethyl acetate/hexane). 1H NMR (CDCl3, 400
MHz): 7.40-7.29 (m, 5 H), 5.79-5.67 (m, 2 H), 5.13 (d, J = 5.60
Hz, 1H), 2.83 (brs, 1 H), 1.75 (d, J = 6.00 Hz, 1 H). 13C NMR
(CDCl3, 100 MHz): 143.4, 133.7, 128.4, 127.4, 127.2, 126.2,
75.0, 17.7.
concentrated in vacuo. 3,4,5-Trichloropyridine was added as an
internal standard, and 1H NMR analysis was performed to
determine a NMR yield.
3. Procedure for H-*BEA zeolite catalyzed substitution of
allyl alcohol 1a with anilines in 1, 4-dioxane at 90 oC
Allyl alcohol 1a (100 mg, 0.48 mmol), aniline 2 (0.96 mmol),
H-*BEA (Si/Al2 = 40, 21 mg), 1,4-dioxane (500 L) and stir bar
were added to a 10 mL-sample vial with a Teflon-sealed
screwcap. Then, a solution of NaOTf in 1, 4-dioxane (14.5 mM,
17 L, about 0.0246 mol) was added to the reaction mixture
and stirred at 90 oC for 16 h under nitrogen atmosphere. After
reaction, H-*BEA was removed by short column (ethyl acetate,
neutral silica gel) and the result solution was concentrated in
vacuo. 3,4,5-Trichloropyridine was added as an internal
[Oxybis(prop-1-ene-3,1,3-triyl)]tetrabenzene (4aa) 28
trans-1,3-Diphenyl-2-propen-1-ol 1a (1.01 g, 4.79 mmol),
p-toluenesulfonamide 2a (1.60 g, 9.37 mmol), Ion Exchange
Resin (Amberlyst 15E, 8.8 mg), toluene (5 mL) and stir bar were
added to a 30 mL-sample vial with a Teflon-sealed screwcap.
o
The reaction mixture was stirred at 50 C for 4 h under nitrogen
1
atmosphere. After reaction, H-*BEA was removed by filtration
and the result solution was concentrated in vacuo. The residue
was purified by Flash column chromatography on neutral silica
gel (0–5% ethyl acetate / hexane) to give compound 4aa as
colorless viscose oil (740 mg, 77%). Rf = 0.51 (40% ethyl
standard, and H NMR analysis was performed to determine a
NMR yield.
4. Procedure for H-*BEA zeolite catalyzed substitution of
allyl alcohol 1a with anilines in toluene at 110 oC
1
acetate/hexane). H NMR (CDCl3, 400 MHz): 7.45-7.20 (m, 20
H), 6.61 (dd, J = 16.0, 4.00 Hz, 2 H), 6.41-6.30 (m, 2 H), 5.11 (t,
J = 7.40 Hz, 2 H). 13C NMR (CDCl3, 100 MHz): 141.4, 141.3,
136.7, 131.7, 131.5, 130.6, 130.4, 128.7, 127.8, 127.2, 126.7,
126.5, 79.3, 79.2.
Allyl alcohol 1a (100 mg, 0.48 mmol), aniline 2 (0.96 mmol),
H-*BEA (Si/Al2 = 40, 21 mg), toluene (500 L) and stir bar were
added to a 10 mL-sample vial with a Teflon-sealed screwcap.
Then, a solution of NaOTf in toluene (14.5 mM, 17 L, about
0.0246 mol) was added to the reaction mixture and stirred at
o
Typical Procedure for H-*BEA Zeolite Catalyzed Substitution
of Allyl Alcohols
110 C for 16 h under nitrogen atmosphere. After reaction, H-
*BEA was removed by short column (ethyl acetate, neutral silica
gel) and the result solution was concentrated in vacuo. 3,4,5-
Trichloropyridine was added as an internal standard, and 1H
NMR analysis was performed to determine a NMR yield.
1. Procedure for H-*BEA zeolite catalyzed substitution of
allyl alcohol 1a with sulfonamides
Allyl alcohol 1a (100 mg, 0.48 mmol), sulfonamide 2 (0.96
mmol), H-*BEA (Si/Al2 = 40, 21 mg), 1,4-dioxane (500 L) and
stir bar were added to a 10 mL-sample vial with a Teflon-sealed
screwcap. Then, a solution of NaOTf in 1, 4-dioxane (14.5 mM,
17 L, about 0.0246 mol) was added to the reaction mixture
5. Procedure for H-*BEA zeolite catalyzed substitution of
allyl alcohols 1 with p-toluenesulfonamide 2a
Allyl alcohols 1 (0.48 mmol), p-toluenesulfonamide 2a (166
mg, 0.96 mmol), H-*BEA (Si/Al2 = 40, 21 mg), 1,4-dioxane (500
L) and stir bar were added to a 10 mL-sample vial with a
Teflon-sealed screwcap. Then, a solution of NaOTf in 1, 4-
dioxane (14.5 mM, 17 L, about 0.0246 mol) was added to the
o
and stirred at 50 or 90 C for 4 h under nitrogen atmosphere.
