Sulfuryl Fluoride Promoted Thiocyanation of Alcohols: A Practical Method for Preparing Thiocyanates

Article abstract of DOI:10.1055/s-0040-1707151

A novel SO ₂F ₂-promoted thiocyanation method for the one-step synthesis of thiocyanates through C-O bond cleavage of readily available alcohols with ammonium thiocyanate as the thiocyanating agent was developed. The method avoids the use of additional catalyst, and a variety of (hetero)arene, alkene and aliphatic alcohols reacted with high efficiency in ethyl acetate under mild conditions to afford the corresponding thiocyanates in excellent to quantitative yields with broad functional-group compatibility.

Full text of DOI:10.1055/s-0040-1707151

SYNLETT
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2
1
4
1
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©
Georg Thieme Verlag Stuttgart · New York
2020, 31, A–E
letter
A
en
Synlett
G. Zhang et al.
Letter
Sulfuryl Fluoride Promoted Thiocyanation of Alcohols: A Practical
Method for Preparing Thiocyanates
Guofu Zhang
SO2F2 (balloon)
Lidi Xuan
NH4SCN, Na2CO3
R
OH
R
SCN
Yiyong Zhao
Chengrong Ding*
EtOAc, r.t., 5 h
30 examples
0
0
0
0-0
0
0
1-6
0
0
0-
3
9
6
5
R = (hetero)aryl, alkenyl
Highly efficient protocol
Good functional-group compatibility
Mild conditions
up to 98% yield
College of Chemical Engineering, Zhejiang University of
Technology, Hangzhou 310014, P. R. of China
dingcr@zjut.edu.cn
Up to gram scale
Received: 29.01.2020
O
Accepted after revision: 28.05.2020
Published online: 16.06.2020
DOI: 10.1055/s-0040-1707151; Art ID: st-2020-l0060-l
O
Br
SCN
N
H
OH
SCN
N
Ph
HO
O
psammaplin B
4-phenoxyphenoxyethyl thiocyanate
OH
Abstract A novel SO F -promoted thiocyanation method for the one-
2
2
step synthesis of thiocyanates through C–O bond cleavage of readily
available alcohols with ammonium thiocyanate as the thiocyanating
agent was developed. The method avoids the use of additional catalyst,
and a variety of (hetero)arene, alkene and aliphatic alcohols reacted
with high efficiency in ethyl acetate under mild conditions to afford the
corresponding thiocyanates in excellent to quantitative yields with
broad functional-group compatibility.
NCS
SCN
thiocyanatin A
Figure 1 Representative bioactive alkyl thiocyanates
ed methods for the preparation of alkyl thiocyanates is the
nucleophilic substitution of alkyl halides or pseudohalides
with thiocyanate salts (Scheme 1a). However, this strategy
Key words sulfuryl fluoride catalysis, alcohols, thiocyanation, ammo-
nium thiocyanate, thiocyanates
5
has certain limitations because of the need for prior instal-
lation at a predetermined position of a halogen atom that is
not an essential part of the target molecule. In recent years,
the functionalization of thiols has become a highly attrac-
tive strategy for assembling alkyl thiocyanates. There is no
doubt that direct thiocyanation of thiols is a more efficient
and attractive alternative to the use of alkyl thiocyanates
because of its high economy of steps and atoms (Scheme
Organic thiocyanate compounds are versatile interme-
diates in organic synthesis, and are widely used in synthe-
ses of pharmaceuticals, dyes, natural products, and agro-
chemicals; they are also used as biologically active mole-
cules. The favorable physiochemical profile and chemical
stability of organic thiocyanates combine to propel the
thiocyanate group to the forefront among the functional
groups employed in the design of modern bioactive mole-
cules. The resulting molecules, which are used in many ap-
plications, include the histone deacetylase inhibitor psam-
6
1b). However, most of the above-mentioned procedures
suffer from such drawbacks as a need for photocatalysts or
ligands or their high cost. In 2009 and 2014, Azadi and
Asgharzadeh reported that cross-coupling of alcohols with
1
maplin B, the Trypanosoma cruzi growth inhibitor (4-phe-
2
noxyphenoxy)ethyl thiocyanate, and the nematocidal
NH SCN to give thiocyanates, providing a more convenient
4
3
agent thiocyanatin A (Figure 1). Furthermore, given the
protocol for the synthesis of these compounds (Scheme
7
wide range of functions that thiocyanates perform in syn-
thetic chemistry, further conversions of such thiocyanates
1c). Regrettably, however, this reaction requires an addi-
tional trivalent phosphorus reagent (Ph PCl) and relatively
2
4
are essential to increasing their utility. As such, efficient
harsh reaction conditions.
