Synthesis of Monofluoromethyl Selenoethers of Aryl and Alkyl from Organoselenocyanate via One-Pot Reaction

Article abstract of DOI:10.1002/adsc.201900480

The first practical and feasible approach for the monofluoromethylselenolation of aryl and alkyl halides via one-pot multistep synthesis using KSeCN and ICFH₂ is described. Good yields and broad functional group compatibility were obtained. The successful preparation of monofluoromethylselenolated drug-like compounds good practicability of this method. This protocol offered a number of new monofluoromethyl selenoethers, which would accelerate the use of such compounds in the areas of life science. (Figure presented.).

Full text of DOI:10.1002/adsc.201900480

Title: Synthesis of Monofluoromethyl selenoethers of Aryl and Alkyl
from Organoselenocyanate via one-pot reaction
Authors: Yuan Cao, Lvqi Jiang, and Wen-bin Yi
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201900480
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10.1002/adsc.201900480
Advanced Synthesis & Catalysis
UPDATE
DOI: 10.1002/adsc.201900480
Synthesis of Monofluoromethyl selenoethers of Aryl and Alkyl
from Organoselenocyanate via one-pot reaction
Yuan Caoa, Lvqi Jianga, Wenbin Yia*
a
School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, P. R. China.
Email : yiwenbin@njust.edu.cn
*
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
(Figure 1), and after testing the topical anti-
monofluoromethylselenolation of aryl and alkyl halides via inflammatory activity of these compounds, Bain and
Abstract. The first practical and feasible approach for the
one-pot multistep synthesis using KSeCN and ICFH2 is
described. Good yields and broad functional group
compatibility were obtained. The successful preparation of
monofluoromethylselenolated drug-like compounds good
practicability of this method. This protocol offered a
number of new monofluoromethyl selenoethers, which
would accelerate the use of such compounds in the areas of
life science.
his co-workers found that fluoro methyl carbothioates
(SCH2F-containing compounds) were in general more
active than other carbothioates.[10] In the same
chalcogen family, the selenium atom possesses
properties similar to those of sulfur. The
fluoroalkylseleno groups containing a larger selenium
atom,[11] can provide a stable, bulkier and more
lipophilic functional group than a fluoroalkylthio
group.[9a,12]
Keywords: First monofluoromethylselenolation; Aryl;
Alkyl; Late-stage monofluoromethylselenolation
In the last few decades, fluorinated compounds have
experienced an incessantly growing interest in various
fields of application from materials to life sciences.[1]
It has been well-demonstrated that new properties such
as high electron-withdrawing characteristics and high
lipophilicity can be expected from the association of
fluorinated moieties with a heteroatom.[2] Therefore,
the introduction of such groups became an important
topic in medicinal, pharmaceutical as well as
agrochemistry.
Figure 1. Halomethyl Androstane-17β-carbothioates.
In recent years, some articles reported the method
of introducing fluoroalkylseleno groups into small
molecules, including trifluoromethylseleno (-
SeCF3)[13] and difluoromethylseleno (-SeCF2H)[14]
Recently, fluoroalkyloxy groups including
trifluoromethoxy (-OCF3),[3] difluoromethoxy (-
OCF2H)[4] groups and fluoroalkylthio groups,
groups.
Among
these
methods,
using
(-SCF3),[5]
organoselenocyanate as a selenium source have been
reported (Figure 2).[13b,13i,14] In 2016, Rueping
reported a straightforward method for the introduction
of the trifluoromethylseleno group into aromatic and
heteroaromatic compounds by using readily available
aryldiazonium tetrafluo roborates, potassium
selenocyanate, and Ruppert-Prakash reagent (Figure 2,
A).[13b] In 2017, Vanelle used 2-phenyl-3-
selenocyanatoimidazo[1,2-a]pyridine to reacted with
Ruppert-Prakash reagent to get 2-phenyl-3-
((trifluoromethyl)selanyl)imidazo[1,2-a]pyridine
(Figure 2, B).[13i] In 2018, Zhang reported an efficient
and transition metal-free method for the synthesis of
aryl or alkyl difluoromethyl selenides (RSeCF2H)
from the corresponding selenocyanates (RSeCN) and
including
trifluoromethylthio
difluoromethylthio
(-SCF2H),[6]
monofluoromethylthio (-SCFH2)[7] groups, have
attracted considerable interests in both pharmaceutical
industry and academia, mainly because of their high
yet tunable lipophilicity that may dramatically
improve the pharmacokinetic properties of a drug
molecule.[7-8] Accordingly, much attention is being
devoted to the development of effective methods and
reagents for their synthesis currently. Although these
emerging groups have been well studied in the past
few years, the combination with the next chalcogen
which named selenium has been less studied despite
the pertinent properties.[9]
It was reported that Halomethyl Androstane-17β-
carbothioates have topical anti-inflammatory activity
1
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10.1002/adsc.201900480
Advanced Synthesis & Catalysis
Table 1. Optimization of the reaction conditions.a)
Entry
X
Base
Solventb)
Temperat Yield
(equiv)
ure (oC)
(%)c)
1
2
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
CsF
Cs2CO3
NaOH
KOH
DMF
DMF
0
0
0
0
0
0
0
0
0
0
19
13
48
71
56
49
66
79
53
37
3
DMF
4
DMF
5
t-BuOK
KOH
DMF
6
MeOH
THF
7
KOH
8
KOH
CH3CN
n-hexane
1,4-
9
KOH
10
KOH
dioxane
MePh
Figure 2. Methods of fluoromethylselenylation from
organoselenocyanate.
