CaCl2-Promoted Dehydroxytrifluoromethylselenolation of Alcohols with [Me4N][SeCF3]

Article abstract of DOI:10.1021/acs.orglett.0c02109

A direct trifluoromethylselenolation of alcohols with the readily accessible [Me4N][SeCF3] salt has been reported. The reaction is significantly promoted by CaCl2 and proceeds smoothly through unprecedented carbonoselenoate intermediates to form the corresponding alkyl trifluoromethyl selenoethers in good yields. This protocol is also applicable to the late-stage dehydroxytrifluoromethylselenolation of complex alcohols owing to its mildness, good compatibility, high efficiency, and broad functional group tolerance.

Full text of DOI:10.1021/acs.orglett.0c02109

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Letter
CaCl2‑Promoted Dehydroxytrifluoromethylselenolation of Alcohols
with [Me4N][SeCF3]
Shuai Wu, Tian-Hao Jiang, and Cheng-Pan Zhang*
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ABSTRACT: A direct trifluoromethylselenolation of alcohols with the
readily accessible [Me4N][SeCF3] salt has been reported. The reaction
is significantly promoted by CaCl2 and proceeds smoothly through
unprecedented carbonoselenoate intermediates to form the corre-
sponding alkyl trifluoromethyl selenoethers in good yields. This
protocol is also applicable to the late-stage dehydroxytrifluoromethyl-
selenolation of complex alcohols owing to its mildness, good
compatibility, high efficiency, and broad functional group tolerance.
luorinated compounds have received broad interest in
various research fields because of their unique phys-
(phenyliodonium) tosylates, organic halides, diaryliodonium
triflates, aryl diazonium tetrafluoroborates, α-diazo carbonyls,
electron-rich (hetero)arenes, alkyl carboxylic acids, and 1,3-
dicarbonyls with [Me4N][SeCF3] was also comprehensively
harnessed, allowing the concise synthesis of various trifluor-
omethyl selenoethers.11 These results proved that [Me4N]-
[SeCF3] is thermally stable, nonvolatile, readily accessible, and
easy to handle, and it represents one of the most promising
trifluoromethylselenolation reagents so far. Despite the
aforementioned progress, trifluoromethylselenolation with
[Me4N][SeCF3] is still much less studied in comparison with
the homologous trifluoromethylthiolation using [Me4N]-
[SCF3].2,3 Thus the further search for new reactivities of
[Me4N][SeCF3] is very necessary for succeeding in more
trifluoromethylselenolation approaches.
F
icochemical and biological properties.1 Among all fluorine-
containing functionalities, the XCF3 (X = O, S) groups have
found wide applications in the synthesis of agrochemicals,
pharmaceuticals, and functional materials.2 In recent years, the
scientific attention has been shifted to the SeCF3 moiety and
the C−SeCF3 bond formation.3 Trifluoromethylselenolated
compounds constitute a new class of valuable molecules with
great potential for application in materials and life sciences.3
Because the known CF3Se-containing compounds are far more
scarce, developing efficient methods to incorporate SeCF3
groups into organic scaffolds is highly sought after.
