Palladium-Catalyzed Trifluoromethylthiolation of Chelation-Assisted C–H Bonds

Article abstract of DOI:10.1002/ejoc.201800451

An efficient palladium-catalyzed trifluoromethylthiolation of chelation-assisted C–H bonds has been accomplished by employing a readily accessible trifluoromethylthiolating reagent. The reaction tolerates various directing groups and functional groups and allows the access to diverse trifluoromethylthiolated arenes in good yield. A plausible mechanism was proposed based on preliminary mechanistic investigations.

Full text of DOI:10.1002/ejoc.201800451

A Journal of
Accepted Article
Title: Palladium Catalyzed Trifluoromethylthiolation of Chelation
Assisted C-H bonds
Authors: Arunachalam Kesavan, Manthena Chaitanya, and
Pazhamalai Anbarasan
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To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201800451
Link to VoR: http://dx.doi.org/10.1002/ejoc.201800451
Supported by

10.1002/ejoc.201800451
European Journal of Organic Chemistry
COMMUNICATION
Palladium Catalyzed Trifluoromethylthiolation of Chelation
Assisted C-H bonds
Arunachalam Kesavan, Manthena Chaitanya and Pazhamalai Anbarasan*[a]
Dedication ((optional))
Abstract: An efficient palladium catalyzed trifluoromethylthiolation of
chelation assisted C-H bond have been accomplished employing
readily accessible trifluoromethylthiolating reagent. The reaction
tolerates various directing groups and functional groups and allows
the access to diverse trifluoromethylthiolated arenes in good yield.
The plausible mechanism was proposed based on the preliminary
mechanistic investigation.
extensively. Surpassing these methods, direct and selective
trifluoromethylthiolation of C-H bonds[7] of arenes were also
documented employing either electrophilic ‘SCF3’ reagent or
under oxidative conditions with AgSCF3 (Scheme 1a). For
instance, Daugulis and co-workers[8] disclosed the first
trifluoromethylthiolation of C-H bond employing substiochimetric
amount of copper catalyst and (CF3S)2. Subsequently, various
palladium, cobalt and rhodium catalyzed trifluoromethylthiolation
of arenes[9] and indoles[10] were reported employing electrophilic
N-SCF3 reagent. Beside, employing nucleophilic AgSCF3
palladium or cobalt catalyzed trifluoromethylthiolation of C-H
bond was also demonstrated under the oxidative conditions.[11]
Introduction
Trifluoromethylthiolated arene and heteroarene have gained
great attention in the recent past, due to their presence in
various therapeutically important molecules as well as their
ability to alter the physical, biological and chemical properties of
the parent molecule.[1] Representative examples of bioactive
molecules containing aryltrifluoromethylthio group is shown in
Figure 1. Hence, there has been a significant interest in the
synthetic community for the development of elegant strategy for
the construction of trifluoromethylthiolated arenes and
heteroarenes.[2]
Although
most
of
these
methods
offer
a
direct
trifluoromethylthiolation of C–H bonds, the major drawback are
the use of N-SCF3 reagents, which are synthesized from
relatively unavailable and expensive AgSCF3 in a multistep
process and the requirement of additional oxidant. Thus, the
development of a general method for the trifluoromethylthiolation
of C-H bond employing readily accessible electrophilic reagent is
highly warranted.
a) Metal catalyzed trifluoromethylthiolation of C(sp2)–H bonds: Previous work
DG
DG
H
N
CN
'SCF3' sources
Pd, Cu, Co
'SCF3' sources
Additive
O
O
H3C
SCF3
SCF3
Cl
N
N
X
H
SCF3
SCF3
N
N
N
SCF3 PhO2S
NH
Et
N
SCF3
