Monatshefte für Chemie - Chemical Monthly (2020) 151:213–222

https://doi.org/10.1007/s00706-019-02544-x

ORIGINAL PAPER

N‑Methylpiperidine assisted catalytic multicomponent reaction

Zahra Keshtegar1 · Reza Heydari1 · Alireza Samzadeh‑Kermani2

Received: 25 September 2019 / Accepted: 27 December 2019 / Published online: 29 January 2020
© Springer-Verlag GmbH Austria, part of Springer Nature 2020

Abstract
A catalytic methodology involving terminal alkynes, elemental sulfur, and three-membered heterocycles has been described.
This domino transformation serves as a useful method for the synthesis of oxathiolane and thiazolidine derivatives from
the readily available starting materials. In situ generated copper acetylides reacted with elemental sulfur and oxiranes or
aziridines in the presence of N-methylpiperidine as sulfur activating agent to form synthetically important heterocycles.
Graphic abstract

Keywords Sulfur activating · Catalytic reaction · Copper acetylide · Oxirane · N-Methylpiperidine

Introduction A particularly robust method in synthesis of heterocy-

Heterocyclic compounds are broadly found as core skeleton
in a wide range of pharmaceutical agents and biologically
active natural products (for selected examples of coinage
metals-catalyzed synthesis of heterocycles, see: [1–3])
[4]. Particularly, sulfur-containing heterocycles exhibited
a decent spectrum of biological properties. Owing to their
importance, myriad strategies have been developed for the
synthesis of the skeletons with sequential synthesis being
among the most reported procedures.
Electronic supplementary material The online version of this
article (https​://doi.org/10.1007/s0070​6-019-02544​-x) contains
supplementary material, which is available to authorized users.
* Alireza Samzadeh‑Kermani
drsamzadeh@gmail.com
1
Department of Chemistry, Faculty of Science, University
of Sistan and Baluchestan, Zahedan, Iran
2
Department of Chemistry, Faculty of Science, University
of Zabol, Zabol, Iran
clic compounds is transition-metal-catalyzed electrophilic
cyclization of alkynes with appropriate nucleophilic partners
[5–9]. These catalytic transformations have revolutionized
the field of heterocyclic synthesis and allow the reactions
to be performed in milder conditions with the use of raw
materials which are not amenable to classical methods.
For instance, the copper catalyzed 1,3-cycloaddition of
organic azides and terminal alkynes fix major drawback
of the thermal versions likes low rate and regioselectivity
[10–12]. The great success in copper-catalyzed the Huisgen
1,3-dipolar cycloaddition resulted in enormous attentions to
explore the precise role of copper salts in activation of the
terminal alkynes [13, 14]. These studies shed light on the
mechanism of activation of alkynes and revealed that the
π-electrons of C–C triple bond are strongly coordinated to
copper species through the reaction progress. Considering
the distortion of π-electron’s density across with the C–C tri-
ple bond is the origin of a great number of reports featuring
synthesis of molecular functionality and complexity using
copper acetylides [15–22].

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Vol.:(0123456789)
214 Z. Keshtegar et al.

Table 1  Optimization of
reaction conditions

Entry Catalyst Base Solvent Yield of 4/%

1 CuI NMP MeCN 49

2 CuBr·SMe2 NMP MeCN 93
3 Cu2O NMP MeCN 67
4 CuCl NMP MeCN 29
5 Cu(BF4)2 NMP MeCN 62
6 CuOTf NMP MeCN 53
7 Cu(OTf)2 NMP MeCN 54
8 CuBr·SMe2 NMP THF 64
9 CuBr·SMe2 NMP DMF 31
10 CuBr·SMe2 NMP Toluene Traces
11 CuBr·SMe2 NMP PEG-400 (61)a
12 CuBr·SMe2 Cs2CO3 MeCN Traces
13 CuBr·SMe2 t-BuOLi MeCN (74)a
14 CuBr·SMe2 NMM MeCN 69
15 CuBr·SMe2 (i-Pr)2EtN MeCN 21
16 CuBr·SMe2 Et3N MeCN 18
17 – NMP MeCN –b

Reaction conditions: 1a (1.0 mmol), 2 (2.0 equiv), 3a (1.5 mmol), catalyst (0.1 mmol), base (1.5 mmol),
4.0 cm3 solvent at 40 °C for 16 h
a
The digit in parentheses refer to the yield of 5
b
2-Methylthiirane was obtained in 42% yield at 90 °C

Based on these findings, Ghazanfarpour-Darjani presented Results and discussion

the electrophilic cyclization of terminal alkynes, carbon
disulfide, and oxiranes leading to oxathiane skeletons in good
yields and excellent regioselectivity [23]. Subsequently, our
group and Khalaj’ labarotary independently developed effi-
cient catalytic methods to form various heterocyclic skeletons
using same protocol [24–26]. Additionally, our group has
developed a non-catalytic reaction between terminal alkynes,
elemental sulfur, and oxiranes to form oxathiolane synthons
[27]. Our study indicated that copper acetylides did not react
effectively with elemental sulfur and oxiranes but require sto-
ichiometric quantities of a strong base to furnish the transfor-
mation. An outcome we attributed to the low nucleophilicity
of copper acetylides toward cyclooctasulfur.
Recently, Nguyen has successfully used N-methylpiperi-
dine (NMP) as a sulfur activator to form more electrophilic
sulfur species which effectively reacted with carbanion spe-
cies [28]. Commencing from previous reports and in contin-
uation of our reports in copper-catalysis [29–31], we became
interested to explore the efficiency of copper acetylides in
a reaction with elemental sulfur and three-membered het-
erocycles to form oxathiolane and thiazolidine derivatives.
We initially examined the reaction of phenyl acetylene (1a),
elemental sulfur (2), and methyl oxirane (3a) under the
catalysis of CuI in MeCN at 50 °C (Table 1). The product
5 derived from the direct attack of copper acetylide on 3a
was obtained in 23% yield together with a traces amount of
the desired compound 4a (not shown Table 1). This result is
consistent with our previous report which the reaction did
not work well with copper catalysts but metal acetylide must
be generated in a separate step to furnish the transformation
in good yield, thus requiring the use of stoichiometric quan-
tities of one metal hydride [27]. We believe that the in situ
generated copper acetylide could not attack on elemental
sulfur without a preliminary activation. Fortunately, the
proposed three-component reaction worked with accept-
able success upon using NMP as an additive and formed the
targeted oxathiolane 4a in 49% yield (entry 1). Encouraged
by this result, we next examined the efficiency of different
catalysts and CuBr·SMe2 identified as the optimum choice
for the reaction (entries 2–7). It is worth mentioning that the
oxidation states of copper salts did not affect the reaction

13
N‑Methylpiperidine assisted catalytic multicomponent reaction 215

Table 2  Synthesis of
functionalized oxathiolanes

Entry Alkyne R1 Oxirane R2,R3 Yield/%

1 1a Ph 3a Me, H 4a, 93
2 1a Ph 3b n-C4H9, H 4b, 87
3 1a Ph 3c PhOCH2, H 4c, 97
4 1a Ph 3d Me2CHOCH2, H 4d, 96
5 1a Ph 3e –(CH2)4– 4e, 89
6 1a Ph 3f Ph, H 4f, 88
7 1a Ph 3g 4-Cl-C6H4, H 4g, 85
8 1a Ph 3h 4-Me-C6H4, H 4h, 79
9 1b 4-Me-C6H4 3a Me, H 4i, 97
10 1c CH3OCH2 3a Me, H 4j, ­85a