11
12
13
14
15
16
1.5
1.5
1.0
2.0
2.0
2.0
KOH
KOH
KOH
KOH
KOH
KOH
0
0
42
49
68
89
80
73
CH2Cl2
CH3CN
CH3CN
CH3CN
CH3CN
0
0
TMSCF2H/t-BuOK (Figure 2, C).[14] Advantages of
these methods include mild reaction conditions, a wide
range of substrates, good functional group tolerance,
and high efficiency. Nevertheless, the introduction of
the monofluoromethylseleno group (-SeCFH2) into
small molecules is still challenging. As a deduction,
we speculate that monofluoromethyl selenoethers
could be synthesized from organoselenocyanate. To
the best of our knowledge, so far there are no examples
rt
50
a)Conditions: 1a (0.5 mmol), HBF4 (2 equiv), tert-butyl
nitrite (2 equiv), CuCl (0.05 mmol), CuCl2 (0.05 mmol),
1,10-phen = 1,10-phenanthroline (0.05 mmol), KSeCN (1.5
equiv), Base (10 equiv). b) anhydrous solvent. c) GC yield.
reaction revealed that using ICFH2 (2 equiv), KOH (10
equiv), in anhydrous CH3CN at 0 ℃for 7 hours could
obtain the product 2g in 89% yield (Table 1, entry 14).
that
describe
the
introduction
of
the
monofluoromethylseleno group (-SeCFH2). Herein we
present the first monofluoromethyl selenoethers of
aryl and alkyl halides via one-pot multistep synthesis
using KSeCN and ICFH2.
With the optimized reaction conditions in hand, the
substrate scope of the reaction with aniline containing
various functional groups was examined. The results
We first examined the application of o-toluidine
(1a) via one-pot three-step reaction. The reaction of 1a, are revealed in Table 2. In general, a variety of aryl-
HBF4, and tert-butyl nitrite was chosen as the model
reaction to generate corr esponding aryldiazonium
tetrafluoroborates.[15] The second step was reacted
substituted amines were applicable and achieved the
desired products in moderate to excellent yields (2a-
2p). The reaction was compatible with all substrates
which bearing different electron-donating groups or
electron-withdrawing groups at a different position in
the aromatic ring. A series of common functional
groups, such as methyl (2a, 2c), methoxy (2k), n-butyl
(2d), halogen (2b, 2e, 2f), cyano (2g) and nitro (2h)
were all well-tolerated. Moreover, disubstituted
aniline and trisubstituted aniline could also be
converted to the corresponding products in moderate
yields (2i-2k). In our previous work of
monofluoromethylthiolation,[16] 1-monofluoromethyl-
thio-3,4,5-trimethoxybenzene could only be detected
by GC-MS and decomposed quickly, while its
monofluoromethylseleno analogue 2k was stable, no
decomposition was observed even after more than
three months of storage on a shelf at ambient
temperature. It indicated that SeCFH2-containing
compounds were more stable than their SCFH2
analogues. Remarkable, substrates containing indane,
o
according to Rueping’s method[13b] under 0 C to get
the corresponding selenocyanates. Then, ICFH2 (1.5
equiv) was added in the reaction for introducing -CFH2
group with the corresponding selenocyanates under 0
oC for 7 h. Different bases were first investigated in
DMF (Table 1, entries 1-5), and among them, KOH
showed the best efficiency to give the desired product
2a in 71% yield (Table 1, entry 4). Other anhydrous
solvents such as MeOH, THF, CH3CN, n-hexane, 1,4-
dioxane, MePh, and CH2Cl2 were tested (Table 1,
entries 6-12), and we found that the reaction occurred
in anhydrous CH3CN can significantly improve the
yield to 79% (Table 1, entry 8). Then, we investigated
the amount of ICFH2 (Table 1, entries 13 and 14), and
it was found that 2.0 equivalent of ICFH2 gave 89%
yield of the desired product 2a (Table 1, entries 14).