After reaction, H-*BEA was removed by short column (ethyl
acetate, neutral silica gel) and the result solution was
concentrated in vacuo. 3,4,5-Trichloropyridine was added as an
internal standard, and 1H NMR analysis was performed to
determine a NMR yield.
o
reaction mixture and stirred at 90 C for 16 h under nitrogen
atmosphere. After reaction, H-*BEA was removed by short
column (ethyl acetate, neutral silica gel) and the result solution
was concentrated in vacuo. 3,4,5-Trichloropyridine was added
as an internal standard, and 1H NMR analysis was performed to
determine a NMR yield.
2. Procedure for H-*BEA zeolite catalyzed substitution of
allyl alcohol 1a with amides
Allyl alcohol 1a (100 mg, 0.48 mmol), amide 2 (0.96 mmol),
H-*BEA (Si/Al2 = 40, 21 mg), 1,4-dioxane (500 L) and stir bar
were added to a 10 mL-sample vial with a Teflon-sealed
screwcap. Then, a solution of NaOTf in 1, 4-dioxane (14.5 mM,
17 L, about 0.0246 mol) was added to the reaction mixture
and stirred at 50 or 90 C for 4 h under nitrogen atmosphere.
After reaction, H-*BEA was removed by short column (ethyl
acetate, neutral silica gel) and the result solution was
6. Procedure for H-*BEA zeolite catalyzed substitution of
ether 4aa with p-toluenesulfonamide 2a
Ether 4aa (94 mg, 0.24 mmol), p-toluenesulfonamide 2a
(166 mg, 0.96 mmol), H-*BEA (Si/Al2 = 40, 21 mg), 1,4-dioxane
(500 L) and stir bar were added to a 10 mL-sample vial with a
Teflon-sealed screwcap. Then, a solution of NaOTf in 1, 4-
dioxane (14.5 mM, 17 L, about 0.0246 mol) was added to the
o
This article is protected by copyright. All rights reserved.

10.1002/ejoc.202000296
European Journal of Organic Chemistry
FULL PAPER
reaction mixture and stirred at 50 oC for 4 h under nitrogen
atmosphere. After reaction, H-*BEA was removed by short
column (ethyl acetate, neutral silica gel) and the result solution
was concentrated in vacuo. 3,4,5-Trichloropyridine was added
as an internal standard, and 1H NMR analysis was performed to
determine a NMR yield.
J = 16.0 Hz, 1 H), 6.11 (dd, J = 16.0, 6.8 Hz, 1 H), 5.25-5.12 (m,
2 H). 13C NMR (CDCl3, 100 MHz): 140.9, 139.6, 136.1, 132.5,
132.3, 129.0, 128.9, 128.6, 128.3, 128.07, 128.05, 127.3, 128.2,
126.7, 59.9. HRMS (EI) Calcd for C21H19O2NS 349.1136, Found
349.1151. FT-IR(KBr, cm-1): 3302 m, 3079 m, 3064 m, 3027 m,
1495 s, 1477 m, 1456 s, 1448 s, 1429 s, 1332 s, 1262 m, 1163 s,
1029 s, 1021 s.
7. Procedure for H-*BEA zeolite catalyzed substitution of
allyl alcohol 1a with sulfonamides 2a (A Gram-Scale)
N-[(2E)-1,3-diphenyl-2-propen-1-yl]-4-methoxy-benzene-
sulfonamide (3ac) 8c
Scheme 4. A gram schale reaction
Rf = 0.43 (40% ethyl acetate/hexane). White solid. 1H NMR
(CDCl3, 400 MHz): 7.72 (d, J = 9.20 Hz, 2 H), 7.29-7.17 (m, 10
H), 6.77 (d, J = 9.20 Hz, 2 H), 6.36 (d, J = 16.0 Hz, 1 H), 6.10
(dd, J = 16.0, 6.80 Hz, 1 H), 5.66 (d, J = 8.00 Hz), 5.12 (t, J =
7.20 Hz, 1 H), 3.72 (s, 3 H). 13C NMR(CDCl3, 100 MHz); 162.7,
139.8, 136.2, 132.3, 132.0, 129.4, 128.7, 128.5, 128.3, 127.9,
127.8, 127.1, 126.6, 114.0, 59.8, 55.5. HRMS (EI) Calcd for
C22H21O3NS 379.1242, Found 379.1243. FT-IR(KBr, cm-1): 3350
m, 3082 m, 3053 m, 3032 m, 2909 w, 1633 s, 1601 s, 1578 s,
1521 s, 1488 s, 1455 m, 1363 m, 1312 s, 1250 m, 1205 m, 1143
m, 1073 m, 1042 m, 1022 m.