8
methods for the construction of alkyl thiocyanates, espe-
cially from readily available starting materials, are of great
significance in organic synthesis.
Because of the versatile applications of thiocyanates,
many routes for their synthesis have been reported in the
literature in recent years. One of the most frequently adopt-
Sulfuryl fluoride (SO F ) is an inexpensive and stable
2
2
reagent that has attracted significant attention in recent
years due to its use in sulfonyl(VI) fluoride ion-exchange
9
(SuFEx) systems. Since 2014, SO F has been widely used in
2
2
other chemical transformations in addition to its applica-
tion in SuFEx-based click reactions. Qin and co-workers re-
©
2020. Thieme. All rights reserved. Synlett 2020, 31, A–E
Georg Thieme Verlag KG, Rüdigerstraße 14, 70469 Stuttgart, Germany

B
Synlett
G. Zhang et al.
Letter
a) The direct thiocyanation of halohydrocarbon by using "SCN" sources
RSCN
Na CO assisted the reaction more efficiently to generate
2
3
the desired product 2b in yields of 70 and 86%, respectively
entries 1 and 5). The solvents 1,4-dioxane, dimethyl sulf-
RX
+ MSCN
(
R = alkyl, aryl
X = Cl, Br
oxide, dichloromethane, and ethyl acetate were also
b) The direct thiocyanation of thiol by using "CN" sources
screened (entries 6–9). Compared with CH CN, 1,4-dioxane
3
and EtOAc were more effective for this transformation and
promoted this reaction to provide product 2b in yields of 91
and 92%, respectively (entries 6 and 9). Subsequently, in-
creasing the loading of Na CO to 4.0 equivalents gave 2b in
"
CN" sources
RSH
RSCN
"
CN" sources: TMSCN
1-cyanoimidazole
cyanobenziodoxol(on)e hypervalent iodine reagents
2
3
an excellent yield of 95% (entry 10). Note, however, that in-
creasing the loading of Na CO to 5.0 equivalents caused an
obvious decrease in the yield of 2b to 84% (entry 11). Fur-
c) The direct thiocyanation of benzyl alcohol by using "SCN" sources
ClPPh2
2
3
R
OH
+
NH4SCN
R
SCN
reflux
thermore, on decreasing the loading of NH SCN to 1.0
4
d) This work:
OH
equivalents, product 2b was obtained in almost quantita-
tive (97%) yield (entry 12). Increasing the amount of
SO2F2, base
r.t.
R
+
NH4SCN
R
SCN
NH SCN did not significantly improve the yield of this
4
Scheme 1 Strategies for the synthesis of thiocyanates
transformation, possibly because of the higher reactivity of
thiocyanate (entries 10 and 12–14). Moreover, reducing the
concentration of the substrate resulted in an inferior 84%
isolated yield of 2b (entry 15). Therefore, the optimal condi-
tions for the reaction of alcohols with thiocyanates involve
the use of Na CO (4.0 equiv), and NH SCN (1.0 equiv) in
ported applications of SO F in syntheses of a range of com-
2
2
10a–e
10f–h
pounds, including heterocycles,
nitriles,
diaryl-
1
0i
arylcarboxylic acids,10j alkynes,10k and
Our group recently reported a mild and practi-
methanes,
amides.