Enhancing the reaction temperature would decrease in
yields (Table 1, entries 15 and 16). Optimization of the
2
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10.1002/adsc.201900480
Advanced Synthesis & Catalysis
Table 2. Scope of monofluoromethylselenolation of aryl.
Table 3. Scope of monofluoromethylselenolation of alkyl.
Conditions: 3 (1 mmol), KSeCN (1.5 equiv), ICFH2 (2
mmol), KOH (10 equiv) in anhydrous CH3CN. Yields are
those for the isolated products.
the scope of this reaction. The alkyl bromides were
applied to get the corresponding products via a one-
pot two-step reaction. The results are shown in Table
3. Generally, a large variety of alkyl bromides were
applicable to obtain the corresponding products in
moderate to excellent yields (4a-4q). Benzyl bromides
containing either electron-donating groups or electron-
withdrawing groups at the p- and m-position gave the
relevant products 4a-4g in 63%-93% yields.
Remarkably, in the reaction of o-methylbenzyl
bromide and o-phenylbenzyl bromide, the desired
products were only observed in less than 5% yields (4i,
4j) while o-fluorobenzyl bromide gave the
corresponding product in 92% yield (4h). Moreover,
disubstituted benzyl bromide and trisubstituted benzyl
bromide could also be converted to the relevant
Conditions: 1 (1 mmol), HBF4 (2 equiv), tert-butyl nitrite (2
equiv), CuCl (0.1 mmol), CuCl2 (0.1 mmol), 1,10-phen =
1,10-phenanthroline (0.1 mmol), KSeCN (1.5 equiv), ICFH2
(2 mmol), KOH (10 equiv) in anhydrous CH3CN. Yields are
those for the isolated products.
naphthalene, and amines with heteroaryl moieties
such as quinoline, benzothiazole, and benzoxazole
were also suitable for this reaction (2l-2p), enabling
the synthesis of more useful biologically relevant
molecules. Although a variety of aryl-substituted
amines were applicable, methyl 4-aminobenzoate, 3-
aminopyridine and 2-aminobenzoxazole could not
provide the desired products. The precise
configurations were unambiguously confirmed by
single-crystal X-ray diffraction analysis of 2h.[17]
Having a successfully developed method for the
introduction of -SeCFH2 group onto sp2-hybridized
aromatic compounds, we turned our attention to inves
tigate a technique for introducing -SeCFH2 group onto
sp3-hybridized carbon atoms. Alkyl bromides were
subjected to the standard reaction conditions to extend
products
in
good
yields
(4k,
4l).
2-
(Bromomethyl)Naphthalene was also applicable (4m).
Then, we increased the length of the alkyl chain, and
we found that the yields of corresponding products
decreased to moderate yields (4n, 4o). Gratifyingly,
aliphatic compounds, ketal (4p) and ester (4q) were
also tolerated in moderate yields. Some sensitive
substrates, such as 4-bromomethylbenzoic acid, 4-
(bromomethyl)phenylboronic acid, 3-methoxybenzyl
bromide and 8-bromomethylquinoline could not
provide the desired products, this may be due to the
use of large quantity of KOH.
3
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10.1002/adsc.201900480
Advanced Synthesis & Catalysis
To further demonstrate the utility of these reactions
in
a
late-stage modification, some drug-like
compounds were investigated (Table 3). To our
delight, nilotinib intermediate (an anticancer drug) and
metsulfuronmethyl
intermediate
(pesticide
intermediate) were also good candidates for our
reactions and provided the corresponding products in
83% and 46% yields, respectively (5a, 5b). When it
comes to more complex molecules, like mosapride, a
gastroprokinetic agent, was selectively converted at
Scheme 1. Synthesis of (2-selenocyanatoethyl)benzene and
phenethyl(Monofluoromethyl)seleno.
the
amino
group
to
get
the
Concerning that lower yields were obtained in non-
benzylic series (4n-4q), we conducted this one-pot
reaction in two separate steps to to determine which
the limiting step. Firstly, (2-bromoethyl)benzene
monofluoromethylselenolated product in 78% yield
(5c). After that, vitamin E derivative was applied.