For all entries except stated otherwise: 1 (1.0 mmol), 2 (2.0 equiv), 3 (1.5 mmol), CuBr∙SMe2 (0.1 mmol),
NMP (1.5 mmol), in 4.0 cm3 dry MeCN at 40 °C for 16 h
a
At 70 °C

outcome in appreciable manner (entry 6 vs. 7). To further
optimize the reaction parameters, we performed the reaction
in different solvent and our selected results are shown in
Table 1 (entries 8–11). Interestingly, the reaction conducted
in PEG-400 (which is known to activate oxiranes through
intermolecular H-bonding [32]) formed the direct coupling
product 5 in 61% yield (entry 11). The reaction was also
conducted with different organic and inorganic bases and
finally, NMP was selected as the base of choice based on the
efficiency both in furnishing the transformation and activa-
tion of elemental sulfur (entries 12–16). To our delight, the
use of t-BuOLi as an inorganic base resulted in formation of
compound 5 in 74% yield (entry 13). The oxygen atom in 3a
would be coordinated preferably to lithium ion, thereby pro-
viding the opportunity for the direct attack of copper acetyl-
ide on activated oxirane. Interestingly, the reaction without
copper catalyst afforded 2-methylthiirane as the main detect-
able compound in crude reaction mixture analysis (entry
17). Based on the spectroscopic analyses, all of the reactions
proceeded through a kinetically favored 5-exo cyclization
route [8], leading to the formations of oxathiolane skeletons
(excepts for the formations of compound 5).
The reaction was then generalized using various terminal
alkynes and oxiranes (Table 2). The reaction of 2-methyl­
oxirane (3a) proceeded cleanly and afforded the desired
oxathiolane 4a in good yield (entry 1). Butyl-linked oxirane
3b reacted with a partially decrease in yield (entry 2).
Oxiranes bearing an additional oxygen atom likes 3c and
3d afforded excellent yields of the corresponding oxathi-
olane structures (entries 3 and 4). An additional oxygen
atom presumably acts as an auxiliary catalyst coordination
site and thereby, increasing the oxirane reactivity toward
copper acetylides nucleophilic attack. Expanding the scope
of 3 to cyclic oxirane like 3e was also possible, allowing the
formations of fused bicyclic oxathiolane in good yield (entry
5). When phenyl-substituted oxirane 3f was subjected to the
optimum reaction conditions, the terminal-attacked product
was formed, exclusively (entry 6). The regioselectivity of
the catalytic reaction is in accordance with that of oxiranes
with similar nucleophiles reported in the literature [33, 34].
4-Chlorophenyl and p-tolyl oxiranes (3g, 3h) engaged pro-
ficiently in this transformation to furnish corresponding
oxathiolane structures (entries 7 and 8). The reaction with
p-tolylacetylene 1b afforded an excellent yield (entry 9).
Alkyl terminal alkyne 1c was also tolerated however, the
reaction required higher temperature to afford the expected
product 4i in good yield (entry 10). It should be noted that
the reactions conducted with aryl oxiranes formed the ben-
zylic attacked products, exclusively.
Recantly, Khalaj and co-workers have developed a novel
catalytic procedure to form thiazolidine derivatives from a
reaction involving terminal alkynes, elemental sulfur, and
aziridines [26]. While the importance of their report could
not be overstated, the reaction suffers from the limitation
such as formation of either oxidative Glaser coupling by-
product or the direct coupling by-product 5. To further dem-
onstrate the utility of the proposed reaction, aziridines 6a–6j
were also examined as the third coupling partner and the
results are shown in Table 3. The reaction of 2-benzyl-1-to-
sylaziridine (6a) proceeded cleanly and afforded the desired

13
216 Z. Keshtegar et al.

Table 3  Synthesis of
functionalized thiazolidines

Entry Alkyne R1 Aziridine R2, ­R3, ­R4 Yield/%

1 1a Ph 6a Bn, H, H 7a, 94
2 1a Ph 6b n-C3H7, H, ­CH3 7b, 73
3 1a Ph 6c PhOCH2, H, H 7c, 96
4 1a Ph 6d –(CH2)3–, H 7d, 71
5 1a Ph 6e –(CH2)4–, H 7e, 90
6 1a Ph 6f Ph, H, H 7f, 90
7 1a Ph 6g 2-Me-C6H4, H, H 7g, ­70a
8 1a Ph 6h 4-Cl-C6H4, H, H 7h, 86
9 1a Ph 6i 4-Me-C6H4, H, H 7i, 87
10 1a Ph 6j Ph, H, C
­ H3 7j, 39
11 1b 4-Me-C6H4 6a Bn, H, H 7k, 92
12 1d 4-MeO-C6H4 6a Bn, H, H 7l, 96
13 1e 3-CF3-C6H4 6a Bn, H, H 7m, ­34a
14 1f n-Bu 6a Bn, H, H 7n, ­83a

For all entries except stated otherwise: 1 (1.0 mmol), 2 (2.0 equiv), 6 (1.5 mmol), CuBr∙SMe2 (0.1 mmol),
NMP (1.5 mmol), in 4.0 cm3 dry MeCN at 40 °C for 16 h
a
At 70 °C

3-tosylthiazolidine 7a in high yield (entry 1). The catalytic
reaction was partially inhibited by steric hindrance from an
additional substituent at the 2-position; as 2-methyl-2-pro-
pyl-1-tosylaziridine (6b) reacted with a notable decrease
in yield (entry 2). Phenoxymethyl-substituted aziridine 6c
afforded an excellent (entry 3). Expanding the scope of aziri-
dine to cyclic aziridines 6d and 6e were also possible, allow-
ing the formations of bicyclic thiazolidines in good yields
(entries 4 and 5). When phenyl-substituted aziridine 6f was
subjected to the optimum reaction conditions, the yield was
increased (entry 6). The reaction of o-tolylaziridine 6g pro-
vided a lower yield (entry 7). Aromatic aziridines 6h–6i
were also tolerated (entries 8 and 9). It should be noted
that the reactions conducted with aryl aziridines formed the
benzylic attacked products, exclusively. gem-Disubstituted
aziridine 6j only afforded a low yield of the desired product
(entry 10). Electron-rich terminal alkynes 1b and 1c effec-
tively participated in this domino transformation (entries 11
and 12). It could be deduced that the nucleophilic attack of
metal acetylide on activated sulphur might be the rate-deter-
mination step of this transformation. This deduction is also
consistent with the fact that 1-tosyl-2-[3-(trifluoromethyl)-
phenyl]aziridine (1d) only afforded a low yield of the
desired product (entry 13). Interestingly, when the reaction
was carried out with 1-hexyne (1e), the reaction proceeded
smoothly to afford the desired thiazolidine structure in good
yield (entry 14).
When chiral oxirane 3f′ was used as the substrate, the
domino ring opening/cyclization reaction proceeded with
racemization at the chiral carbon (Scheme 1). This result

