(: Z)-Tetrahydrothiophene and (Z)-tetrahydrothiopyran synthesis through nucleophilic substitution and intramolecular cycloaddition of alkynyl halides and EtOCS2K

Article abstract of DOI:10.1039/c9ob01370a

This protocol provides a novel, environmentally friendly and simple method for the synthesis of (Z)-tetrahydrothiophene derivatives using the nucleophilic thiyl radical intramolecular cycloaddition cascade process to construct C-S bonds under transition-m

Full text of DOI:10.1039/c9ob01370a

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DOI: 10.1039/C9OB01370A
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(Z)-Tetrahydrothiophenes and (Z)-Tetrahydrothiopyrans Synthesis
through Nucleophilic Substitution and Intramolecular
Cycloaddition of Alkynyl Halide and EtOCS2K
Received 00th January 20xx,
Accepted 00th January 20xx
Xianglin Luo, Xiuwen Chen, Zhiyan Song, Junyi Liang, Chunshu Liao, Zhongzhi Zhu, Lu
Chen, Yibiao Li*
DOI: 10.1039/x0xx00000x
www.rsc.org/
This protocol provides a novel, environmentally friendly and simple disadvantages of low yields, poor selectivity, multistep reaction
method for synthesis of (Z)-tetrahydrothiophene derivatives using sequences and requirements for metal catalysts.
the nucleophilic thiyl radical intramolecular cycloaddition cascade Scheme
1
The major pathways for the synthesis of
process to construct C–S bonds under transition-metal-free. This tetrahydrothiophene derivatives.
transformation process offers a broad substrate scope, good
functional group tolerance, and excellent stereoselectivity (Z/E
ratios up to 99/1). Moreover, the process uses odourless, stable
Previous work:
Ni Cat.
SCOMe
(a)
(b)
and cheap EtOCS2K as the sulfur source.
S
S
Na S 9H2O
Sulfur is increasingly occurring in the structures of modern medicines
because sulfur compounds exhibit various valence states and rich
stereoscopic conformations. Sulfides with the same or similar
skeletons and different valence states may exhibit different
physiological activities. Tetrahydrothiophenes are versatile
structural scaffolds found widely throughout the synthesis of natural
products,1 biological sensors,2 materials chemistry,3 organocatalysts4
and reaction intermediates.5 Over the past decade, the development
of efficient methodologies for the synthesis of tetrahydrothiophene
skeletons has attracted considerable interest in synthetic ch emistry.
Ozaki and co-workers proposed a straightforward approach which
synthesizes cyclic sulfides using the Ni-catalysed electroreduction of
unsaturated thioacetates and thiosulphonates (Scheme 1, a).6 The
tetrahydrothiophene derivatives can also be synthesized through
conversion to the corresponding alkynyl thiouronium salts by
treatment with hydroxide via intramolecular trans addition to the
acetylenic linkage.7 Recently, Ji and co-workers proposed a simple
strategy to construct tetrahydrothiophene derivatives using a
[1+3+1] cycloaddition reaction with cyclopropyl alkyne and
Na2S·9H2O (Scheme 1, b).8 It is worth noting that Scanlan and co-
workers developed a novel intramolecular thiol-yne ionic and radical
mediated cyclisation strategy for the synthesis of thioglycals.9a
Photolysis of acetylenic thiols tends to provide thiacycloalkanes with
different numbers in the ring and has some problem that acetylenic
thiols are unstable and polimerize even at low temperature
conditions.9b However, some of these methods have the
·
2
S
This work:
KS
OEt
Cl
)n
S
( )n
(c)
Metal-free
n = 1, 2
(
Jiang and co-workers use the green reagent to adjust the nature
of free radicals by using the “masked strategy” and achieve selective
sulfoxide and thioetherification.10 Despite the existence of numerous
techniques for the synthesis and derivatization of sulfur-containing
organic skeletons and heterocycles, the development of novel,
odourless and efficient strategy is still very important. Xanthates are
attractive starting materials in chemistry transformations due to
their high reactivity and availability; they are readily prepared from
inexpensive alcohols and carbon disulphide.11 Xanthates and related
derivatives are particularly convenient precursors for a variety of
radicals that can be captured in both inter- and intramolecular
fashions.12 Xanthates can also be used as a sulfur source for the
introduction of sulfur atoms into organic molecules and for
formation of sulfur-containing heterocycles.13 Our group developed
a series of methods for synthesis of heterocyclic compounds, in
14a-c
which thiol was formed as reaction intermediate.