trans-1,3-Diphenyl-2-propen-1-ol 1a (1.01 g, 4.80 mmol),
p-toluenesulfonamide 2a (1.66 g, 9.70 mmol), H-*BEA (Si/Al2 =
40, 420 mg) 1, 4-dioxane (5.0 mL) and stir bar were added to a
30 mL-sample vial with a Teflon-sealed screwcap. Then, a
solution of NaOTf in 1, 4-dioxane (14.5 mM, 166 L, about 0.24
mol) was added to the reaction mixture and stirred at 50 oC for
4 h under nitrogen atmosphere. After reaction, H-*BEA was
removed by short column (ethyl acetate, neutral silica gel) and
the result solution was concentrated in vacuo. The residue was
purified by column chromatography on neutral silica gel (0 –
N-[(2E)-1,3-diphenyl-2-propen-1-yl]-4-chloro-benzenesulfon-
amide (3ad)
Rf = 0.52 (40% ethyl acetate/hexane). White needle crystal. Mp:
115-116 oC. 1H NMR (CDCl3, 400 MHz): 7.66 (d, J = 8.80 Hz, 2
H), 7.30-7.15 (m, 12 H), 6.39 (d, J = 16.0 Hz, 1 H), 6.10 (dd, J =
16.0, 6.8 Hz, 1 H), 5.16 (t, J = 7.0 Hz, 1 H), 5.09-5.07 (m, 1 H).
13C NMR (CDCl3, 100 MHz): 139.5, 139.3, 139.1, 135.9, 132.7,
129.2, 129.0, 128.8, 128.7, 128.3, 128.2, 128.0, 127.2, 126.7,
60.1. HRMS (EI) Calcd for C21H18O2NSCl 383.0747, Found
383.0744. FT-IR(KBr, cm-1): 3264 m, 3061 m, 3034 m, 2936 m,
2819 m, 1649 m, 1585 s, 1574 s, 1497 s, 1475 s, 1456 s, 1416 s,
1695 s, 1332 s, 1275 s, 1177 s, 1155 s, 1089 s, 1017 s.
20% ethyl acetate / hexane) to give compound 3aa as white
solid (1.53 g, 88%).
Spectroscopic Data of Products
N-[(2E)-1,3-diphenyl-2-propen-1-yl]-4-methylbenzenesulfon-
amide (3aa) 6a
N-[(2E)-1,3-diphenyl-2-propen-1-yl]-4-(trifluoromethyl)-
benzenesulfonamide (3ae)
Rf
0.51(40% ethyl acetate/hexane). White solid. 1H NMR
=
Rf = 0.54 (40% ethyl acetate/hexane). White solid. Mp: 109-110
oC. 1H NMR (CDCl3, 400 MHz): 7.78-7.72 (m, 2 H), 7.30-7.09 (m,
12 H), 6.42 (d, J = 16.0 Hz, 1 H), 6.12 (dd, 15.6, 6.40 Hz, 1 H),
5.36-5.33 (m, 1 H), 5.20 (t, J = 6.40 Hz, 1 H). 13C NMR (CDCl3,
100 MHz): 151.9, 139.4, 139.1, 135.9, 132.7, 129.5, 128.9,
128.7, 128.3, 128.2, 128.0, 127.2, 126.6, 121.6, 120.8, 60.2.
HRMS (EI) Calcd for C22H18O3NSF3 433.0959, Found 433.0966.
FT-IR(KBr, cm-1): 3263 m, 3029 m, 1650 m, 1599 s, 15879 s,
1497 s, 1457 s, 1431 s, 1327 s, 1255 s, 1213 s, 1164 s, 1095 s,
1041 s.
(CDCl3, 400 MHz): 7.66 (d, J = 8.40 Hz, 2 H), 7.29-7.13 (m, 12
H), 6.35 (d, J = 16.0 Hz, 1 H), 6.08 (dd, J = 16.0, 6.80 Hz, 1 H),
5.12 (t, J = 6.80 Hz, 1 H), 5.03-5.01 (m, 1 H), 2.33 (s, 3 H). 13C
NMR (CDCl3, 100 MHz): 143.4, 139.8, 137.9, 136.2, 132.3,
129.6, 128.9, 128.6, 128.3, 128.2, 128.0, 127.5, 127.2, 126.7,
59.9, 21.6. HRMS (EI) Calcd for C22H21O2NS 363.1293, Found
363.1289. FT-IR(KBr, cm-1): 3298 s, 3029 w, 1599 m, 1494 m,
1451 m, 1429 m, 1339 m, 1322 s, 1303 m, 1290 m, 1162 s,
1151 s, 1092 m, 1019 m.
N-[(2E)-1,3-diphenyl-2-propen-1-yl]-benzenesulfonamide
(3ab) 29
N-[(2E)-1,3-diphenyl-2-propen-1-yl]-4-nitrobenzenesulfon-
amide (3af) 30
Rf = 0.45 (40% ethyl acetate/hexane). White solid. 1H NMR
(CDCl3, 400 MHz): 7.77 (d, J = 7.20 Hz, 2 H), 7.41 (t, J = 7.60
Hz, 1 H), 7.34 (t, J = 7.60 Hz, 2 H), 7.28–7.16(m, 10 H), 6.38 (d,
Rf = 0.50 (40% ethyl acetate/hexane). White solid. 1H NMR
(CDCl3, 400 MHz): 8.14-8.10 (m, 2 H), 7.87-7.84 (m, 2 H), 7.30 -
This article is protected by copyright. All rights reserved.