Scheme 1

13
N‑Methylpiperidine assisted catalytic multicomponent reaction 217
Scheme 2
indicated that the reaction proceeded through a SN1 pathway.
This outcome is further supported by the fact that the nucle-
ophilic attack occurred exclusively at the benzylic carbon
using phenyl-substituted oxiranes (see entries 6–8, Table 2).
To get insights on the detail of the reaction pathway,
some control experiments were performed and the results
are shown in Scheme 2. Initially, phenyl acetylene was
reacted with elemental sulfur to form phenylethynylthiolate
Scheme 3
species 8. Control experiments revealed that the reaction did
not afford the desired phenylethynylthiolate 8 neither in the
presence or absence of presence of NMP using copper salt
as the catalyst. Additionally, the reaction conducted under
air formed the expected oxidative Glaser coupling product 9
in 71% (Scheme 1a). It is worth mentioning that the reaction
formed the species 10 as the main detectable product with
copper catalyst and NMP under N ­ 2. A compound which is
formed through dimerization of phenylethynylthiolate 8. For
ring opening of oxirane with sodium phenylacetylide 11, it
was found that the presence of copper catalyst completely
inhibited formation of ring-opened compound 12 and
instead the desired product 4a was obtained in 92% yield,
while, the reaction conducted in the absence of copper in
i-PrOH formed the ring-opened compound 12 in 89% yield
(Scheme 1b). This data demonstrated that copper catalyst
may not be involved in formation of compound 12. Finally,
control experiment revealed that electrophilic cyclization of
alkynol 12 to oxathiolane 4a takes place only in the pres-
ence of copper catalyst and NMP (Scheme 1c).
Based on the above findings and previous reports, ele-
mental sulfur was initially activated with NMP to provide
species A [31]. Acetylide B, derived from the reaction of
terminal alkyne with Cu(I) by the action of NMP, reacted
with A to afford alkyne polysulfide C [35]. The copper
thiolate species C subsequently attacks on oxirane 3a to
form the ring-opened intermediate D [27]. Finally, nucleo-
philic attack of alkoxide or amide ion (in the presence of
13
218
oxirane or aziridine, respectively) across activated triple
bond (through a kinetically favored 5-exo electrophilic
cyclization) lead to formation of intermediate E which
further transferred to the desired product 4 or 7 [36] by
the action of ­NMPH+ (Scheme 3).
Conclusion
In summary, we have documented a general, mild, and effi-
cient reaction between terminal alkynes, elemental sulfur,
and either oxiranes or aziridines as third coupling partner in
the presence of CuBr·SMe2 as the catalyst and N-methylpi-
peridine as sulfur activating reagent to access synthetically
important oxathiolane and thiazolidine structures. In contrast
to previous reports, the reaction proceeded in regio- and
chemoselective manner and no compounds arising from the
direct attack of copper acetylides on oxiranes are detected
under the optimum reaction conditions [26, 27]. Control
experiments indicated that an inert atmosphere is necessary
to furnish the transformation in good yield.
Experimental
All reactions were carried out in Schlenk tubes (25 cm3)
under nitrogen atmosphere. All the reagents, catalysts, and
additives were obtained from commercial sources. All the
solvents were purchased from PALAENERGY Pure Chemi-
cal Industries, and were dried and degassed before use.
N-Tosylaziridines were prepared using the literature proce-
dures [37]. Melting points were measured with Electrother-
mal-9100 apparatus. IR spectra were determined on a Nicolet
6700 spectrometer. 1H and 13C NMR spectra were recorded
with Bruker DRX-500 AVANCE instrument; in C ­ DCl3 at
500 and 125 MHz, resp; δ in ppm, J in Hz. Mass spectra were
determined on a EIMS (70 eV): Finnigan-MAT-8430 mass
spectrometer. Elemental analyses were performed with a Her-
aeus Rapid analyser. The results agreed favorably with the
calculated values. Silica gel 60 (particle size 63–200 µm or
40–100 mesh) was used for column chromatography. (Merck,
item number 7734-3). TLC analyses were performed on com-
mercial glass plates bearing a 0.25-mm layer of Merck Silica
gel 60 (Merck, item number 116835).
General procedure for the preparation
of compounds 4 or 7
A Schlenk tube (25 cm3) equipped with a magnetic stir bar
was charged with elemental sulfur (2.0 equiv., based on
terminal alkyne amount), NMP (1.5 mmol), and 4.0 cm3
13
Z. Keshtegar et al.
MeCN. After the mixture was stirred at 40 °C for 1 h,