Monofluoromethylselenolated vitamin E derivative
(5d) was isolated in 71% yield. These reactions
provide convenient access to highly functionalized
o
reacted with KSeCN in CH3CN at 25 C for 3h
provided (2-selenocyanatoethyl)benzene with a 58%
molecules
by
a
late-stage
yield (Scheme 1, a). And monofluoromethylation of
monofluoromethylselenolation reaction.
(2-selenocyanatoethyl)benzene
obtained
the
corresponding product in 83% yield (Scheme 1, b).
These results indicated that the formation of
selenocyanate resulted in the lower yields of non-
benzylic series.
Table 3. Later-stage monofluoromethylselenolation of
drug-like compounds.
Scheme 2. Control experiments.
To gain insights into the reaction, especially the
formation of monofluoromethyl selenoethers from
RSeCN and ICFH2, we monitored the reaction in the
presence of RSeCN, ICFH2 and KOH. It was found
that amount of RSeSeR was generated at the beginning
of the reaction. As the reaction proceeded, RSeCFH2
product was formed accompanied by a decrease in
RSeSeR. This indicated that RSeCFH2 products were
transferred from RSeSeR. To gain more insights, some
control experiments were conducted (Scheme 2).
Treatment of selenocyanatobenzene with KOH could
afford PhSeSePh in 92% yield (Scheme 2, a).[18a,b] To
confirm that KOH indeed promoted the
monofluoromethylation, we performed a reaction with
PhSeSePh and ICFH2 in the absence of KOH. There
was only trace of desired product, while 90% yield
observed with 10 equivalent of KOH. Based on these
observations,
a
plausible mechanism to help
rationalize this monofluoromethylselenolation was
proposed (Scheme 3). Initially, RSeSeR would be
formed from RSeCN in the presence of KOH. KOH
was proposed to promote the nucleophilic attack[19] of
RSe- to ICFH2 to form RSeCFH2 products. In the
meantime, CN- in the reaction mixture could react with
RSe+ to generate RSeCN.
In summary, we have successfully developed the
first example of synthesizing monofluoromethyl
selenoethers from organoselenocyanate via one-pot
multistep reactions. The reactions start with amines or
alkyl bromides to construct the corresponding C(sp2)-
SeCFH2 or C(sp3)-SeCFH2 bonds. The reactions are
a) Conditions: arylamine (1 mmol), HBF4 (2 equiv), tert-
butyl nitrite (2 equiv), CuCl (0.1 mmol), CuCl2 (0.1 mmol),
1,10-phen = 1,10-phenanthroline (0.1 mmol), KSeCN (1.5
equiv), ICFH2 (2 mmol), KOH (10 equiv) in anhydrous
b)
CH3CN. Conditions: vitamin E derivative (1 mmol),
KSeCN (1.5 equiv), ICFH2 (2 mmol), KOH (10 equiv) in
anhydrous CH3CN. Yields are those for the isolated
products.
4
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10.1002/adsc.201900480
Advanced Synthesis & Catalysis
easy to handle ， broad substrate scope, wide
poured into water (100 mL) and extracted with CH2Cl2. The
organic phase was washed with 2% NaOH (2 × 20 mL) and
water (2 × 10 mL), dried over MgSO4, followed by
concentrated and purification on silica gel column
functional groups, and can be applicative in late-stage
monofluoromethylselenolation
of
drug-like
compounds. We believe that these reactions could be
a general method for the synthesis of a variety of -
SeCFH2 compounds and may find broader application
in the future.
chromatography.
(R)-6-(4-bromobutoxy)-2,5,7,8-
tetramethyl-2-((4R,8R)-4,8,12-trimethyltridecyl)chro man
was obtained as a light-yellow oil in 47% yield.
Acknowledgements
We gratefully acknowledge the National Natural Science
Foundation of China (21776138, 21476116), the Fundamental
Research Funds for the Central Universities (30916011102,
30918011314), Natural Science Foundation of Jiangsu
(BK20180476), the Qing Lan and Six Talent Peaks in Jiangsu
Province, the Priority Academic Program Development of
Jiangsu Higher Education Institutions, and the Center for
Advanced Materials and Technology in Nanjing University of
Science and Technology for financial support.
Scheme 3. Proposed mechanism.
Experimental Section
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of aryl (4a-4q, 5d)
The reaction mixture of alkyl bromides (3, 1 mmol) and
KSeCN (1.5 mmol) was stirred in anhydrous CH3CN at 25
oC for 3h. Then KOH (10 equiv) and ICFH2 (2 mmol) were
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5
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10.1002/adsc.201900480
Advanced Synthesis & Catalysis
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Crystallographic
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10.1002/adsc.201900480
Advanced Synthesis & Catalysis
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Synthesis of Monoflouoromethyl selenoethers of
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