The last several years have witnessed a flourish in the
construction of C−SeCF3 bonds along with advances in SeCF3
reagents and catalytic systems.3 Weng, Xiao, and Cook
reported the Cu-mediated trifluoromethylselenolation of
organic halides, terminal alkynes, α-diazo esters, and a series
of Csp3−H bonds with a copper(I) trifluoromethylselenolate
Alcohols are abundant, cheap, environmentally benign, easily
accessible, and frequently used raw materials in organic
synthesis.12 The combination of alcohols with fluorination
and fluoroalkylation reagents has constructed a large number
of useful fluorine-containing molecules.13 Qing et al. disclosed
a direct trifluoromethylthiolation/fluorination of alkyl alcohols
with AgSCF3/n-Bu4NI,14 and Tang et al. uncovered a
dehydroxytrifluoromethoxylation of alcohols using trifluoro-
methyl arylsulfonate as the OCF3 reagent and CsF/[Me4N]Br
as activators (Scheme 1).15 These reactions took full advantage
complex ([LCuSeCF3]2), a Ph3P+CF2CO2 /Se8/CsF mixture,
−
and a AgSeCF3/CsBr system, respectively.4−6 Billard, Tlili, and
others disclosed the electrophilic or radical trifluoromethylse-
lenolation of electron-rich arenes, Grignard reagents, carbonyl
compounds, alkynes and their metal derivatives, alkenes,
boronic acids, aryl diazonium salts, and alkyl halides with the
powerful trifluoromethylselenenyl chloride (CF3SeCl) and
trifluoromethyl tolueneselenosulfonate (TsSeCF3).7−9 How-
ever, these reagents suffered from high cost, low atomic
economy, high volatility, toxicity, harsh reaction conditions,
and tedious preparation procedures. Notably, tetramethylam-
monium trifluoromethylselenate ([Me4N][SeCF3]), synthe-
sized from TMSCF3/Se8/[Me4N]F, was investigated as a
versatile nucleophilic trifluoromethylselenolation reagent
under Cu, Pd, and Ni catalysis by the research groups of
Rueping, Goossen, Schoenebeck, and Zhang.10 Recently, the
transition-metal-free trifluoromethylselenolation of alkynyl-
−
of the equilibria between XCF3 (X = S, O) anions and X
CF2 with fluoride ions to produce trifluoromethyl (thio)ethers.
Nevertheless, as a comparison, the known MSeCF3 complexes
Received: June 26, 2020
https://dx.doi.org/10.1021/acs.orglett.0c02109
© XXXX American Chemical Society
Org. Lett. XXXX, XXX, XXX−XXX
A

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Letter
Scheme 1. Direct Trifluoromethylchalcogenation of
Alcohols
Table 1. Dehydroxytrifluoromethylselenolation of 1a by
a
[Me4N][SeCF3] under Different Reaction Conditions
b
entry
1a/x/y
additive
none
conditions
r.t./6 h
r.t./6 h
yield (2a, %)
1
2
3
4
5
6
7
8
1:3:0
1:3:1
1:3:1
1:3:1
1:3:1
1:3:1
1:3:1
1:3:1
1:3:1
1:3:1
1:3:1
1:3:1
1:3:1
1:3:2
1:2:1
1:2:0.5
1:3:1
1:3:1
0
52
c
CaCl2
CaCl2
CaCl2
CaCl2
CaCl2
Ca(COO)2
CaBr2
Ca(OTf)2
CaF2
CaSO4
HCl
LiI
CaCl2
CaCl2
CaCl2
CaCl2
CaCl2
40 °C/overnight
60 °C/overnight
80 °C/overnight
100 °C/ovenight
60 °C/overnight
60 °C/overnight
60 °C/overnight
60 °C/overnight
60 °C/overnight
80 °C/overnight
80 °C/overnight
80 °C/overnight
80 °C/overnight
80 °C/overnight
80 °C/2 h
63
81
94
88
30
76
63
37
38
(M = SnMe3, 1/3B, 1/2Hg) decomposed to form carbon-
oselenoic difluoride (SeCF2) under very harsh conditions.16
The decay of MSeCF3 was slower and had a smaller tendency
than that of the homologous −OCF3 and −SCF3 anions to O
CF2 and SCF2, respectively,16,17 according to the calculated
free energies of the similar conversions.17a More seriously, the
SeCF2 species was very easy to polymerize upon its
formation under the reaction conditions.16 These circum-
stances indicated that the synthesis and application of the Se
CF2 intermediate is a challenging task. In this context, we
envisioned that the removal of fluoride ions from the reversible
decomposition of −SeCF3 anion would be conducive to the