CuBr∙SMe2 (0.1 mmol), terminal alkyne (1.0 mmol), and
three-membered heterocycle (1.5 mmol) were added under
inert atmosphere. The tube was evacuated and backfilled
with argon (three times). Subsequently, the mixture was
stirred for 16 h at appropriate temperature (see Tables 2,
3). After cooling to room temperature, the mixture was
passed through silica gel pad and concentrated under
reduced pressure. The resulting residue was purified with
column chromatography on silica gel (eluent gradient of
EtOAc/hexane, see spectroscopic analysis section) to give
the corresponding products 4 or 7 in the yields listed in
Tables 2 and 3.
2‑Benzylidene‑5‑methyl‑1,3‑oxathiolane (4a, ­C11H12OS) The
crude product was purified by column chromatography
­(SiO 2, hexane/EtOAc 13/1, R f = 0.29) affording 0.18 g
(93%) of 4a. Pale yellow oil; 1H NMR (500.1 MHz, ­CDCl3):
δ = 1.32 (3H, d, 3J = 6.1 Hz, Me), 3.47 (1H, dd, 2J = 12.3 Hz,
3
J = 10.1 Hz, CH), 3.55 (1H, dd, 2J = 12.3 Hz, 3J = 5.2 Hz,
CH), 4.51–4.57 (1H, m, CH), 5.31 (1H, s, CH), 7.32 (1H,
t, 3J = 7.1 Hz, CH), 7.41 (2H, t, 3J = 7.2 Hz, 2 CH), 7.64
(2H, d, 3J = 7.3 Hz, 2 CH) ppm; 13C NMR (125.7 MHz,
­CDCl3): δ = 23.1 (Me), 48.1 ­(CH2), 81.4 (CH), 87.1 (CH),
126.5 (CH), 129.4 (2 CH), 130.7 (2 CH), 137.8 (C), 167.8
(C) ppm.
2‑Benzylidene‑5‑butyl‑1,3‑oxathiolane (4b, ­C14H18OS) The
crude product was purified by column chromatography
­(SiO2, hexane/EtOAc 12/1, Rf = 0.48) affording 0.20 g (87%)
of 4b. Pale yellow oil; IR (KBr): v̄ = 3014, 2973, 1651, 1473,
1286, 1095 cm−1; 1H NMR (500.1 MHz, ­CDCl3): δ = 1.09
(3H, t, 3J = 6.0 Hz, Me), 1.55–1.95 (6H, m, 3 C ­ H2), 3.11
(1H, dd, 2J = 11.8 Hz, 3J = 5.0 Hz, CH), 3.40 (1H, dd,
2
J = 11.8 Hz, 3J = 9.7 Hz, CH), 4.41–4.47 (1H, m, CH),
5.29 (1H, s, CH), 7.31 (1H, t, 3J = 7.6 Hz, CH), 7.40 (2H,
t, 3J = 7.6 Hz, 2 CH), 7.59 (2H, d, 3J = 7.6 Hz, 2 CH) ppm;
13
C NMR (125.7 MHz, C ­ DCl3): δ = 11.2 (Me), 28.1 (­ CH2),
30.4 ­(CH2), 37.9 (­ CH2), 47.9 (­ CH2), 84.1 (CH), 87.2 (CH),
126.5 (CH), 128.9 (2 CH), 130.1 (2 CH), 137.8 (C), 167.1
(C) ppm; EI-MS (70 eV): m/z (%) = 234 ­(M+, 1), 177 (23),
100 (65), 91 (43), 77 (100), 54 (48).
2‑Benzylidene‑5‑(phenoxymethyl)‑1,3‑oxathiolane (4c,
­C17H16O2S) The crude product was purified by column chro-
matography ­(SiO2, hexane/EtOAc 10/1, Rf = 0.27) afford-
ing 0.28 g (97%) of 4c. Yellow oil; 1H NMR (500.1 MHz,
­CDCl3): δ = 3.41 (1H, dd, 2J = 12.1 Hz, 3J = 9.1 Hz, CH),
3.53 (1H, dd, 2J = 12.1 Hz, 3J = 5.1 Hz, CH), 4.27 (1H, dd,
2
J = 11.2 Hz, 3J = 8.2 Hz, CH), 4.36 (1H, dd, 2J = 11.2 Hz,
3
J = 5.2 Hz, CH), 4.98–5.02 (1H, m, CH), 5.34 (1H, s, CH),
6.87 (1H, t, 3J = 6.9 Hz, CH), 6.93 (2H, d, 3J = 6.9 Hz, 2 CH),
7.21 (2H, t, 3J = 6.9 Hz, 2 CH), 7.34 (1H, t, 3J = 7.2 Hz, CH),
N‑Methylpiperidine assisted catalytic multicomponent reaction 219
7.43 (2H, t, 3J = 7.3 Hz, 2 CH), 7.66 (2H, d, 3J = 7.3 Hz, 2
CH) ppm; 13C NMR (125.7 MHz, ­CDCl3): δ = 43.6 ­(CH2),
71.8 ­(CH2), 85.4 (CH), 87.2 (CH), 114.3 (2 CH), 120.7
(CH), 127.1 (CH), 128.8 (CH), 129.7 (2 CH), 130.1 (2 CH),
137.1 (C), 160.3 (C), 165.9 (C) ppm.
2‑Benzylidene‑5‑(isopropoxymethyl)‑1,3‑oxathiolane (4d,
­C14H18O2S) The crude product was purified by column chro-
matography ­(SiO2, hexane/EtOAc 13/1, Rf = 0.36) affording
0.24 g (96%) of 4d. Yellow oil; IR (KBr): v̄ = 3038, 3012,
2958, 1639, 1542, 1326, 1118 cm−1; 1H NMR (500.1 MHz,
­CDCl3): δ = 1.23 (6H, d, 3J = 6.7 Hz, 2 Me), 3.36 (1H, dd,
2
J = 11.1 Hz, 3J = 7.7 Hz, CH), 3.49 (1H, dd, 2J = 11.1 Hz,
3
J = 5.1 Hz, CH), 3.67 (1H, dd, 2J = 11.3 Hz, 3J = 8.0 Hz,
CH), 3.73 (1H, dd, 2J = 11.3 Hz, 3J = 5.0 Hz, CH), 3.88–3.93
(1H, m, CH), 4.51–4.55 (1H, m, CH), 5.19 (1H, s, CH), 7.34
(1H, t, 3J = 6.9 Hz, CH), 7.42 (2H, t, 3J = 6.9 Hz, 2 CH),
7.59 (2H, d, 3J = 6.9 Hz, 2 CH) ppm; 13C NMR (125.7 MHz,
­CDCl3): δ = 21.5 (2 Me), 38.1 ­(CH2), 67.2 ­(CH2), 74.1 (CH),
82.9 (CH), 87.3 (CH), 126.5 (CH), 128.9 (2 CH), 130.8
(2 CH), 137.1 (C), 167.6 (C) ppm; EI-MS (70 eV): m/z
(%) = 250 ­(M+, 3), 235 (14), 177 (52), 101 (73), 91 (38),
77 (100).
2‑Benzylidenehexahydrobenzo[d][1,3]oxathiole (4e,
­C14H16OS) The crude product was purified by column chro-
matography ­(SiO2, hexane/EtOAc 8/1, Rf = 0.42) afford-
ing 0.21 g (89%) of 4e. Yellow oil; 1H NMR (500.1 MHz,
­CDCl3): δ = 1.47–2.05 (8H, m, 4 ­CH2), 3.01–3.05 (1H, m,
CH), 4.11–4.15 (1H, m, CH), 5.31 (1H, s, CH), 7.32 (1H,
t, 3J = 7.8 Hz, CH), 7.41 (2H, t, 3J = 7.8 Hz), 7.67 (2H, d,
3
J = 7.7 Hz, 2 CH) ppm; 13C NMR (125.7 MHz, C ­ DCl3):
δ = 28.1 ­(CH2), 29.4 ­(CH2), 32.7 ­(CH2), 39.2 ­(CH2), 52.4
(CH), 83.9 (CH), 86.5 (CH), 127.2 (CH), 129.8 (2 CH),
130.9 (2 CH), 137.5 (C), 167.2 (C) ppm.