O
Tiflorex
(used for treatment of
nervous anorexia)
O
PhO2S
O
Cl
Cl
X = CO, SO2
Rh
Nifedipin analogue
(controls blood pressure)
Toltrazuril
(antiprotozoal agent)
SCF3
AgSCF3
+ Oxidant
N
'SCF3' source
Additive
N
F3CS SCF3
DG
DG
b) Palladium catalyzed trifluoromethylthiolation of C(sp2)–H bonds: This work!
Figure 1. Biologically important trifluoromethylthioaryl moiety containing
molecules.
DG
DG
· 25 examples
· up to 85% yield
· readily accessible reagent
R
N
Pd(OAc)2
+
Ts
SCF3
H
SCF3
DG = pyridine, pyrimidine, pyrazole,
quinoline and isoquinoline
Typically, syntheses of trifluoromethylthiolated arene have been
achieved through either formation of S-CF3 bond[3] or the
halogen exchange with the prefunctionalized sulfur-containing
molecule[4]. However, these methods are highly limited to
specific substrates, due to the harsh reaction conditions. The
most viable method that has been practiced in last decade is the
direct introduction of ‘SCF3’ moiety through C–SCF3 bond
formation. In this context, transition metal catalyzed cross
coupling of prefunctionalized aryl electrophiles[5] and
nucleophiles[6] with appropriate nucleophilic or electrophilic
trifluoromethylthio sources, respectively, have been studied
Scheme 1. Synthesis of trifluoromethylthioarene via C–H bond
functionalization.
Recently, Billard and co-workers[12] developed
a one-step
access to various N-SCF3 reagents from readily available
amines, DAST and CF3TMS, which are also shown to be an
excellent electrophilic ‘ SCF3 ’ source. Our long standing
interest in the synthesis of trifluoromethylthiolated arenes[13] and
C-H bond functionalization[14] as well as importance of
trifluoromethylthiolated arenes in combination with ready access
to N-SCF3 reagents through Billard protocol prompted us to
develop a direct trifluoromethylthiolation of C-H bonds employing
readily accessible reagent.[15] Thus, we herein disclose the
[a]
Mr. A. Kesavan, Dr. M. Chaitanya, Prof. Dr. P. Anbarasan
Department of Chemistry
Indian Institute of Technology Madras
Chennai – 600036
palladium-catalyzed
trifluoromethylthiolation
of
chelation
E-mail: anbarasansp@iitm.ac.in
Homepage: https://home.iitm.ac.in/anbarasansp/
assisted C-H bonds of arenes (Scheme 1b).
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
Results and Discussion
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10.1002/ejoc.201800451
European Journal of Organic Chemistry
COMMUNICATION
We initiated our studies with synthesis of various N-SCF3 (3a-3f)
reagents employing the protocol of Billard and co-workers. Next,
the synthesized reagents were subjected under the palladium
yield of 2a (Table 1, entry 9). Thus, the optimized conditions for
the trifluoromethylthiolation of C-H is 1.5 equivalents of 3e or 1.1
equivalents of 3f in the presence of 5 mol% of Pd(OAc)2 in TFAA
at 130 or 120 °C.
catalyzed
trifluoromethylthiolation
conditions
using
2-
phenylpyridine 1a model substrate. Reaction of 1a with 1.1
equivalents of N-SCF3 reagents 3a-3d in the presence of 5
mol% of palladium acetate in trifluoroacetic acid (TFAA) at
120 °C didn’t afford the expected product, only decomposition
of N-SCF3 reagents were observed (Table 1, entry 1).
Having identified the suitable conditions for the
trifluoromethylthiolation of chelation assisted C-H bonds, scope
and limitation of the developed method was investigated.
Keeping pyridine as directing group various substituted 2-
arylpyridines were subjected under the optimized conditions
(Scheme 2). Electron donating alkyl and alkoxy substituted aryl
derivatives furnished the corresponding trifluoromethylthiolated