10.1002/ejoc.202000296
European Journal of Organic Chemistry
FULL PAPER
7.15 (m, 10 H), 6.42 (d, J = 16.0 Hz, 1 H), 6.09 (dd, J = 16.0,
7.00 Hz, 1 H), 5.25 (t, J = 7.00 Hz, 1 H), 5.07 (d, J = 7.60 Hz). 1H
NMR (DMSO-d6, 400 MHz): 8.83 (d, J = 8.80 Hz, 1 H), 8.18 (d, J
= 8.60 Hz, 2 H), 7.92 (d, J = 8.60 Hz, 2 H), 7.26-7.16 (m, 10 H),
6.28 (d, J = 16.0 Hz, 1 H), 6.09 (dd, J = 16.0, 8.00 Hz, 1 H), 5.09
(t, J = 8.00 Hz, 1 H). 13C NMR (DMSO-d6, 100 MHz): 149.0,
147.1, 140.1, 135.7, 130.7, 128.5, 128.4, 128.2, 127.8, 127.4,
127.0, 126.2, 124.1, 59.5. HRMS (EI) Calcd for C21H18O4N2S
394.0987, Found 349.1007. FT-IR(KBr, cm-1): 3287 s, 1606 w,
1529 s, 1499 m, 1457 m, 1420 m, 1345 s, 1336 s, 1314 m, 1158
s, 1088 m, 1031 m.
Rf = 0.39 (40% ethyl acetate/hexane). White solid. Mp: 75-76 oC.
1H NMR (CDCl3, 400 MHz): 7.71 (d, J = 8.80 Hz, 2 H), 7.29-7.17
(m, 10 H), 6.78 (d, J = 8.80 Hz, 2 H), 6.36 (d, J = 16.0 Hz, 1 H),
6.10 (dd, J = 16.0, 6.80 Hz, 1 H), 5.51-5.49 (m, 1H), 5.11 (t, J =
7.00 Hz, 1 H), 3.73 (s, 3 H). 13C NMR (CDCl3, 100 MHz): 162.8,
139.8, 136.2, 132.4, 132.2, 129.6, 128.9, 128.6, 128.4, 128.0,
127.2, 126.7, 114.1, 59.9, 55.6. HRMS (EI) Calcd for C23H21O2N
343.1572, Found 343.1566. FT-IR(KBr, cm-1): 3348 m, 1625 s,
1607 s, 1574 m, 1538 s, 1504 s, 1448 m, 1348 m, 1322 m, 1302
m, 1302s, 1254 s, 1177 s, 1107 w, 1028 m.
N-[(2E)-1,3-diphenyl-2-propen-1-yl]-benzamide (3al) 6a
N-[(2E)-1,3-diphenyl-2-propen-1-yl]-methanesulfonamide
(3ag) 8c
Rf 0.43 (40% ethyl acetate/hexane). White solid. 1H NMR (CDCl3,
400 MHz): 7.83 (d, J = 7.60 Hz, 2 H), 7.53-7.49 (m, 1 H), 7.45-
7.22 (m, 12 H), 6.64-6.60 (m, 2 H), 6.45 (dd, J = 16.0, 6.00 Hz, 1
H), 6.03 (t, J = 7.00 Hz 1 H). 13C NMR (CDCl3, 100 MHz): 166.6,
140.9, 136.5, 134.4, 131.9, 131.8, 129.0, 128.9, 128.74, 128.69,
128.0, 127.96, 127.92, 127.4, 127.2, 126.7, 55.3. HRMS (EI)
Calcd for C22H19ON 313.1467, Found 313.1460. FT-IR(KBr, cm-
1): 3352 s, 1635 s, 1602 m, 1578 m, 1516 s, 1487 s, 1456 m,
1363 m, 1312 m, 1249 w, 1204 m, 1079 w, 1071 m, 1043 w,
Rf = 0.36 (40% ethyl acetate/hexane). White solid. 1H NMR
(CDCl3, 400 MHz): 7.41-7.26 (m, 10 H), 6.63 (d, J = 16.0 Hz, 1
H), 6.34 (dd, J = 16.0, 6.80 Hz, 1 H), 5.30 (t, J = 6.60 Hz, 1 H),
4.80 (brs, 1 H), 2.79 (s, 3 H). 13C NMR (CDCl3, 100 MHz): 140.0,
136.0, 132.7, 129.2, 128.8, 128.53, 128.46, 128.4, 127.3, 126.8,
59.9, 42.4. HRMS (EI) Calcd for C16H17O2NS 287.0980, Found
287.0994. FT-IR(KBr, cm-1): 3306 m, 1651 m, 1497 m, 1458 m,
1432 s, 1417 s, 1353 s, 1315 s, 1265 s, 1154 s, 1086 m, 1040 s. 1026 m.