2‑Benzylidene‑4‑phenyl‑1,3‑oxathiolane (4f, ­C16H14OS) The
crude product was purified by column chromatography
­(SiO2, hexane/EtOAc 7/1, Rf = 0.46) affording 0.22 g (88%)
of 4f. Yellow oil; IR (KBr): v̄ = 3021, 2981, 1632, 1482,
1251, 1092 cm−1; 1H NMR (500.1 MHz, C ­ DCl3): δ = 4.44–
4.49 (1H, m, CH), 4.89 (1H, dd, 2J = 11.9 Hz, 3J = 9.1 Hz,
CH), 4.97 (1H, dd, 2J = 11.9 Hz, 3J = 6.0 Hz, CH), 5.29
(1H, s, CH), 7.23 (2H, d, 3J = 7.6 Hz, 2 CH), 7.27 (1H, t,
3
J = 7.5 Hz, CH), 7.31 (2H, t, 3J = 7.5 Hz, 2 CH), 7.36 (1H,
t, 3J = 7.8 Hz, CH), 7.43 (2H, t, 3J = 7.8 Hz, 2 CH), 7.66 (2H,
d, 3J = 7.9 Hz, 2 CH) ppm; 13C NMR (125.7 MHz, C ­ DCl3):
δ = 55.7 (CH), 78.1 (­ CH2), 85.4 (CH), 126.1 (CH), 127.0
(CH), 128.2 (2 CH), 128.8 (CH), 129.4 (2 CH), 130.1 (2
CH), 138.1 (C), 143.5 (C), 166.1 (C) ppm; EI-MS (70 eV):
m/z (%) = 254 ­(M+, 2), 177 (32), 153 (47), 100 (62), 91 (39),
77 (100).
2‑Benzylidene‑4‑(4‑chlorophenyl)‑1,3‑oxathiolane (4g,
­C16H13ClOS) The crude product was purified by column
chromatography ­( SiO 2, hexane/EtOAc 7/1, R f = 0.17)
affording 0.24 g (85%) of 4g. Yellow oil; IR (KBr):
v̄ = 3052, 2972, 1648, 1522, 1267, 1076 cm−1; 1H NMR
(500.1 MHz, ­CDCl3): δ = 4.25–4.30 (1H, m, CH), 4.73
(1H, dd, 2J = 12.6 Hz, 3J = 9.0 Hz, CH), 4.84 (1H, dd,
2
J = 12.6 Hz, 3J = 5.2 Hz, CH), 5.32 (1H, s, CH), 7.19 (2H,
d, 3J = 7.8 Hz, 2 CH), 7.30 (1H, t, 3J = 7.1 Hz, CH), 7.37
(2H, d, 3J = 7.8 Hz, 2 CH), 7.43 (2H, t, 3J = 7.1 Hz, CH),
7.59 (2H, d, 3J = 7.2 Hz, 2 CH) ppm; 13C NMR (125.7 MHz,
­CDCl3): δ = 52.1 (CH), 76.9 ­(CH2), 84.7 (CH), 126.9 (CH),
128.1 (2 CH), 128.9 (2 CH), 129.6 (2 CH), 129.9 (2 CH),
134.2 (C), 138.1 (C), 141.3 (C), 164.9 (C) ppm; EI-MS
(70 eV): m/z (%) = 288 ­(M+, 1), 211 (14), 177 (28), 111
(79), 100 (41), 119 (78), 91 (39), 77 (100).
2 ‑ B e n z y l i d e n e ‑ 4 ‑ ( p‑ t o l y l ) ‑ 1 , 3 ‑ ox at h i o l a n e ( 4 h ,
­C17H16OS) The crude product was purified by column chro-
matography ­(SiO2, hexane/EtOAc 11/1, Rf = 0.22) affording
0.22 g (79%) of 4h. Yellow oil; IR (KBr): v̄ = 3041, 2971,
2942, 1670, 1482, 1252, 1075 cm−1; 1H NMR (500.1 MHz,
­CDCl3): δ = 2.34 (3H, s, Me), 4.12–4.18 (1H, m, CH),
4.83 (1H, dd, 2J = 12.5 Hz, 3J = 8.2 Hz, CH), 4.95 (1H, dd,
2
J = 12.5 Hz, 3J = 4.9 Hz, CH), 5.25 (1H, s, CH), 7.11 (2H,
d, 3J = 7.4 Hz, 2 CH), 7.17 (2H, d, 3J = 7.4 Hz, 2 CH), 7.33
(1H, t, 3J = 7.3 Hz, CH), 7.44 (2H, d, 3J = 7.3 Hz, 2 CH),
7.65 (2H, d, 3J = 7.1 Hz, 2 CH) ppm; 13C NMR (125.7 MHz,
­CDCl3): δ = 22.7 ­(CH3), 53.9 (CH), 79.8 (­ CH2), 86.2 (CH),
125.2 (2 CH), 126.8 (CH), 128.1 (2 CH), 129.8 (2 CH),
130.3 (2 CH), 135.4 (C), 137.2 (C), 140.9 (C), 166.7 (C)
ppm; EI-MS (70 eV): m/z (%) = 268 ­(M+, 3), 191 (17), 177
(21), 176 (34), 100 (69), 91 (49), 77 (100).
5‑Methyl‑2‑(4‑methylbenzylidene)‑1,3‑oxathiolane (4i,
­C12H14OS) The crude product was purified by column chro-
matography ­(SiO2, hexane/EtOAc 11/1, Rf = 0.31) affording
0.20 g (97%) of 4i. Yellow oil; IR (KBr): v̄ = 3019, 2942,
1621, 1542, 1466, 1258, 1109 cm−1; 1H NMR (500.1 MHz,
­CDCl3): δ = 1.32 (3H, d, 3J = 5.8 Hz, Me), 2.45 (3H, s, Me),
3.45 (1H, dd, 2J = 12.2 Hz, 3J = 8.8 Hz, CH), 3.53 (1H, dd,
2
J = 12.2 Hz, 3J = 5.1 Hz, CH), 4.11–4.16 (1H, m, CH), 5.25
(1H, s, CH), 7.42 (2H, d, 3J = 7.3 Hz, 2 CH), 7.64 (2H, d,
3
J = 7.3 Hz, 2 CH) ppm; 13C NMR (125.7 MHz, C ­ DCl3):
δ = 22.5 (Me), 24.1 (Me), 46.2 (­ CH2), 82.1 (CH), 87.7 (CH),
129.1 (2 CH), 129.8 (2 CH), 134.1 (C), 138.9 (C), 166.2 (C)
ppm; EI-MS (70 eV): m/z (%) = 206 ­(M+, 3), 191 (17), 100
(71), 91 (42), 77 (100).
2‑(4‑Methoxybenzylidene)‑5‑methyl‑1,3‑oxathiolane (4j,
­C12H14O2S) The crude product was purified by column chro-
matography ­(SiO2, hexane/EtOAc 9/1, Rf = 0.17) affording
0.19 g (85%) of 4j. Yellow oil; IR (KBr): v̄ = 3042, 2972,
13
220
1671, 1523, 1471, 1276, 1092 cm−1; 1H NMR (500.1 MHz,
­CDCl3): δ = 1.32 (3H, d, 3J = 6.2 Hz, Me), 3.90 (3H, s,
­OCH3), 3.37 (1H, dd, 2J = 12.0 Hz, 3J = 8.5 Hz, CH), 3.44
(1H, dd, 2J = 12.0 Hz, 3J = 5.1 Hz, CH), 4.11–4.17 (1H, m,
CH), 5.27 (1H, s, CH), 7.12 (2H, d, 3J = 7.8 Hz, 2 CH),
7.53 (2H, d, 3J = 7.8 Hz, 2 CH) ppm; 13C NMR (125.7 MHz,
­CDCl3): δ = 23.5 (Me), 43.8 ­(CH2), 54.2 ­(OCH3), 82.1 (CH),
85.3 (CH), 114.1 (2 CH), 129.1 (C), 131.3 (2 CH), 156.2
(C), 161.4 (C) ppm; EI-MS (70 eV): m/z (%) = 222 ­(M+, 3),
207 (19), 177 (26), 121 (89), 107 (53), 100 (42), 77 (100).
4‑Benz yl‑2‑benz ylidene ‑3‑tosylthiazolidine (7a,
­C24H23NO2S2) The crude product was purified by column
chromatography ­( SiO 2, hexane/EtOAc 5/1, R f = 0.34)
affording 0.40 g (94%) of 7a. Pale yellow solid; m.p.:
105–107 °C; IR (KBr): v̄ = 3015, 2951, 1611, 1547, 1312,