production of SeCF2 under mild conditions, which possibly
slows down its polymerization. In other words, the use of a
fluoride scavenger along with ionic SeCF3 salt would accelerate
the degradation of −SeCF3 to SeCF2 and benefit the
targeted reactions. Very recently, Hopkinson et al. reported a
deoxytrifluoromethylselenolation of alcohols with benzothia-
zolium salt (BT−SeCF3) in the presence of NEt(iPr)2,18
which, however, suffered from the laborious synthesis of the
SeCF3 reagent from bis(2-benzothiazolyl)diselenide/CF3I/
MeOTf via stepwise procedures. As a part of our continuing
interest in the development of facile trifluoromethylselenola-
tion reactions, we examined in this Letter the dehydroxytri-
fluoromethylselenolation of alcohols with the readily accessible
[Me4N][SeCF3] reagent in the presence of a fluoride
scavenger. This reaction is more convenient and efficient
than Hopkinson’s method and likely proceeds through a
different mechanism from that of Qing and Tang’s
reactions.14,15
9
10
11
12
d
c
69
67
c
13
14
15
16
17
18
57
54
(75)
c
92 (89)
c
80 °C/1 h
81
a
Reaction conditions: 1a (0.2 mmol), [Me4N][SeCF3] (0.4 or 0.6
mmol), CaCl2 (0, 0.1, 0.2, or 0.4 mmol), CH3CN (2 mL), N2,
b
c
conditions. Yields were determined by GC. Yields were determined
by 19F NMR. Isolated yield is depicted in the parentheses.
d
Anhydrous HCl in 1,4-dioxane (4 mol/L) was used.
Ca(COO)2 (calcium oxalate), CaBr2, Ca(OTf)2, CaF2, and
CaSO4 instead of CaCl2 in the reactions of 1a and
[Me4N][SeCF3] (3 equiv) at 60 °C furnished 2a in 30, 76,
63, 37, and 38% yield (entries 7−11, Table 1), which
suggested that CaCl2 and CaBr2 are comparably effective
promoters for the conversion. The frustrated results of
Ca(COO)2, CaF2, and CaSO4 might be attributed to their
inertness and insolubility in CH3CN. Other additives such as
HCl and LiI under similar conditions supplied 2a in 67−69%
yield, implying that the Brønsted acid and lithium salt could
moderately improve the reaction (entries 12 and 13, Table 1
and the SI). The equivalents of CaCl2 and [Me4N][SeCF3]
also considerably affected the trifluoromethylselenolation.
Varying the molar ratios of 1a, [Me4N][SeCF3], and CaCl2
from 1:3:1 to 1:3:2, 1:2:1, and 1:2:0.5 at 80 °C resulted in 54,
57, and 75% of 2a, indicating that superfluous CaCl2 harmed
the transformation, whereas excess [Me4N][SeCF3] benefited
the reaction (entries 14−16, Table 1). Furthermore, the
reaction time could be reduced. A mixture of 1a, [Me4N]-
[SeCF3] (3 equiv) and CaCl2 (1 equiv) heated to 80 °C for 2
or 1 h furnished 2a in 92 or 81% yield, implying a fast
trifluoromethylselenolation (entries 17 and 18, Table 1).
Next, the substrate scope of this dehydroxytrifluoromethyl-
selenolation was tested by using a combination of 1,
[Me4N][SeCF3] (3 equiv), CaCl2 (1 equiv), 80 °C, N2, and
2 h or overnight as the optimal conditions (entry 17, Table 1,
Scheme 2). To our delight, a series of benzyl alcohols bearing
either electron-withdrawing (e.g., F, Cl, Br, I, CN, CHO,
CO2Me) or electron-donating groups (e.g., OMe, CH3,
O(CH2)O) on the phenyl rings were smoothly converted to
form the corresponding products (2b−k) in good yields (48−
98%). Aliphatic alcohols such as 2-phenylethan-1-ol (1l),
It is well known that calcium salt has been widely used as a
cheap and strong scavenger for fluoride removal from water by
chemists in both academic and industrial research fields,19
which may be a good choice for our design to enhance the
−
decomposition of the SeCF3 anion to SeCF2 under mild
conditions. The preliminary study showed that the treatment
of 3-phenylpropan-1-ol (1a) with [Me4N][SeCF3] (3 equiv) in
CH3CN at room temperature under a nitrogen atmosphere for
6 h gave no trifluoromethylselenolated product, and the
starting materials could be recovered (entry 1, Table 1).