N-[(2E)-1,3-diphenyl-2-propen-1-yl]- 2-thiophenesulfonamide
(3ah) 31
N-[(2E)-1,3-diphenyl-2-propen-1-yl]-propanamide (3am)
Rf = 0.24 (40% ethyl acetate/hexane). White solid. Mp: 117-118
oC. 1H NMR (CDCl3, 400 MHz): 7.38-7.21 (m, 10 H), 6.51 (d, J =
16.0 Hz, 1 H), 6.33 (dd, J = 16.0, 6.40 Hz, 1 H), 6.22 (d, J = 8.40
Hz, 1 H) 5.82 (t, J = 7.20 Hz, 2 H), 2.26 (dq, J = 8.00, 1.60 Hz, 2
H), 1.17 (t, J = 8.00 Hz, 3 H). 13C NMR (CDCl3, 100 MHz) :173.0,
141.1, 136.5, 131.3, 129.1, 128.8, 128.6, 127.8, 127.7, 127.2,
126.6, 54.7, 29.8, 9.9. HRMS (EI) Calcd for C18H19ON 265.1467,
Found 265.1455. FT-IR(KBr, cm-1): 3314 s, 3030 m, 2978 m,
2938 w, 1646 s, 1527 s, 1495 m, 1372 m, 1275 m, 1231 m.
Rf = 0.47 (40% ethyl acetate/hexane). White solid. 1H NMR
(CDCl3, 400 MHz): 7.49-7.44 (m, 2 H), 7.29-7.23 (m, 10 H),
6.95-6.93 (m, 1 H), 6.45 (d, J = 16.0 Hz, 1 H), 6.18 (dd, J = 16.0,
6.40 Hz, 1 H), 5.21 (t, J = 7.20 Hz, 1 H), 5.18-5.05 (brs, 1 H). 13
C
NMR (CDCl3, 100 MHz): 141.9, 139.5, 136.1, 132.8, 132.4,
132.1, 129.0, 128.7, 128.2, 128.1, 127.3, 127.2, 126.7, 30.1.
HRMS (EI) Calcd for C19H17O2NS2 355.0701, Found 355.0746.
FT-IR(KBr, cm-1): 3265 s, 3095 m, 1494 m, 1456 m, 1437 s,
1403 m, 1343 s, 1326 s, 1232 m, 1155 s, 1091 s, 1067 m, 1020
s.
N-(4-nitrophenyl)-α-[(1E)-2-phenylethenyl]-benzenemethan-
amine (3an) 6a
N-[(2E)-1,3-diphenyl-2-propen-1-yl]-4-fluoro- benzamide (3aj)
Rf = 0.44 (40% ethyl acetate/hexane). White solid. Mp: 141-142
Rf = 0.56 (40% ethyl acetate/hexane). Yellow viscose oil. 1H
NMR (CDCl3, 400 MHz): 8.08-8.04 (m, 2 H), 7.41-7.24 (m, 10 H),
oC. 1H NMR (CDCl3, 400 MHz): 7.86-7.81 (m, 2 H), 7.44-7.22 (m, 6.63-6.55 (m, 3 H), 6.38 (dd, J = 16.2, 5.80 Hz, 1 H), 5.23-5.19
10 H), 7.14-7.09 (m, 2 H), 6.61 (d, J = 16.0 Hz, 1 H), 6.47-6.41
(m, 2 H), 6.00 (t, J = 7.20 Hz, 1H). 13C NMR (CDCl3, 100 MHz):
165.6, 164.9 (d, JC-F = 253.9 Hz), 140.8, 136.4, 132.0, 130.6 (d,
JC-F = 2.9 Hz), 129.6 (d, JC-F =10.4 Hz), 129.1, 128.7, 128.0 (d,
JC-F = 2.9 Hz), 127.4, 126.7, 115.8 (d, JC-F = 22.1 Hz), 55.5.
HRMS (EI) Calcd for C22H18ONF 331.1372, Found 331.1365.
FT-IR(KBr, cm-1): 3341 s, 3029 m, 1635 s, 1603 s, 1593 m, 1541
s, 1499 s, 1449 s, 1351 m, 1341 m, 1314 m, 1286 m, 1268 m,
1238 s, 1158 m, 1097 m.
(m, 1 H), 4.91-4.89 (m, 1 H). 13C NMR (CDCl3, 100 MHz): 152.2,
140.4, 138.7, 136.1, 132.4, 129.3, 128.8, 128.7, 128.35, 128.30,
127.3, 126.7, 126.4, 112.3, 60.2. HRMS (EI) Calcd for
C21H18O2N2 330.1368, Found 330.1359. FT-IR(KBr, cm-1): 3377
m, 1596 s, 1531 s, 1494 s, 1467 s, 1357 m, 1329 s, 1298 s,
1182 m, 1110 s, 1087 m.