1276, 1032 cm−1; 1H NMR (500.1 MHz, ­CDCl3): δ = 2.29
(3H, s, Me), 2.73 (1H, dd, 2J = 12.5 Hz, 3J = 9.0 Hz, CH),
2.84 (1H, dd, 2J = 12.5 Hz, 3J = 5.1 Hz, CH), 3.21 (1H, dd,
2
J = 11.5 Hz, 3J = 9.3 Hz, CH), 3.35 (1H, dd, 2J = 11.5 Hz,
3
J = 5.3 Hz, CH), 3.81–3.90 (1H, m, CH), 5.47 (1H, s, CH),
7.14–7.54 (10H, m, 10 CH), 7.58 (2H, d, 3J = 7.3 Hz, 2 CH),
7.71 (2H, d, 3J = 7.1 Hz, 2 CH) ppm; 13C NMR (125.7 MHz,
­CDCl3): δ = 23.2 (Me), 38.2 (­ CH2), 44.2 (­ CH2), 60.8 (CH),
87.6 (CH), 125.6 (CH), 125.9 (CH), 127.5 (2 CH), 128.3 (2
CH), 128.7 (2 CH), 129.5 (2 CH), 129.9 (2 CH), 131.3 (2
CH), 134.1 (C), 135.9 (C), 138.7 (C), 139.5 (C), 158.9 (C)
ppm; EI-MS (70 eV): m/z (%) = 421 ­(M+, 3), 330 (28), 287
(17), 135 (43), 91 (100), 77 (79), 54 (32).
2‑Benzylidene‑4‑methyl‑4‑propyl‑3‑tosylthiazolidine (7b,
­C21H25NO2S2) The crude product was purified by column
chromatography ­(SiO2, hexane/EtOAc 6/1, Rf = 0.28) afford-
ing 0.28 g (73%) of 7b. Pale yellow oily solid; IR (KBr):
v̄ = 3022, 2941, 1614, 1547, 1287, 1211, 1098 cm−1; 1H
NMR (500.1 MHz, ­CDCl3): δ = 0.96 (3H, t, 3J = 6.2 Hz,
Me), 1.35 (3H, s, Me), 1.41–1.63 (4H, m, 2 ­CH2), 2.36
(3H, s, Me), 3.04 (1H, d, 2J = 11.5 Hz, CH), 3.08 (1H,
d, 2J = 11.5 Hz, CH), 5.37 (1H, s, CH), 7.35–7.49 (5H,
m, 5 CH), 7.64 (2H, d, 3J = 7.2 Hz, 2 CH), 7.73 (2H, d,
3
J = 7.6 Hz, 2 CH) ppm; 13C NMR (125.7 MHz, C ­ DCl3):
δ = 14.6 (Me), 19.6 (­ CH2), 22.1 (Me), 23.5 (Me), 40.1 (­ CH2),
50.9 ­(CH2), 68.1 (C), 89.4 (CH), 126.5 (CH), 127.5 (2 CH),
128.2 (2 CH), 128.7 (2 CH), 130.5 (2 CH), 135.1 (C), 135.9
(C), 139.4 (C), 157.1 (C) ppm; MS: m/z (%) = 387 ­(M+, 4),
372 (13), 232 (36), 155 (67), 105 (78), 77 (100), 54 (41).
2‑Benzylidene‑4‑(phenoxymethyl)‑3‑tosylthiazolidine (7c,
­C24H23NO3S2) The crude product was purified by column
chromatography ­(SiO2, hexane/EtOAc 4/1, Rf = 0.31) afford-
ing 0.42 g (96%) of 7c. Pale yellow solid; m.p.: 88–90 °C; IR
(KBr): v̄ = 3031, 2943, 1608, 1550, 1302, 1276, 1085 cm−1;
1
H NMR (500.1 MHz, C ­ DCl3): δ = 2.35 (3H, s, Me), 3.11
13
Z. Keshtegar et al.
(1H, dd, 3J = 11.8 Hz, 3J = 9.79 Hz, CH), 3.25 (1H, dd,
2
J = 11.8 Hz, 3J = 5.8 Hz, CH), 3.57–3.69 (1H, m, 1 CH),
4.11 (1H, dd, 3J = 11.5 Hz, 3J = 9.6 Hz, CH), 4.18 (1H, dd,
2
J = 11.5 Hz, 3J = 5.3 Hz, CH), 5.33 (1H, s, CH), 6.89 (2H, d,
3
J = 7.4 Hz, 2 CH), 6.97 (1H, t, 3J = 7.1 Hz, CH), 7.25 (2H,
d, 3J = 7.1 Hz, 2 CH), 7.35–7.46 (5H, m, 5 CH), 7.61 (2H, d,
3
J = 7.1 Hz, 2 CH), 7.72 (2H, d, 3J = 7.5 Hz, 2 CH) ppm; 13C
NMR (125.7 MHz, ­CDCl3): δ = 22.1 (Me), 38.2 (­ CH2), 61.7
­(CH2), 67.1 (CH), 90.1 (CH), 114.1 (2 CH), 121.2 (CH),
124.3 (CH), 126.2 (2 CH), 128.2 (2 CH), 128.9 (2 CH),
130.1 (2 CH), 130.8 (2 CH), 135.1 (C), 136.2 (C), 139.7 (C),
157.1 (C), 160.2 (C) ppm; MS: m/z (%) = 437 ­(M+, 1), 330
(15), 195 (43), 155 (59), 105 (73), 77 (100), 54 (48).
2‑Benzylidene‑3‑tosylhexahydro‑2H‑cyclopenta[d]thiazole
(7d, ­C20H21NO2S2) The crude product was purified by col-
umn chromatography ­(SiO2, hexane/EtOAc 5/1, Rf = 0.28)
affording 0.26 g (71%) of 7d. Pale yellow solid; m.p.: 122–
124 °C; IR (KBr): v̄ = 3042, 2951, 1604, 1554, 1311, 1256,
1051 cm−1; 1H NMR (500.1 MHz, C ­ DCl3): δ = 1.64–2.08
(6H, m, 3 C­ H2), 2.32 (3H, s, Me), 2.61–2.67 (1H, m, 1 CH),
3.12–3.19 (1H, m, CH), 5.32 (1H, s, CH), 7.33–7.49 (5H,
m, 5 CH), 7.61 (2H, d, 3J = 7.1 Hz, 2 CH), 7.67 (2H, d,
3
J = 7.5 Hz, 2 CH) ppm; 13C NMR (125.7 MHz, C ­ DCl3):
δ = 22.9 (Me), 26.3 (­ CH2), 31.5 (­ CH2), 33.2 (­ CH2), 48.2
(CH), 67.2 (CH), 88.3 (CH), 126.2 (CH), 128.5 (2 CH),
129.3 (2 CH), 130.4 (2 CH), 130.9 (2 CH), 134.2 (C), 136.2
(C), 139.5 (C), 157.4 (C) ppm; MS: m/z (%) = 371 ­(M+, 2),
216 (32), 181 (50), 155 (69), 128 (54), 77 (100), 54 (69).
2‑Benzylidene‑3‑tosyloctahydrobenzo[d]thiazole (7e,
­C21H23NO2S2) The crude product was purified by column
chromatography ­( SiO 2, hexane/EtOAc 4/1, R f = 0.39)
affording 0.35 g (90%) of 7e. Pale yellow solid; m.p.: 122–
124 °C; IR (KBr): v̄ = 3016, 2955, 1603, 1531, 1308, 1278,
1068 cm−1; 1H NMR (500.1 MHz, C ­ DCl3): δ = 1.28–2.02
(8H, m, 4 C­ H2), 2.32 (3H, s, Me), 2.55–2.62 (1H, m, 1 CH),
3.08–3.14 (1H, m, CH), 5.23 (1H, s, CH), 7.32–7.42 (5H,
m, 5 CH), 7.62 (2H, d, 3J = 7.6 Hz, 2 CH), 7.72 (2H, d,
3
J = 7.5 Hz, 2 CH) ppm; 13C NMR (125.7 MHz, C ­ DCl3):
δ = 22.6 (Me), 24.7 (­ CH2), 28.3 (­ CH2), 30.2 (­ CH2), 34.8
­(CH2), 44.6 (CH), 68.2 (CH), 88.3 (CH), 126.7 (CH), 128.2
(2 CH), 128.5 (2 CH), 129.6 (2 CH), 130.4 (2 CH), 134.1
(C), 135.7 (C), 139.7 (C), 157.2 (C) ppm; MS: m/z (%) = 385
­(M+, 1), 230 (17), 155 (67), 128 (54), 77 (100), 54 (46).