2
3
4
1
0l–m
EtOAc (2.0 mL) with stirring at room temperature under an
SO F atmosphere (SO F balloon) for five hours, and these
cal method for efficiently converting aldehydes or aldoxim-
es into the corresponding nitriles that is mediated by SO F
2
2
2 2
2
2
and a base in an economical and green manner.11 Soon af-
terwards, we also reported the use of SO F and a base as a
Table 1 Optimization of the Reaction Conditionsa
2
2
simple catalyst system for effectively promoting Beckmann
rearrangement of ketoximes into amides or lactams12 and a
cascade process for directly converting nitriles into cyana-
OH
SO2F2 (balloon)
base, solvent, r.t.
SCN
+
NH4SCN
1
b
2b
13
mides through a SO F -activated Tiemann rearrangement.
2
2
Inspired by our preliminary research results14 and the
unique properties of SO F , we surmised that SO F might
Entry
Base (equiv)
Solvent
Isolated yield (%)
2
2
2 2
1
2
Et
3
N (3.0)
CH
CH
CH
3
3
3
CN
CN
CN
70
38
58
77
86
91
67
21
92
95
84
97
94
95
84
similarly be able to react with alcohols to form intermedi-
ate sulfonyl esters that should serve as excellent leaving
groups. Here, we report a highly efficient, mild, and widely
applicable SO F -promoted thiocyanation of alcohols with
DBU (3.0)
3
t-BuOK (3.0)
2
2
4
K CO (3.0)
2
3
CH CN
3
ammonium thiocyanate (NH SCN) at room temperature
4
5
Na CO (3.0)
CH CN
2
2
2
2
2
3
3
3
3
3
3
(Scheme 1d).
6
Na
Na
Na
Na
CO
CO
CO
CO
(3.0)
(3.0)
(3.0)
(3.0)
1,4-dioxane
We chose 4-methylbenzyl alcohol (1b) as a model sub-
7
DMSO
strate to test the feasibility of our proposed cross-coupling
of alcohols with thiocyanates (Table 1). To our delight, the
desired product, 4-methylbenzyl thiocyanate (2b), was iso-
lated in 70% yield under an SO F atmosphere at room tem-
8
2 2
CH Cl
9
EtOAc
EtOAc
EtOAc
EtOAc
EtOAc
EtOAc
EtOAc
2
2
10
11
2 3
Na CO (4.0)
perature when 3.0 equivalents of triethylamine (Et N) were
3
Na CO (5.0 )
2
2
2
2
2
3
3
3
3
3
employed with CH CN (Table 1, entry 1). Encouraged by this
3
2b
1
1
1
Na
Na
Na
Na
CO
CO
CO
CO
(4.0)
(4.0)
(4.0)
(4.0)
initial result, we performed a further screening of the reac-
tion conditions with respect to the base and solvent (see
the Supporting Information for a more detailed account of
the optimization process). The examination indicated that
the performance of inorganic bases was superior to that of
organic bases (Table 1, entries 1–5). Interestingly, we found
that the yields of 2b decreased markedly when the organic
and inorganic strong bases DBU and t-BuOK, respectively,
3c
4d
15e
a
Reaction conditions:1b (1.0 mmol), NH
4
SCN (4.0 equiv), base, solvent
(
2.0 mL, 0.5 M), SO balloon, r.t., 5.0 h.
2 2
F
b
c
NH
NH
NH
4
SCN (1.0 equiv).
SCN (2.0 equiv).
4
SCN (3.0 equiv).
4
d
e
EtOAc (5.0 mL, 0.25 M).
were used (entries 2 and 3), whereas the use of Et N and
3
©
2020. Thieme. All rights reserved. Synlett 2020, 31, A–E

C
Synlett
G. Zhang et al.
Letter
were chosen as the standard conditions for examinations of
the functional-group tolerance and substrate scope of the
reaction.
several polyfunctionalized benzylic alcohols and naphthyl-
methanols were also successfully converted into the corre-
sponding thiocyanates 2t–v, 2w, and 2x in moderate to ex-
cellent yields. Two heteroarylmethanols were also assessed:
excitingly, the novel system showed promising activity for
the thiocyanation of pyridin-2-ylmethanol and 2-thienyl-
methanol, giving the corresponding products 2y and 2z in
yields of 98 and 63%, respectively. Moreover, cinnamyl and
aliphatic alcohols underwent thiocyanation to give the cor-
responding thiocyanates 2aa–ac, 2af, and 2ag in yields of
77, 83, 61, 46 and 52%, respectively. Notably, secondary
benzylic alcohols also underwent thiocyanation to give the
corresponding thiocyanates 2ad and 2ae in isolated yields
of 89 and 58%, respectively.