N-(2-nitrophenyl)-α-[(1E)-2-phenylethenyl]-benzenemethan-
amine (3ao) 6a
Rf = 0.58 (40% ethyl acetate/hexane). Yellow viscose oil. 1H
NMR (CDCl3, 400 MHz): 8.55-8.53 (m, 1 H), 8.21 (dd, J = 8.80,
1.60 Hz, 1 H), 7.49-7.23 (m, 12 H), 6.85 (d, J = 8.40 Hz, 1 H),
6.69-6.61 (m, 2 H), 6.44 (dd, J = 16.0, 5.60 Hz, 2 H), 5.34 (t, J =
N-[(2E)-1,3-diphenyl-2-propen-1-yl]-4-methoxy-benzamide
(3ak) 19a
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10.1002/ejoc.202000296
European Journal of Organic Chemistry
FULL PAPER
5.80 Hz, 1 H). 13C NMR (CDCl3, 100 MHz): 144.3, 140.5, 136.18, 129.8, 128.9, 128.7, 127.8, 127.6, 127.4, 127.0, 126.7, 113.9,
136.15, 132.5, 132.0, 129.2, 129.0, 128.7, 128.14, 128.10, 127.0, 61.1, 20.5. HRMS (EI) Calcd for C22H21N 299.1674, Found
126.8, 126.7, 116.0, 115.2, 59.8. HRMS (EI) Calcd for
C21H18O2N2 330.1368, Found 330.1364. FT-IR(KBr, cm-1): 3377
m, 1618 s, 1572 s, 1512 s, 1450 m, 1416 m, 1347 s, 1257 s,
1152 m.
229.1682. FT-IR(KBr, cm-1): 3407 m, 1616 m, 1518 s, 1465 m,
1449 m, 1412 w, 1317 m, 1301 m, 1259 m, 1237 w.
4-[[(2E)-1,3-diphenyl-2-propen-1-yl]amino]-benzonitrile (3at)
31
N-(4-bromophenyl)-α-[(1E)-2-phenylethenyl]-benzene-
methanamine (3ap)
Rf = 0.56 (40% ethyl acetate/hexane). White solid. 1H NMR
(CDCl3, 400 MHz): 7.42-7.24 (m, 12 H), 6.64-6.59 (m, 3 H), 6.39
(dd, J = 16.0, 6.40 Hz, 1 H), 5.16 (t, J = 5.40 Hz, 1 H), 4.76 (brs,
1 H). 13C NMR (CDCl3, 100 MHz): 150.3, 140.7, 136.2, 133.7,
132.0, 129.1, 128.7, 128.1, 127.2, 126.6, 120.4, 113.2, 99.3,
60.0. HRMS (EI) Calcd for C22H18N2 310.1470, Found 310.1486.
FT-IR(KBr, cm-1): 3393 s, 2211 s, 1607 s, 1520 s, 1493 m, 1452
m, 1336 s, 1310 m, 1258 m, 1245 m, 1173 s, 1132 m, 1094 w.
Rf = 0.60 (40% ethyl acetate/hexane). Yellow viscose oil. 1H
NMR (CDCl3, 400 MHz): 7.50-7.28 (m, 12 H), 6.68 (d, J = 16.0
Hz, 1 H), 6.59-6.55 (m, 2 H), 6.44 (dd, J = 16.0, 6.40 Hz, 1 H),
5.11 (d, J = 6.00 Hz, 1 H), 4.22 (brs, 1 H). 13C NMR (CDCl3, 100
MHz): 146.2, 141.6, 136.5, 131.9, 131.4, 130.2, 129.0, 128.8,
128.7, 127.9, 127.8, 127.2, 126.6, 126.5, 115.3, 109.4, 60.6.
HRMS (EI) Calcd for C21H18NBr 363.0623, Found 363.0617. FT-
IR(KBr, cm-1): 3410 m, 1690 w, 1595 s, 1495 s, 1450 s, 1394 m,
1315 s, 1294 s, 1259 m, 1241 m, 1178 m, 1121 w, 1073 s, 1027
w.
N-[(2E)-1,3-bis(4-fluorophenyl)-2-propen-1-yl]-4-methyl-
benzenesulfonamide (3ba)
Rf = 0.40 (40% ethyl acetate/hexane). White solid. Mp: 136-137
oC. 1H NMR (CDCl3, 400 MHz): 7.63 (d, J = 8.40 Hz, 2H), 7.17-
7.13 (m, 6 H), 6.98-6.90 (m, 4 H), 6.30 (d, J = 16.0 Hz, 2 H),
5.97 (dd, J = 16.0, 6.40 Hz, 1 H), 5.23 (d, J = 8.40 Hz, 1 H), 5.08
(t, J = 7.00 Hz, 1 H), 2.33 (s, 3 H). 13C NMR (CDCl3, 100 MHz):
N-(4-chlorophenyl)-α-[(1E)-2-phenylethenyl]-benzene-
methanamine (3aq) 8a
Rf = 0.58 (40% ethyl acetate/hexane). Yellow viscose oil. 1H
NMR (CDCl3, 400 MHz): 7.48-7.28 (m, 10 H), 7.19-7.12 (m, 2 H), 162.6 (d, JC-F = 249.1 Hz), 162.4 (d, JC-F = 248.2 Hz), 143.6,
6.71-6.58 (m, 3 H), 6.47-6.39 (m, 1 H), 5.15-5.08 (m, 1 H), 4.19
(brs, 1 H). 13C NMR (CDCl3, 100 MHz): 145.8, 141.7, 136.6,
131.4, 130.3, 129.1, 129.0, 128.7, 127.9, 127.8, 127.3, 126.6,
122.4, 114.8, 60.8. HRMS (EI) Calcd for C21H18NCl 319.1128,
Found 319.1108. FT-IR(KBr, cm-1): 3411 m, 1689 w, 1596 s,
1497 s, 1449 s, 1397 m, 1309 s, 1257 m, 1236 w, 1177 m, 1091
m.