In addition,
xanthate was used for the key mediated synthesis of (E)-alkenes
through semi-hydrogenation of alkynes.14d Recently, we reported an
NH4I-promoted and H2O-controlled intermolecular bis-sulfenylation
and hydroxysulfenylation of alkenes via a radical process.14e Herein,
we developed a transition-metal-free radical mediated cyclisation
strategy for the synthesis of (Z)-tetrahydrothiophene derivatives in
which thiyl radical is produced in situ from xanthates and acts as an
active intermediate.
aSchool of Biotechnology and Health Sciences, Wuyi University, Jiangmen,
Guangdong Province 529020, China, E-mail: leeyib268@126.com
†Electronic Supplementary Information (ESI) available: General Experimental
information, experimental procedure for product synthesis, full characterization
data, 1H and 13C NMR spectra of all products. See DOI: 10.1039/x0xx00000x
Initially, 1-(5-chloropent-1-ynyl) benzene was selected as a
model substrate for the optimization of the reaction conditions
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(Table 1). The screening of various sulfur sources revealed that the Moreover, a number of electrons withdrawing substituents on the
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sources played a very important role in this cyclisation process. aryl rings, including –F, –Cl, –CN, –NO and –CF , could be employed
DOI: 10.1039/C9OB01370A
2
3
Different sulfur sources, including Na2S·9H2O, C6H12CuN2S4, S8, to produce the corresponding products in good yields (3i-3l). Next,
thiourea, C5H14N2S2, C3H6NNaS2·2H2O and EtOCS2K, were tested in when 6-chloro-1-phenylhex-2-yn-1-one was employed as the
this reaction (Table 1, entries 1-8). The results indicated that EtOCS2K substrate, the expected sulfur cyclisation product 3o was obtained in
was the superior sulfur source, with a product yield of 95% (Table 1, 93% yield. It should be noted that (6-chlorohex-1-yn-1-yl)benzene
entry 8). The continued screening of various solvents revealed that bearing four methylene units was compatible with the reaction
DMF was the superior solvent (Table 1, entries 8-12). The reaction protocol (shemee 2,3p). Unfortunately, the reaction of terminal
was most efficient when it was conducted at 80 °C, and higher or alkynes and silyl-substituted alkynes, such as 5-chloropent-1-yne and
lower temperatures resulted in lower yields (Table 1, entry 13). By (5-chloropent-1-yn-1-yl)trimethylsilane, produced
a mixture of
decreasing the amount of EtOCS2K (1.5 equiv and 1.0 equiv), the yield products (Scheme 2, 3q).
was reduced to 71% and 55%, respectively (Table 1, entry 14), and Scheme
2
Synthesis of (Z)-2-benzylidene tetrahydrothiophene
only a trace amount of 3a was detected when the reaction was derivatives.a
carried out in dry DMF (anhydrous conditions) (Table 1, entry 15).
The sulfur cyclisation reaction was not affected under oxygen
S
DMF, H2O
80 oC, 12 h
n=1,2
Cl
+
S
KS
OEt
CH3
atmosphere condition (Table 1, entry 16). Under N2 condition, the
R
R
1
2
3
yield of the sulfur cyclisation reaction is significantly affected (Table
1, entry 17). Therefore, the optimal reaction conditions were 1a (0.5
mmol) and EtOCS2K (1.0 mmol) in DMF (2.0 mL) at 80 °C for 12 h
(Table 1, entry 8).
S
S
S
H3C
3b, 89%
Z/E =83:17
3a
, 95%
Z/E = 91:9
3c
, 76%
Table 1 Optimization of reaction conditionsa
Z/E =90:10
H3C
CH3
S
S
H3C
S
DMF, H2O
80oC, 12 h
Cl
+
KS
OEt
S
3d
, 68%
3e
, 77%
Z/E = 90:10
CH3
3e
1a
2
3a
Z/E =89:11
H3C
H3C
H3CO
H2N
NC
S
Yield b (%)
S
S
Entry
Sulfur source
Solvent
1
2
3
4
5
6
7
8
Na2S·9H2O
C6H12CuN2S4
S8
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMSO
DMAc
CH3CN
H2O
DMF
DMF
DMF
DMF
DMF
11
n.r.
n.r.
trace
trace
n.r.
n.r.
95
8
67
16
< 5
(8, 62, 75)
(71, 55)
trace
93
3f
3g
3h
, 83%
Z/E = 96:4
, 73%
Z/E =88:12
, 83%
Z/E =90:10
F
Cl
S
S
S
thiourea
3k
, 85%
3i
3j
, 86%
Z/E = 90:10
, 89%
Z/E = 93:7
thioacetamide
C5H14N2S2
C3H6NS2Na·2H2O
EtOCS2K
EtOCS2K
EtOCS2K
EtOCS2K
EtOCS2K
EtOCS2K
EtOCS2K
Z/E = 93:7
F3C
Ph
S
S
S
3l
, 87%
Z/E = 90:10
3m
Z/E = 88:12
, 72%
3n
, 64%
Z/E = 79:21
9
O
S
S
S
10
11
12
13c
14d
15e
16f
17g
TMS
3q
3o
, 93%
Z/E = 97:3
3p.