Encouragingly, the use of CaCl2 (1 equiv) in the same reaction
led to (3-phenylpropyl)(trifluoromethyl)selane (2a) in 52%
yield, suggesting that the trifluoromethylselenolation could be
significantly promoted by CaCl2 (entry 2, Table 1). Elevating
the reaction temperature from room temperature to 40, 60,
and 80 °C in the reactions of 1a, [Me4N][SeCF3] (3 equiv),
and CaCl2 (1 equiv) overnight provided 2a in 63, 81, and 94%
yield, respectively (entries 3−5, Table 1). The choice of
calcium salts had an influence on the reaction. Taking
B
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equivalent of [Me4N][SeCF3] (5 equiv) and lowering the
reaction temperature (60 °C), which afforded 2aa in 77%
yield. In addition, the dehydroxytrifluoromethylselenolation
was applicable to secondary alcohols. The treatment of
diphenylmethanol (1ab), 4-phenylbutan-2-ol (1ac), and
1,2,3,4-tetrahydronaphthalen-1-ol (1ad) with [Me4N]-
[SeCF3]/CaCl2 under the slightly modified conditions
supplied 2ab−ad in 40−54% yields. Interestingly, the reaction
of 1-phenylprop-2-en-1-ol (1ae) with [Me4N][SeCF3] and
CaCl2 in the same way formed cinnamyl(trifluoromethyl)-
selane (2p) rather than 2ae as the product, which might be
attributed to the thermodynamically preferable rearrangement
of the independent carbon−carbon double bond (1ae) to the
conjugated one (2p). The use of excess [Me4N][SeCF3] or the
relatively low reaction temperature in some cases was
beneficial to transforming the intermediates (e.g., 3, see
Scheme 3) or inhibiting the elimination byproducts. None-
Scheme 2. CaCl2-Promoted
Dehydroxytrifluoromethylselenolation of Alcohols by
a
[Me4N][SeCF3]
Scheme 3. Studies for Mechanistic Insights
a
Reaction conditions: 1 (0.2 mmol), [Me4N][SeCF3] (0.6 mmol),
CaCl2 (0.2 mmol), MeCN (2 mL), N2, 80 °C (oil bath), 2 h, isolated
b
c
d
e
yield. Overnight. 60 °C. [Me4N][SeCF3] (1.0 mmol). 2 days.
f
[Me4N][SeCF3] (0.8 mmol).
theless, tertiary alcohol (e.g., 1af) reacted with [Me4N]-
[SeCF3] and CaCl2 under either standard or modified
conditions provided a complicated mixture.
dodecan-1-ol (1m), dec-9-en-1-ol (1n), and 3,7-dimethyloct-6-
en-1-ol (1o) reacted with [Me4N][SeCF3] and CaCl2 under
the standard conditions to provide 2l−o in 62−87% yields.
(E)-3-Phenylprop-2-en-1-ol (1p) and 3-phenylprop-2-yn-1-ol
(1q) were also successfully trifluoromethylselenolated in the
reaction, giving products (2p−q) in 50−84% yields. Other
complex alcohols like 2-(5-methoxy-2-methyl-1H-indol-3-yl)-
ethan-1-ol (1r), 2-(hydroxymethyl)isoindoline-1,3-dione (1s),
1-(2-hydroxyethyl)pyrrolidine-2,5-dione (1t), benzo[b]-
thiophen-2-ylmethanol (1u), anthracen-9-ylmethanol (1v),
ferrocenemethanol (1w), and tert-butyl (S)-(1-hydroxy-4-
methylpentan-2-yl)carbamate (1x) reacted similarly with
[Me4N][SeCF3] and CaCl2 to furnish 2r−x in 37−93% yields.