137.7, 135.5 (d, JC-F = 3.90 Hz), 132.2 (d, JC-F = 2.80 Hz), 131.3,
129.6, 128.9 (d, JC-F = 8.60 Hz), 128.2 (d, JC-F = 8.70 Hz), 127.8,
127.4, 115.7 (d, JC-F = 12.5 Hz), 115.5 (d, JC-F = 12.5 Hz), 59.2,
21.5. HRMS (EI) Calcd for C22H19O2NSF2 399.1105, Found
399.1104. FT-IR(KBr, cm-1): 3226 s, 1601 m, 1508 s, 1434 m
1324 s, 1306 m, 1222 s, 1162 s, 1151 s, 1095 m, 1037 s.
N-[(2E)-1,3-bis(4-methylphenyl)-2-propen-1-yl]-4-methyl-
N-(4-methoxyphenyl)-α-[(1E)-2-phenylethenyl]-benzene-
methanamine (3ar) 32
benzenesulfonamide (3ca)
Rf = 0.43 (40% ethyl acetate/hexane). White solid. Mp: 123-124
oC. 1H NMR (CDCl3, 400 MHz): 7.65 (d, J = 8.00 Hz, 2 H), 7.17-
7.07 (m, 10 H), 6.31 (d, J = 16.0 Hz, 1 H), 6.10 (dd, J = 16.0,
6.40 Hz, 1 H), 5.06 (t, J = 6.80 Hz, 1 H), 4.89-4.85 (m, 1 H), 2.34
(s, 1 H), 2.32 (s, 1 H), 2.30 (s, 1 H). 13C NMR (CDCl3, 100 MHz):
143.3, 137.94, 137.86, 137.77, 136.96, 133.5, 132.0, 129.55,
129.49, 129.3, 127.49, 127.46, 127.1, 126.6, 59.7, 21.6, 21.3,
21.2. HRMS (EI) Calcd for C24H19O2NS 391.1606, Found
391.1608. FT-IR(KBr, cm-1): 3251 s, 1510 m, 1432 m, 1330 s,
1177 m, 1159 s, 1093 m, 1051 w.
Rf = 0.61 (40% ethyl acetate/hexane). White solid. Mp: 75-76 oC.
1H NMR (CDCl3, 400 MHz): 7.48-7.45 (m, 2 H), 7.41-7.36 (m, 4
H), 7.34-7.21 (m, 4 H), 6.78-6.75 (m, 2 H), 6.66-6.62 (m, 3 H),
6.42 (dd, J = 16.0, 5.60 Hz, 1 H), 5.04 (d, J = 6.40 Hz, 1 H), 3.74
(s, 3 H). 13C NMR (CDCl3, 100 MHz): 152.4, 142.5, 141.6, 136.8,
131.3, 131.0, 128.9, 128.7, 127.8, 127.6, 127.3, 126.6, 115.1,
114.9, 61.7, 55.9. HRMS (EI) Calcd for C22H21ON 315.1623,
Found 315.1652. FT-IR(KBr, cm-1): 3393 m, 1597 m, 1587 m,
1508 s, 1467 s, 1446 s, 1400 s, 1336 s, 1313 s, 1277 m, 1250 s,
1234 s, 1181 s, 1170 s, 1119 m, 1088 m, 1062 m, 1032 s.
4-Methyl-N-[(2E)-1-methyl-3-phenyl-2-propen-1-yl]-benzene-
sulfonamide (3ea) 33
N-(4-methylphenyl)-α-[(1E)-2-phenylethenyl]-benzene-
methanamine (3as)
Rf = 0.53 (40% ethyl acetate/hexane). White solid. 1H NMR
(CDCl3, 400 MHz): 7.41-7.23 (m, 9 H), 6.62 (d, J = 16.0 Hz, 1 H),
6.34 (dd, J = 16.0, 6.40 Hz, 1 H), 5.29-5.24 (m, 2 H), 2.77 (s,
3H). 13C NMR (CDCl3, 100 MHz):143.3, 138.1, 136.4, 130.5,
130.2, 129.75, 129.65, 129.5, 128.5, 127.7, 127.3, 126.5, 51.8,
22.0, 21.5. HRMS (EI) Calcd for C17H19O2NS 301.1136, Found
1
Rf = 0.64 (40% ethyl acetate/hexane). Colorless viscose oil. H
NMR (CDCl3, 400 MHz): 7.46-7.22 (m, 12 H), 6.97 (d, J = 7.60
Hz, 2 H), 6.66-6.57 (m, 3 H), 6.31 (dd, J = 16.0, 5.60 Hz, 1 H),
7.07 (d, J = 6.40 Hz, 1 H), 4.01 (brs, 1 H), 2.24 (s, 3 H). 13C
NMR (CDCl3, 100 MHz): 145.1, 142.4, 136.9, 131.12, 131.08,
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10.1002/ejoc.202000296
European Journal of Organic Chemistry
FULL PAPER
301.1142. FT-IR(KBr, cm-1): 3234 s, 1597 s, 1494 s, 1451 s,
1434 s, 1376 m, 1325 s, 1160 s, 1139 m, 1088 s, 1067 s, 1021
m.