Having established the optimal conditions, we turned
our attention to examining the substrate scope of this
method (Scheme 2). Various substituted alcohols were suc-
cessfully thiocyanated to give the corresponding alkyl thio-
cyanates. Gratifyingly, a broad range of para-substituted
benzylic alcohols reacted smoothly to afford the corre-
sponding thiocyanates in good to excellent yields with
15
broad functional-group tolerance. Benzylic alcohols bear-
ing electron-donating (R = Me, OMe, i-Pr, Ph) substituents
on the aromatic ring reacted smoothly to give the corre-
sponding alkyl thiocyanates 2b–d and 2k in good to excel-
lent yields. Moreover, substrates bearing an electron-with-
drawing group such as F, Cl, Br, NO , CN, or CF on the aro-
To explore the synthetic utility of this SO F -promoted
2
2
cross-coupling in the presence of Na CO , a gram-scale
2
3
2
3
matic ring similarly afforded the products 2e–j in yields of
5–98%. Of particular note was the effective reaction of ste-
preparation of methyl 4-(thiocyanatomethyl)benzoate (2l),
a synthetic precursor for the assembly of trifluoromethyl
sulfides,4e was performed (Scheme 3). On extending the re-
action time to nine hours under otherwise standard condi-
tions, the reaction of methyl 4-(hydroxymethyl)benzoate
(1l) proceeded smoothly, delivering the desired product 2l
8
rically hindered m- and o-substituted benzylic alcohols,
which provided the products 2n–s in excellent yields. In the
presence of triethylamine as base, 4-(hydroxymethyl)phe-
16
nol gave the fluoridosulfate 2m in 78% yield. Furthermore,
SO2F2 (balloon)
Na2CO3 (4.0 equiv)
R
OH + NH4SCN
R
SCN
EtOAc, r.t., 5 h
1
2
SCN
R
SCN
SCN
SCN
R
2
R
FO2SO
a, R = H, 88%
2
2
2
n, R = Me, 80%
o, R = Cl, 83%
p, R = NO2, 97%
2q, R = Me, 87%
2r, R = Cl, 89%
2s, R = NO2, 83%
2m, 78%a
2
2
2
2
2
2
2
2
2
2
2
b, R = Me, 97%
c, R = OMe, 87%
d, R = i-Pr, 88%
e, R = F, 85%
f, R = Cl, 95%
g, R = Br, 98%
h, R = NO2, 92%
i, R = CN, 93%
j, R = CF3, 93%
k, R = Ph, 95%
l, R = CO2Me, 98%
MeO
MeO
SCN
SCN
SCN
Cl
Cl
2v, 97%
2t, 87%
2u, 86%
S
SCN
SCN
SCN
SCN
SCN
N
2w, 94%
2x, 88%
2y, 98%
2z, 63%
SCN
SCN
SCN
2aa, 77%
2ab, 83%
2ac, 61%
2ad, 89%
SCN
SCN
SCN
2ae, 58%
2af, 46%
2ag, 52%
Scheme 2 Substrate scope for the thiocyanation of alcohols. Reagents and conditions: 1 (1.0 mmol), NH SCN (1.0 mmol, 1.0 equiv), Na CO (4.0 mmol,
4
2
3
a
4
.0 equiv), EtOAc (2.0 mL, 0.5 M), stirring, r.t., SO F balloon. Isolated yields based on 1 are reported. Et N (4 mmol).
2
2
3
©
2020. Thieme. All rights reserved. Synlett 2020, 31, A–E

D
Synlett
G. Zhang et al.
Letter
in 96% isolated yield, confirming that this method could
serve as a valuable and convenient tool for practical appli-
cations in the laboratory.
Y.-q.; Limburg, D. C.; Wilkinson, D. E.; Hamilton, G. S. Org. Lett.