These results demonstrated that the carbon−carbon double
bonds and triple bond, heterocycles, imides, ferrocene, and
carbamate groups in alcohols were well tolerated in the
dehydroxytrifluoromethylselenolation. When pyridine-2,6-diyl-
dimethanol (1y) was mixed with [Me4N][SeCF3] and CaCl2
under the same conditions, the doubly trifluoromethylseleno-
lated product (2y) was obtained in 37% yield. Increasing the
equivalents of [Me4N][SeCF3]/CaCl2 or decreasing the
reaction temperature did not obviously change the yield of
2y. Moreover, the drug and drug-like molecule, for example, N-
(4-(4-fluorophenyl)-5-(hydroxymethyl)-6-isopropyl-4,5-dihy-
dropyrimidin-2-yl)-N-methylmethanesulfonamide (1z) and
idebenone (1aa), reacted under the standard conditions to
give 2z in 87% (or 73%) yield and 2aa in 52% yield. The
reaction of 1aa could be further improved by increasing the
To probe the possible reaction mechanisms, several control
experiments were carried out (Scheme 3 and the SI). It was
found that a mixture of 1a and [Me4N][SeCF3] (3 equiv) at
room temperature for 6 h gave no trifluoromethylselenolated
product, whereas the treatment of 1a with [Me4N][SeCF3] (3
equiv)/CaCl2 (1 equiv) under the same conditions provided
2a in 52% yield (entries 1 and 2, Table 1). Further exploration
showed that the reaction of 1a with [Me4N][SeCF3] (3 equiv)
in the absence of CaCl2 at 80 °C overnight formed 2a in 38%
yield (Scheme 3). It seemed that [Me4N][SeCF3] itself could
also initiate the dehydroxytrifluoromethylselenolation at an
elevated temperature but with much poorer efficiency than that
using CaCl2. Additionally, when 1a was mixed with CaCl2 (1
equiv) without [Me4N][SeCF3] at 80 °C for 2 h, no reaction
occurred, and the starting alcohol was recovered (Scheme 3).
In contrast, the treatment of [Me4N][SeCF3] with CaCl2 in
the absence of 1a at room temperature led to the rapid
conversion of [Me4N][SeCF3] as the signals of [Me4N]-
[SeCF3] disappeared within 1 h in the 19F NMR spectra of the
reaction mixtures. (See the SI.) The expected peaks of Se
CF2 and its polymers were not observed; nonetheless, Se
C(SeCF3)2 was detected by 19F NMR and GC−MS analyses of
the mixtures, which might work as an intermediate for the
reactions of [Me4N][SeCF3]/CaCl2/1a.16 Moreover, the
standard reaction of 1ab with [Me4N][SeCF3] (3 equiv) and
CaCl2 (1 equiv) formed 2ab in 39% total yield, accompanied
C
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by a considerable amount of Ph2CHOC(Se)SeCF3 (3,
Condition A, Scheme 3). This byproduct could not be
separated from 2ab by column chromatography but could
almost completely be transformed in the reaction with 5 equiv
of [Me4N][SeCF3] under the same conditions (47%) or in the
reaction with 3 equiv of [Me4N][SeCF3] overnight followed by
treatment with another 3 equiv of [Me4N][SeCF3] for 8 h at
80 °C (39%) (Condition B or C, Scheme 3 and the SI),
indicating that the dehydroxytrifluoromethylselenolation pos-
sibly involves a carbonoselenoate intermediate (ROC(Se)-
SeCF3).
functional group tolerance, wide range of substrates, and easily
accessible starting materials. The application of [Me4N]-
[SeCF3] as a useful SeCF2 source for other systems is
currently underway in our laboratory.