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4-Methyl-N-[(2E)-1-phenyl-2-buten-1-yl]-benzenesulfonamide
(3fa) 34
Rf = 0.51 (40% ethyl acetate/hexane). White solid. Mp: 81-82 oC.
1H NMR (CDCl3, 400 MHz): 7.76 (d, J = 8.40 Hz, 2 H), 7.29-7.21
(m, 5 H), 7.17-7.16 (m, 2 H), 6.30 (d, J = 16.0 Hz, 1 H), 5.84 (dd,
J = 16.0, 7.00 Hz, 1 H), 4.76 (d, J = 7.20 Hz, 1 H), 4.12-4.06 (m,
1 H), 2.34 (s, 3 H), 1.28 (d, J = 6.80 Hz, 3 H). 13C NMR (CDCl3,
100 MHz): 143.4, 138.2, 136.3, 130.6, 130.2, 129.7, 128.6,
127.8, 127.4, 126.5, 51.8, 22.1, 21.6. HRMS (EI) Calcd for
C17H19O2NS 301.1136, Found 301.1113. FT-IR(KBr, cm-1): 3292
s, 1599 m, 1493 m, 1447 s, 1429 s, 1377 m, 1340 s, 1317 s,
1303 s, 1156 s, 1147 s, 1120 m, 1092 s, 1072 m, 1047 m.
[2]
N-2-cyclohexen-1-yl-4-methyl-benzenesulfonamide (3ga) 35
Rf = 0.43 (40% ethyl acetate/hexane). White solid. 1H NMR
(CDCl3, 400 MHz): 7.75 (d, J = 8.40 Hz, 2 H), 7.23 (d, J = 8.40
Hz, 2 H), 5.68-5.64 (m, 1 H), 5.35-5.28 (m, 2 H), 3.72 (brs, 1 H),
2.35 (s, 3 H), 1.95-1.75 (m, 2 H), 1.65-1.41 (m, 4 H). 13C NMR
(CDCl3, 100 MHz): 143.0, 138.3, 131.1, 129.5, 127.0, 126.9,
48.8, 30.0, 24.3, 21.4, 19.3. HRMS (EI) Calcd for C13H17O2NS
251.0980, Found 251.0982. FT-IR(KBr, cm-1): 3274 s, 1916 m,
1650 m, 1597 m, 1494 m, 1446 s, 1421 s, 1389 m, 1352 m,
1321 s, 1286 m, 1160 s, 1090 s, 1068 s.
N-(diphenylmethyl)-4-methyl-benzenesulfonamide (3ha) 36
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Rf = 0.44 (40% ethyl acetate/hexane). White solid. 1H NMR
(CDCl3, 400 MHz): 7.56 (d, J = 8.00 Hz, 2H), 7.23-7.17 (m, 6 H),
7.13-7.10 (m, 6 H), 5.80 (d, J = 7.60 Hz, 1 H), 5.45-5.40 (m, 1 H),
2.37 (s, 3 H). 13C NMR (CDCl3, 100 MHz): 143.3, 140.7, 137.5,
129.4, 128.6, 127.6, 127.5, 127.3, 61.4, 21.6. HRMS (EI) Calcd
for C20H19O2NS 337.1136, Found 337.1117. FT-IR(KBr, cm-1):
3249 s, 1599 m, 1495 m, 1451 s, 1316 s, 1161 s, 1096 m, 1086
m, 1058 m, 1028m
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This study was partly supported by JST CREST Grant
Number JPMJCR17P1, Japan and JSPS KAKENHI Grant
Number 19K05156, Japan. We also thank associate professor
Eiko Yasui for assistance with HRMS.
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Keywords: Allyl alcohols • Amidation • Solid acid catalyst • H-
*BEA Zeolite
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This article is protected by copyright. All rights reserved.

10.1002/ejoc.202000296
European Journal of Organic Chemistry
FULL PAPER
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10.1002/ejoc.202000296
European Journal of Organic Chemistry
FULL PAPER
Entry for the Table of Contents
Key topic: Allyl alcohols • Amidation • Solid acid catalyst • H-*BEA Zeolite
Towards efficient conversion of ally alcohol into value-added compounds: The first examples of
zeolite catalyzed substitution of the hydroxy group in allyl alcohols with nucleophiles were developed.
The zeolite catalyzed substitution reaction was broadly adaptable to substrates under relatively mild
reaction conditions.
This article is protected by copyright. All rights reserved.