2000, 2, 795. (d) Guo, W.; Tan, W.; Zhao, M.; Zheng, L.; Tao, K.;
Chen, D.; Fan, X. J. Org. Chem. 2018, 83, 6580.
(
7) (a) Mokhtari, B.; Azhdari, A.; Azadi, R. J. Sulfur Chem. 2009, 30,
5
85. (b) Aghapour, G.; Asgharzadeh, A. Phosphorus, Sulfur
SO2F2 (balloon)
Na2CO3 (4.0 equiv)
OH
SCN
Silicon Relat. Elem. 2014, 189, 796.
MeO
+
NH4SCN
MeO
EtOAc, r.t.
(8) (a) Silbaek Andersen, M. P.; Blake, D. R.; Rowland, F.; Hurley, M.
D.; Wallington, T. J. Environ. Sci. Technol. 2009, 43, 1067.
(b) SO2F2 is commercially available from chemical vendors
worldwide: see for example: http://synquestlabs.com/prod-
uct/id/51619.html (accessed June 3, 2020).
9
h
O
O
1
l, 3.32 g, 20 mmol
2l, 3.19 g, 96% isolated yield
Scheme 3 Gram-scale synthesis of methyl 4-(thiocyanatomethyl)ben-
zoate
(
9) For selected SuFEx chemistry, for see: (a) Dong, J. J.; Krasnova,
L.; Finn, M. G.; Sharpless, K. B. Angew. Chem. Int. Ed. 2014, 53,
In conclusion, an efficient, general, atom-economical
method has been developed for the synthesis of thiocya-
nates from alcohols, catalyzed by readily available and inex-
pensive SO F . A wide range of alcohols underwent this
transformation, producing the corresponding alkyl thiocya-
nates in modest to high yields with excellent functional-
group compatibility and high efficiency. In addition, the re-
action can be readily conducted on a gram scale in excellent
yield.
9430. (b) Chen, W.; Dong, J.; Plate, L.; Mortenson, D. E.; Brighty,
G. J.; Li, S.; Liu, Y.; Galmozzi, A.; Lee, P. S.; Hulce, J. J.; Cravatt, B.
F.; Saez, E.; Powers, E. T.; Wilson, I. A.; Sharpless, K. B.; Kelly, J.
W. J. Am. Chem. Soc. 2016, 138, 7353. (c) Gao, B.; Zhang, L.;
Zheng, Q.; Zhou, F.; Klivansky, L. M.; Lu, J.; Liu, Y.; Dong, J.; Wu,
P.; Sharpless, K. B. Nat. Chem. 2017, 9, 1083. (d) Liu, Z.; Li, J.; Li,
S. H.; Li, G.; Sharpless, K. B.; Wu, P. J. Am. Chem. Soc. 2018, 140,
2
2
2919. (e) Wang, H.; Zhou, F.; Ren, G.; Zheng, Q.; Chen, H.; Gao,
B.; Klivansky, L.; Liu, Y.; Wu, B.; Xu, Q.; Lu, J.; Sharpless, K. B.;
Wu, P. Angew. Chem. Int. Ed. 2017, 56, 11203. (f) Marra, A.;
Dong, J.; Ma, T.; Giuntini, S.; Crescenzo, E.; Cerofolini, L.;
Martinucci, M.; Luchinat, C.; Fragai, M.; Nativi, C.; Dondoni, A.
Chem. Eur. J. 2018, 24, 18981. (g) Guo, T.; Meng, G.; Zhan, X.;
Yang, Q.; Ma, T.; Xu, L.; Sharpless, K. B.; Dong, J. Angew. Chem.
Int. Ed. 2018, 57, 2605. (h) Smedley, C. J.; Zheng, Q.; Gao, B.; Li, S.
H.; Molino, A.; Duivenvoorden, H. M.; Parker, B. S.; Wilson, D. J.
D.; Sharpless, K. B.; Moses, J. E. Angew. Chem. Int. Ed. 2019, 58,
Funding Information
We acknowledge financial support from the National Natural Science
Foundation of China (20702051) and the Natural Science Foundation
of Zhejiang Province (LY13B020017).