2‑Benz ylidene ‑5‑phenyl‑3‑tosylthiazolidine (7f,
­C23H21NO2S2) The crude product was purified by column
chromatography ­(SiO2, hexane/EtOAc 4/1, Rf = 0.23) afford-
ing 0.37 g (90%) of 7f. Pale yellow solid; m.p.: 87–89 °C; IR
(KBr): v̄ = 3033, 2951, 1632, 1534, 1302, 1254, 1087 cm−1;
1
H NMR (500.1 MHz, C ­ DCl3): δ = 2.36 (3H, s, Me), 3.57
(1H, dd, 3J = 11.8 Hz, 3J = 8.7 Hz, CH), 3.68 (1H, dd,
N‑Methylpiperidine assisted catalytic multicomponent reaction 221
2
J = 11.8 Hz, 3J = 5.4 Hz, CH), 4.53–4.68 (1H, m, CH),
5.35 (1H, s, CH), 7.18–7.45 (10H, m, 10 CH), 7.63 (2H,
d, 3J = 7.4 Hz, 2 CH), 7.72 (2H, d, 3J = 7.5 Hz, 2 CH) ppm;
13
C NMR (125.7 MHz, C ­ DCl3): δ = 23.4 (Me), 38.1 (­ CH2),
69.5 (CH), 89.2 (CH), 124.9 (CH), 125.3 (CH), 126.2 (2
CH), 126.8 (2 CH), 127.9 (2 CH), 129.2 (2 CH), 129.5 (2
CH), 132.1 (2 CH), 133.9 (C), 135.1 (C), 138.2 (C), 139.5
(C), 160.4 (C) ppm; MS: m/z (%) = 407 ­(M+, 4), 330 (27),
177 (51), 155 (62), 105 (49), 77 (100).
2‑Benzylidene ‑4‑(o‑tolyl)‑3‑tosylthiazolidine (7g,
­C24H23NO2S2) The crude product was purified by column
chromatography ­(SiO2, hexane/EtOAc 4/1, Rf = 0.31) afford-
ing 0.30 g (70%) of 7g. Pale yellow solid; m.p.: 70–72 °C; IR
(KBr): v̄ = 3025, 2967, 1613, 1555, 1314, 1251, 1107 cm−1;
1
H NMR (500.1 MHz, C ­ DCl3): δ = 2.31 (3H, s, Me), 2.42
(3H, s, Me), 3.51 (1H, dd, 3J = 12.3 Hz, 3J = 9.5 Hz, CH),
3.72 (1H, dd, 2J = 12.3 Hz, 3J = 5.9 Hz, CH), 4.47–4.61 (1H,
m, CH), 5.39 (1H, s, CH), 6.87 (1H, d, 3J = 7.1 Hz, CH),
7.17 (1H, t, 3J = 7.1 Hz, CH), 7.23 (1H, t, 3J = 7.2 Hz, CH),
7.29–7.45 (6H, m, 6 CH), 7.62 (2H, d, 3J = 7.1 Hz, 2 CH),
7.70 (2H, d, 3J = 7.7 Hz, 2 CH) ppm; 13C NMR (125.7 MHz,
­CDCl3): δ = 20.8 (Me), 22.9 (Me), 36.2 ­(CH2), 68.8 (CH),
87.8 (CH), 122.7 (CH), 124.1 (CH), 125.2 (CH), 126.4
(CH), 127.9 (2 CH), 128.2 (2 CH), 128.8 (2 CH), 129.7 (2
CH), 131.7 (CH), 133.6 (C), 134.5 (C), 135.1 (C), 139.2 (C),
143.2 (C), 157.8 (C) ppm; MS: m/z (%) = 421 ­(M+, 1), 330
(16), 177 (64), 155 (71), 105 (36), 77 (100).
2‑Benzylidene‑4‑(4‑chlorophenyl)‑3‑tosylthiazolidine (7h,
­C23H20ClNO2S2) The crude product was purified by column
chromatography ­(SiO2, hexane/EtOAc 3/1, Rf = 0.46) afford-
ing 0.38 g (86%) of 7h. Pale yellow solid; m.p.: 113–115 °C;
IR (KBr): v̄ = 3031, 2973, 2935, 1612, 1552, 1303, 1178,
1092 cm−1; 1H NMR (500.1 MHz, C ­ DCl3): δ = 2.33 (3H, s,
Me), 3.43 (1H, dd, 3J = 12.0 Hz, 3J = 10.3 Hz, CH), 3.55 (1H,
dd, 2J = 12.0 Hz, 3J = 5.9 Hz, CH), 4.16–4.26 (1H, m, CH),
5.32 (1H, s, CH), 7.12 (2H, d, 3J = 7.6 Hz, 2 CH), 7.24–7.41
(9H, m, 9 CH), 7.60 (2H, d, 3J = 7.8 Hz, 2 CH), 7.70 (2H,
d, 3J = 7.4 Hz, 2 CH) ppm; 13C NMR (125.7 MHz, ­CDCl3):
δ = 23.4 (Me), 38.1 ­(CH2), 67.8 (CH), 87.1 (CH), 126.1 (CH),
126.7 (2 CH), 128.1 (2 CH), 129.2 (2 CH), 129.8 (2 CH),
131.7 (2 CH), 132.6 (2 CH), 132.8 (C), 133.5 (C), 134.7 (C),
135.7 (C), 139.1 (C), 159.2 (C) ppm; MS: m/z (%) = 441 ­(M+,
3), 288 (22), 178 (55), 155 (67), 111 (72), 77 (100).
2‑Benzylidene ‑4‑(p‑tolyl)‑3‑tosylthiazolidine (7i,
­C24H23NO2S2) The crude product was purified by column
chromatography ­( SiO 2, hexane/EtOAc 4/1, R f = 0.40)
affording 0.37 g (87%) of 7i. Pale yellow solid; m.p.:
134–136 °C; IR (KBr): v̄ = 3025, 2967, 1613, 1555, 1314,
1251, 1107 cm−1; 1H NMR (500.1 MHz, ­CDCl3): δ = 2.29
(3H, s, Me), 2.38 (3H, s, Me), 3.43 (1H, dd, 3J = 12.3 Hz,
3
J = 9.5 Hz, CH), 3.55 (1H, dd, 2J = 12.3 Hz, 3J = 5.9 Hz,
CH), 4.47–4.61 (1H, m, CH), 5.39 (1H, s, CH), 7.06 (2H, d,
3
J = 7.1 Hz, 2 CH), 7.17 (2H, d, 3J = 7.1 Hz, 2 CH), 7.23–
7.58 (7H, m, 7 CH), 7.70 (2H, d, 3J = 7.7 Hz, 2 CH) ppm;
13
C NMR (125.7 MHz, C ­ DCl3): δ = 23.1 (Me), 26.5 (Me),
33.7 ­(CH2), 68.1 (CH), 87.2 (CH), 124.7 (2 CH), 126.5
(CH), 127.8 (2 CH), 128.8 (2 CH), 129.1 (2 CH), 130.2 (2
CH), 131.8 (2 CH), 134.1 (C), 134.9 (C), 136.3 (C), 138.0
(C), 140.1 (C), 158.7 (C) ppm; MS: m/z (%) = 421 ­(M+, 1),
266 (14), 178 (54), 155 (68), 105 (72), 77 (100).
2‑Benzylidene‑5‑methyl‑5‑phenyl‑3‑tosylthiazolidine (7j,
­C24H213NO2S2) The crude product was purified by column
chromatography ­(SiO2, hexane/EtOAc 5/1, Rf = 0.34) afford-
ing 0.26 g (61%) of 7j. Pale yellow solid; m.p.: 77–79 °C;
IR (KBr): v̄ = 3042, 2977, 1615, 1528, 1311, 1289, 1132,
1053 cm−1; 1H NMR (500.1 MHz, ­CDCl3): δ = 1.61 (3H, s,
Me), 2.39 (3H, s, Me), 3.47–3.63 (2H, m, 2 CH), 5.28 (1H,
s, CH), 7.20–7.48 (10H, m, 10 CH), 7.60 (2H, d, 3J = 7.6 Hz,
2 CH), 7.73 (2H, d, 3J = 7.2 Hz, 2 CH) ppm; 13C NMR
(125.7 MHz, ­CDCl3): δ = 22.0 (Me), 27.4 (Me), 47.1 ­(CH2),
74.8 (C), 88.6 (CH), 125.1 (CH), 126.6 (2 CH), 126.9 (CH),
127.3 (2 CH), 128.2 (2 CH), 129.1 (2 CH), 129.9 (2 CH),