75%
Z/E = 90:10
. < 5%
a Reaction conditions: alkyne 1a (0.5 mmol), EtOCS2K (1.0 mmol) in
DMF (2.0 mL), H2O (5 mmol.) at 80 °C for 12 h; b Isolated yields; C the
Z/E ratio was detected by GC-MS.
EtOCS2K
EtOCS2K
EtOCS2K
72
To continue our investigation of the reaction scope, we explored
various pyridine-based substrates for this process under the
optimized reaction conditions (Scheme 2). Overall, it was found that
most of the substrates could be converted to the corresponding (Z)-
tetrahydrothiophene products in good to excellent yields with
excellent stereoselectivity. Furthermore, when the pyridine ring was
substituted at the ortho-, meta-, and para-positions, the yields were
not affected (Scheme 2, 3r-3t). These results show that the sulfur
cyclisation reaction is not affected by electron-withdrawing or -
donating substituents on the pyridine ring and that the desired
product can be successfully obtained. In addition, the bromine-
substitution on the ortho- or meta-pyridine was well tolerated,
resulting in good yields of 84% and 80%, respectively (Scheme 2, 3w-
3x). It is important to note that the heterocyclic compounds,
including quinoline (3z), thiophene (3aa) and pyrazole (3ab-3ac)
derivatives, produced good yields. Finally, the six-membered cyclic
tetrahydro-2H-thiopyran compounds 3ac and 3ad were successfully
produced (88% and 87% yield, respectively), by 6-exo-dig cyclization
in our sulfur cyclisation protocol.
a Reaction conditions: alkyne 1 (0.5 mmol), sulfur source (1.0 mmol)
in solvent (2.0 mL) and H2O (5 mmol, normal distilled water) at 80 °C
b
c
for 12 h; Isolated yields; Yields were with respect to the
temperatures at 40 °C, 60 °C and 100 °C, respectively; d EtOCS2K (0.75
e
f
mmol, 0.5 mmol) was used; Anhydrous DMF (2 mL); under O2
(1atm) atmosphere;
g
under N2 atmosphere. C6H12CuN2S4 =
Bis(dimethylcarbamodithioato-S,S') copper, C3H6NS2Na·2H2O = N,N-
Dimethyldithiocarbamate sodium salt.
With the optimized reaction conditions in hand, we turned our
attention to the sulfur cyclisation reaction by varying alkynyl halide
components (Scheme 2). Both electron-donating and withdrawing
substituents on the benzene rings were compatible under the
standard conditions and enabled conversion to the corresponding
(Z)-tetrahydrothiophene products. Electron-donating groups, such
as -Me, -tBu, -OMe, also successfully enabled sulfur cyclisation
(Scheme 2, 3a–3g, 68%–95% yield). The structure of 3e was further
investigated using single-crystal XRD analysis (CCDC no. 1881760).
2 | J. Name., 2015, 00, 1-3
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S
Scheme 3 Substrate scope of alkynyl halides.a
EtOCS2K
5,
V
6
ie
4
w
%
A
yi
r
e
t
l
i
d
cle Online
(eq 1)
S
Cl
DMF, H2O, rt, 12h
OEt
DOI: 10.1039/C9OB01370A
1a
S
S
DMF, H2O
80 oC, 12 h
n=1,2
Standard conditions
S
Cl
N
+
3a
(eq 2)
(eq 3)
, 81% yield
, trace yield
N
S
KS
O
2
S
(
)
(
)
n
n
OEt
R
5
R
3
1
n=1, 2
S
Standard conditions
3a
N
Cl
S
S
S
TEMPO (2.0 equiv.)
or BHT (2.0 equiv.)
N
N
1a
1a
1a
N
(100%)
S
D
3r
3s
3t
, 78%
Z:E >99:1
, 82%
Z:E = 95:5
, 89%
Z:E = 92:8
EtOCS2K, dry DMF
D2O (10 equiv.)
(eq 4)
3a-d
, 92% yield
Cl
Cl
Br
S
S
H3CO
S
N
S
Standard conditions
AIBN (0.1 equiv.)