ASSOCIATED CONTENT
* Supporting Information
■
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.orglett.0c02109.
Brief description of screening the optimal reaction
conditions, general procedure for CaCl2-promoted
dehydroxytrifluoromethylselenolation, control experi-
ments for mechanistic insights, characterization data,
and NMR spectra of the products (PDF)
On the basis of these results and the knowledge that the
calcium cation has a strong affinity for fluoride and that
−SeCF3 has high nucleophilicity, a plausible reaction
mechanism is suggested in Scheme 4. Carbonoselenoic
Scheme 4. Proposed Reaction Mechanism for CaCl2-
Promoted Dehydroxytrifluoromethylselenolation
AUTHOR INFORMATION
Corresponding Author
■
Cheng-Pan Zhang − School of Chemistry, Chemical Engineering
and Life Science, Wuhan University of Technology, Wuhan
430070, China; orcid.org/0000-0002-2803-4611;
Email: cpzhang@whut.edu.cn, zhanghengpan1982@
hotmail.com
Authors
Shuai Wu − School of Chemistry, Chemical Engineering and Life
Science, Wuhan University of Technology, Wuhan 430070,
China
Tian-Hao Jiang − School of Chemistry, Chemical Engineering
and Life Science, Wuhan University of Technology, Wuhan
430070, China
difluoride (I) is first generated from the decomposition of
−SeCF3 with CaCl2 as a fluoride scavenger, which, upon
generation, reacts with another two equivalents of SeCF3 in
−
the presence of Ca2+ cations to form bis(trifluoromethyl)-
carbonotriselenoate (II) as a key intermediate (path A). In the
latter step, the Ca2+ species might behave as both a fluoride
scavenger and a Lewis acid to promote the formation of II
from I. Because there were no signals of selenocarbonyl
fluorides detected by 19F NMR during the reactions, this
process may be rapid and complete. Subsequently, the
nucleophilic substitution of II by ROH provides a carbon-
oselenoate (III), which is finally attacked by the −SeCF3 anion
to provide the trifluoromethylselenolated product (path A).
Furthermore, the production of RSeCF3 via a straightforward
reaction of I and ROH followed by the nucleophilic attack of
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.orglett.0c02109
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We thank Wuhan University of Technology, the National
Natural Science Foundation of China (21602165), the
“Hundred Talent” Program of Hubei Province (China), and
the Chongqing Research Program of Basic and Frontier
Technology (cstc2017jcyjAX0303) for financial support.
−
FC(Se)OR (V) with SeCF3 cannot be excluded in this stage
(path B). This pathway is not likely the major process in the
Ca-mediated dehydroxytrifluoromethylselenolation, especially
when using a large excess [Me4N][SeCF3]. Combining all of
the observations might hint at a different reaction profile of
[Me4N][SeCF3]/CaCl2 for alcohols from those of AgSCF3/n-
Bu4NI and ArSO2OCF3/CsF/[Me4N]Br,14,15 wherein alcohols
probably reacted solely with XCF2 (X = S, O) to yield the
corresponding trifluoromethylchalcogenated products. Never-
theless, the exact roles of CaCl2 in these reactions remain
unclear.
In conclusion, we have developed an efficient method for the
CaCl2-promoted dehydroxytrifluoromethylselenolation of al-
cohols with [Me4N][SeCF3]. A variety of primary and
secondary alcohols, including complex bioactive molecules,
were readily converted to form the respective alkyl
trifluoromethyl selenoethers in good yields. A mechanistic
study showed that this reaction might mainly proceed though a
bis(trifluoromethyl)carbonotriselenoate (II) intermediate,
which was in situ generated from SeCF2 and −SeCF3 anions.
The advantages of the method include its simplicity,
convenience, high efficiency, mild reaction conditions, good
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