133.1 (2 CH), 134.3 (C), 135.9 (C), 138.2 (C), 146.8 (C),
157.4 (C) ppm; MS: m/z (%) = 421 ­(M+, 1), 406 (21), 330
(41), 177 (60), 155 (71), 77 (100).
4‑Benzyl‑2‑(4‑methylbenzylidene)‑3‑tosylthiazolidine
(7k, ­C25H25NO2S2) The crude product was purified by col-
umn chromatography ­(SiO2, hexane/EtOAc 5/1, Rf = 0.29)
affording 0.40 g (92%) of 7k. Pale yellow solid; m.p.:
121–123 °C; IR (KBr): v̄ = 3028, 2971, 1573, 1562, 1312,
1243, 1072 cm−1; 1H NMR (500.1 MHz, ­CDCl3): δ = 2.19
(3H, s, Me), 2.41 (3H, s, Me), 2.79 (1H, dd, 2J = 11.8 Hz,
3
J = 10.3 Hz, CH), 2.86 (1H, dd, 2J = 11.8 Hz, 3J = 5.4 Hz,
CH), 3.21 (1H, dd, 2J = 11.0 Hz, 3J = 8.7 Hz, CH), 3.32 (1H,
dd, 2J = 11.0 Hz, 3J = 5.4 Hz, CH), 3.47–3.55 (1H, m, CH),
5.32 (1H, s, CH), 7.21–7.56 (11H, m, 11 CH), 7.65 (2H, d,
3
J = 7.3 Hz, 2 CH), 7.74 (2H, d, 3J = 7.52 Hz, 2 CH) ppm;
13
C NMR (125.7 MHz, C ­ DCl3): δ = 22.1 (Me), 24.8 (Me),
37.1 ­(CH2), 40.3 ­(CH2), 69.7 (CH), 88.5 (CH), 124.6 (CH),
125.5 (2 CH), 127.7 (2 CH), 128.2 (2 CH), 129.1 (2 CH),
130.1 (2 CH), 131.5 (2 CH), 134.1 (C), 135.2 (C), 138.1
(C), 139.2 (C), 139.7 (C), 158.2 (C) ppm; MS: m/z (%) = 435
­(M+, 1), 344 (16), 190 (31), 155 (51), 91 (100), 88 (59).
4‑Benzyl‑2‑(4‑methoxybenzylidene)‑3‑tosylthiazolidine
(7l, ­C25H25NO3S2) The crude product was purified by col-
umn chromatography ­(SiO2, hexane/EtOAc 3/1, Rf = 0.44)
affording 0.43 g (96%) of 7l. Pale yellow solid; m.p.:
142–144 °C; IR (KBr): v̄ = 3042, 2989, 1603, 1534, 1264,
1187, 1034 cm−1; 1H NMR (500.1 MHz, ­CDCl3): δ = 2.32
(3H, s, Me), 2.72 (1H, dd, 2J = 11.5 Hz, 3J = 10.0 Hz, CH),
13
222
2.86 (1H, dd, 2J = 11.5 Hz, 3J = 5.8 Hz, CH), 3.11 (1H, dd,
2
J = 11.9 Hz, 3J = 10.1 Hz, CH), 3.24 (1H, dd, 2J = 11.9 Hz,
3
J = 5.9 Hz, CH), 3.62–3.71 (1H, m, CH), 3.78 (3H, s,
MeO), 5.29 (1H, s, CH), 7.09–7.45 (9H, m, 9 CH), 7.61
(2H, d, 3J = 6.9 Hz, 2 CH), 7.72 (2H, d, 3J = 7.52 Hz, 2 CH)
ppm; 13C NMR (125.7 MHz, C ­ DCl3): δ = 23.1 (Me), 37.2
­(CH2), 40.5 (­ CH2), 57.0 (MeO), 69.1 (CH), 88.3 (CH), 114.5
(2 CH), 125.1 (CH), 125.5 (C), 127.7 (2 CH), 128.1 (2 CH),
128.9 (2 CH), 129.8 (2 CH), 131.3 (2 CH), 134.2 (C), 138.1
(C), 139.5 (C), 157.2 (C), 160.2 (C) ppm; MS: m/z (%) = 451
­(M+, 2), 360 (23), 206 (38), 155 (62), 91 (100), 77 (81).
4‑Benzyl‑3‑tosyl‑2‑[3‑(trifluoromethyl)benzylidene]thiazo‑
lidine (7m, ­C25H22F3NO2S2) The crude product was puri-
fied by column chromatography ­(SiO2, hexane/EtOAc 2/1,
Rf = 0.46) affording 0.17 g (34%) of 7m. Pale yellow solid;
m.p.: 91–93 °C; IR (KBr): v̄ = 3043, 2989, 1537, 1521, 1276,
1240, 1082 cm−1; 1H NMR (500.1 MHz, ­CDCl3): δ = 2.34
(3H, s, Me), 2.78 (1H, dd, 2J = 12.3 Hz, 3J = 10.8 Hz, CH),
2.90 (1H, dd, 2J = 12.3 Hz, 3J = 5.9 Hz, CH), 3.13 (1H, dd,
2 17. Yooa WJ, Lia CJ (2008) Adv Synth Catal 350:1503
J = 11.8 Hz, 3J = 8.5 Hz, CH), 3.26 (1H, dd, 2J = 11.8 Hz,
3
J = 5.9 Hz, CH), 3.56–3.64 (1H, m, CH), 5.36 (1H, s, CH),
7.15–7.36 (11H, m, 11 CH), 7.69 (2H, d, 3J = 7.1 Hz, 2 CH)
ppm; 13C NMR (125.7 MHz, C ­ DCl3): δ = 27.1 (Me), 35.9
­(CH2), 39.2 (­ CH2), 67.9 (CH), 86.2 (CH), 122.6 (CH, q,
3
J = 3.8 Hz), 124.5 (CH, q, 3J = 4.9 Hz), 125.8 (CH), 127.0
­(CF3, q, 1J = 270.2 Hz), 127.9 (2 CH), 128.7 (2 CH), 129.1
(2 CH), 130.4 (CH), 131.2 (C, q, 2J = 32.9 Hz), 132.5 (2
CH), 133.6 (CH), 134.0 (C), 135.1 (C), 137.8 (C), 140.0
(C), 158.3 (C) ppm; MS: m/z (%) = 489 ­(M+, 1), 398 (7),
246 (21), 155 (67), 91 (100), 88 (72).
4‑Benz yl‑2‑pentylidene ‑3‑tosylthiazolidine (7n,
­C22H27NO2S2) The crude product was purified by column
chromatography ­(SiO2, hexane/EtOAc 6/1, Rf = 0.21) afford-
ing 0.33 g (83%) of 7n. Pale yellow solid; m.p.: 91–93 °C;
IR (KBr): v̄ = 3018, 2968, 1534, 1282, 1132, 1108 cm−1; 1H
NMR (500.1 MHz, C ­ DCl3): δ = 0.89 (3H, t, 3J = 6.2 Hz, Me),
1.37–1.60 (4H, m, 2 ­CH2), 2.43 (3H, s, Me), 2.67–2.78 (2H,
m, ­CH2), 2.87–2.94 (2H, m, 2 CH), 3.21 (1H, dd, 2J = 12.8 Hz,
3 33. Yavari I, Ghazanfarpour-Darjani M, Solgi Y, Ahmadian S (2011)
J = 5.2 Hz, CH), 3.34 (1H, dd, 2J = 12.8 Hz, 3J = 8.9 Hz, CH),
3.79–3.89 (1H, m, CH), 4.95 (1H, t, 3J = 6.0 Hz, CH), 7.21–
7.37 (7H, m, 7 CH), 7.64 (2H, d, 3J = 7.2 Hz, 2 CH) ppm; 13C
NMR (125.7 MHz, ­CDCl3): δ = 13.7 (Me), 22.6 (Me), 25.1
­(CH2), 28.3 (­ CH2), 35.4 ­(CH2), 37.1 ­(CH2), 39.8 ­(CH2), 68.7
(CH), 89.2 (CH), 126.5 (CH), 126.8 (2 CH), 128.2 (2 CH),
129.5 (2 CH), 130.6 (2 CH), 134.5 (C), 136.9 (C), 140.3 (C),
158.1 (C) ppm; MS: m/z (%) = 401 ­(M+, 1), 310 (14), 156
(67), 155 (52), 91 (100), 77 (67).
Acknowledgements We wish to thank for a grant from University of
Zabol.
13
Z. Keshtegar et al.
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