N
atural S
c
i
e
n
c
e
F
o
u
n
d
ati
o
n
of
Z
h
e
j
i
a
n
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Pro
v
i
n
c
e
(L
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1
3
B
0
2
0
0
1
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of
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i
n
a
(2
0
7
0
2
0
5
1)
4552.
(
10) (a) Li, C.; Qin, H.-L. Org. Lett. 2019, 21, 4495. (b) Lekkala, R.;
Lekkala, R.; Moku, B.; Rakesh, K.-P.; Qin, H.-L. Beilstein J. Org.
Chem. 2019, 15, 976. (c) Zhang, X.; Rakesh, K.-P.; Qin, H.-L.
Chem. Commun. 2019, 55, 2845. (d) Chen, X.; Zha, G.-F.; Fang,
W.-Y.; Rakesh, K.-P.; Qin, H.-L. Chem. Commun. 2018, 54, 9011.
Supporting Information
Supporting information for this article is available online at
https://doi.org/10.1055/s-0040-1707151.
S
u
p
p
orti
n
g Inform ati
o
n
S
u
p
p
orit
n
g Inform ati
o
n
(e) Chen, X.; Zha, G.-F.; Bare, G.; Leng, J.; Wang, S.-M.; Qin, H.-L.
Adv. Synth. Catal. 2017, 359, 3254. (f) Fang, W.-Y.; Qin, H.-L.
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3
2
(
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4
4
mmol, 1.0 equiv), Na CO (4.0 mmol, 4.0 equiv), and EtOAc (2.0
2
3
mL, 0.5 M) were added sequentially to an oven-dried 30 mL
reaction tube equipped with a stirrer bar. The tube was sealed
©
2020. Thieme. All rights reserved. Synlett 2020, 31, A–E

E
Synlett
G. Zhang et al.
Letter
with a plastic stopper and SO2F2 gas was introduced into the
stirred mixture by slow bubbling from an SO F -filled balloon at
(16) 4-(Thiocyanatomethyl)phenyl Fluoridosulfate (2m)
4-(Hydroxymethyl)phenol (1m; 1.0 mmol, 1.0 equiv), NH SCN
2
2
4
r.t. for 5 h. The mixture was then diluted with H O and
(1.0 mmol, 1.0 equiv), Et N (4.0 mmol, 4.0 equiv), and EtOAc
2
3
extracted with EtOAc (3 × 25 mL). The combined organic layers
were washed with brine, dried (Na SO ), and concentrated to
dryness. The residue was purified by chromatography (silica
(2.0 mL, 0.5 M) were added sequentially to an oven-dried 30 mL
reaction tube equipped with a stirrer bar. The tube was sealed
with a plastic stopper and SO2F2 gas was introduced into the
stirred mixture by slow bubbling from an SO F -filled balloon at
2
4
gel, EtOAc–PE) to give a yellow oil; yield: 158 mg (97%).
2
2
1
H NMR (500 MHz, CDCl ):  = 7.31–7.21 (m, 2 H), 7.18 (d,
r.t. for 5 h. Workup as described above gave a colorless oil; yield:
3
J = 7.9 Hz, 2 H), 4.13 (s, 2 H), 2.35 (s, 3 H). 1 C NMR (125 MHz,
3
193 mg (78%).
1
CDCl ):  = 138.9, 131.3, 129.8, 128.9, 112.1, 38.3, 21.2. HRMS
H NMR (500 MHz, CDCl ):  = 7.50 (d, J = 8.7 Hz, 2 H), 7.38 (d,
3
3
+
13
(
EI): m/z [M ] calcd for C H NS: 163.0456; found: 163.0458.
J = 8.5 Hz, 2 H), 4.16 (s, 2 H). C NMR (125 MHz, CDCl ):

9
9
3
= 150.1, 135.5, 131.1, 121.8, 111.2, 37.1. HRMS (EI): m/z [M+]
calcd for C H FNO S : 246.9773; found: 246.9796.
8
6
3 2
©
2020. Thieme. All rights reserved. Synlett 2020, 31, A–E