3a
, 91% yield (eq 5)
N
OCH3
3w
, 84%
Z:E = 96:4
3u
3v
, 83%
, 94%
Z:E = 96:4
Z:E = 96:4
The postulated reaction mechanism based on the literature and
our control experimental results are depicted in Scheme 6.8, 16 The
sulfur cyclisation reaction is initiated by the nucleophilic substitution
of EtOCS2K to (5-chloropent-1-yn-1-yl)benzene, yielding xanthate A,
and is followed by the slow hydrolysis of the xanthate A to yield thiol
B with the aid of H2O and EtOCS2K. Next, the small quantities of thiyl
radical C were generated by oxidation under oxygen atmosphere.
This rapidly cyclizes thiyl radical C onto the Csp-Csp triple bonds to
produce radical D, which abstracts hydrogen (or deuterium) from the
thiol to generate the observed product and regenerates thiyl radical
C to propagate the chain (Scheme 6, Path A). In addition, an ionic
chain reaction cannot be excluded, whereby the nucleophilic
addition of thiolate E (formed by partial deprotonation of the thiol
by the xanthate salt) to the Csp-Csp triple bonds yields anion F, which
is then protonated by water or thiol B (Scheme 6, Path B).
Br
S
Cl
S
N
S
N
N
S
3y
, 93%
3z
, 86%
Z/E > 99:1
3x
, 80%
Z:E = 96:4
Z:E = 91:9
S
S
S
S
N
N
N
N
N
CH3
CH3
3aa
, 88%
Z:E = 97:3
3ad
, 87%
Z:E > 99:1
3ac
, 88%
Z:E > 99:1
3ab
, 90%
Z:E > 99:1
a Reaction conditions: alkyne 1a (0.5 mmol), EtOCS2K (1.0 mmol) in
DMF (2.0 mL) and H2O (5 mmol) at 80 °C for 12 h; b Isolated yields; C
the Z/E ratio was detected by GC-MS.
To further develop the methodology, the oxidation of
tetrahydrothiophenes was performed to produce sulfone
derivatives. Several selected compounds (3a, 3m and 3x) were
treated with m-CPBA in CH2Cl2 at room temperature for 48 h,
producing sulfone derivatives in good yields (Scheme 4).15 In
addition, 2-((dihydrothiophen-2(3H)-ylidene)methyl)thiophene (3x)
contains two sulfur atoms, whereas oxidation occurs selectively on
the tetrahydrothiophene ring (4c).
5-exo-dig
cyclization
S
S
abstract H
Ph
C
C
thiyl radical
thiol B
H
S
D
S
+
Path A
O2
S
EtO
Ph
SK
H2O
Ph
Ph
Ph
S
OEt
A
B
SH
Cl
EtOCS2K
EtOCS2H
Path B
S
O
5-exo-dig
cyclization
O
4a
, R = Ph, 82%
4b, R = 4-Ph-C6H4, 88%
4c
S
S
H2O
m-CPBA (1.1 mmol)
CH2Cl2
S
R
R
B
or thiol
H
SK
, R = 2-thienyl, 86%
E
F
3
4
Scheme 6 Proposed reaction pathway.
Scheme 4 Oxidation of sulfides to sulphones with m-CPBA.
In summary, a simple and efficient method was developed to
produce tetrahydrothiophene derivatives using cycloaddition
reactions with EtOCS2K as a thiol precursor under mild reaction
conditions. Excellent regioselectivity, excellent functional group
compatibility and good to excellent yields were achieved. This
intramolecular sulfur cyclisation reaction provides a simple and
robust strategy to produce (Z)-tetrahydrothiophenes and (Z)-
tetrahydrothiopyrans for application in pharmaceutical chemistry
and organic synthesis.
To gain mechanistic insights into the reaction, several control
experiments were conducted (Scheme 5). First, the probable
intermediate O-ethyl S-(5-phenylpent-4-yn-1-yl) carbonodithioate 5
was prepared under mild conditions in moderate yields (Scheme 5,
eq 1). Next, the intermediate 5 was successfully converted to the
desired product under standard conditions (Scheme 5, eq 2). When
the 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) or butylated
hydroxytoluene (BHT) were added as radical scavengers, the sulfur
cyclisation reaction was cancelled (Scheme 5, eq 3). These results
suggest that the present reaction presumably was triggered through
a radical pathway. In addition, the reaction of (5-chloropent-1-yn-1-
yl)benzene under anhydrous DMF (2 mL) and D2O (10 equiv.)
conditions produced the deuterium products 3a-d in 92% yields,
suggesting that water acted as a proton donor in this transformation
(Scheme 5, eq 4). The sulfur cyclisation reaction was not affected
under radical initiator AIBN condition (Scheme 5, eq 5).
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
We thank the Foundation of the Department of Education of
Guangdong Province (2017KZDXM085 and 2018KZDXM070),
Science and Technology Foundation of Jiangmen City (2017012)
Scheme 5 Control experiments.
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