product (2a-2d) in good yield. Sterically congested 2,3-
benzofused 2-arylprydine gave the product 2e in 46% yield.
Additional coordination containing methylaryl thioether afforded
the product 2g in 38% yield with 3f as trifluoromethylthiolating
reagent. In addition, relative electron withdrawing, halo
substituted trifluoromethylthio arenes (2f, 2h-2j) were also
achieved in moderate to good yield via C-H bond
functionalization.
Interestingly,
employing
an
more
electrophilic
trifluoromethylthiolating reagent 3e under the above conditions,
the formation of expected trifluoromethylthiolated product 2a
was observed in 59% yield (Table 1, entry 2).
Table 1. Palladium catalyzed trifluoromethylthiolation of 2-phenylpyridine 1a:
Optimization[a]
Entry
SCF3 source
Solvent
TFAA
Temp (°C)
120
Yield (%)[b]
1
2
3
4
5
6
7
8
9
3a-3d
3e
-
TFAA
120
59
Pd(OAc)2 (5 mol%)
N
N
3e (1.5 equiv.)
R
R
3f
TFAA
120
93
H
SCF3
TFA, 130 °C, 12 h
2
1
3f
TFAA
110
82
MeO
3e
AcOH
120
-
N
N
N
N
SCF3 Me
2a: 81% (78%)‡
SCF3 MeO
2b: 53%
SCF3
2c: 77%
SCF3
2d: 74%
3e
TfOH
120
-
3e
DCE/TFAA[c]
TFAA
120
<5
F
Cl
3e[d]
3e[d]
120
77
N
N
N
N
SCF3 EtO
2e: 46%
SCF3 MeS
SCF3
2g: 38%†
SCF3
2h: 63%†
TFAA
130
90 (63)[e]
2f: 31%
[a] Reaction conditions: 1a (1 equiv.), 3a-3f (1.1 equiv.), Pd(OAc)2 (5 mol%),
solvent (0.32 M), temp, 12 h. [b] yield is based on 19F NMR using
hexafluorobenzene as internal standard. [c] Ratio of solvent is 1:1. [d] 1.5
equiv. of 3e was used. [e] 2.5 mol% of Pd(OAc)2.
N
N
F
SCF3
2i: 44%†
Cl
SCF3
2j: 23%†
R
N
H
N
O O
S
Scheme 2. Palladium catalyzed trifluoromethylthiolation of 2-arylpyridines 1
SCF3
†
SCF3
SCF3
N
with 3e/3f: Scope and limitation. Reaction was performed with 1.1 equiv. of
3f at 120 °C. ‡ Yield of gram scale reaction.
R
R = H, 3e
R = Me, 3f
X
Me
R = H, 3a
R = Me, 3b
X = Me, 3c
X = Cl, 3d
Next, compatibility of various directing group under the
present trifluoromethylthiolation conditions were examined.
Replacing 3e with the relatively electrophilic[16] methylated
derivative 3f afforded the product 2a in 93% yield (Table 1, entry
3). Decreasing the reaction temperature with 3f also slightly
decrease the yield (82%) of 2a (Table 1, entry 4). Since the
synthesis of reagent 3f requires the addition step, best
conditions were optimized with reagent 3e. Thus, changing the
reaction medium to acetic acid, triflic acid or the 1:1 mixture of
1,2-dichloroethane (DCE) and trifluoroacetic acid with reagent
3e gave either no reaction or only detectable amount of product
(Table 1, entries 5-7). Interestingly, increase in yield (77%) was
observed with 1.5 equivalents of 3e in TFAA at 120 °C (Table 1,
entry 8). The best result (90%) was achieved at 130 °C with 1.5
equivalents of 3e and 5 mol% of palladium acetate in TFAA.
Decreasing the catalyst loading to 2.5 mol% also decrease the
Simple
4-methylpyridine
efficiently
directed
the
trifluoromethylthiolation of C-H bond and led to the product 2l in
77% yield (Scheme 3). Sterically hindered 3-methyl and 6-
methoxy substituted pyridine derivatives also afforded the
product 2k and 2m in excellent yield. Similarly, 5-fluoropyridine
derivative also furnished the corresponding product 2n in 42%
yield. In place of pyridine, isoquinoline and quinoline showed
high compatibility as directing group and let the formation of 2o
and 2p in 66 and 65% yield, respectively. However, pyrimidine,
which has additional coordination site gave the corresponding
product (2q) in relatively lower yield. Trifluoromethylthiolation of
benzo[h]quinoline under the present conditions gave the product
2r in 63% yield. The formation of trifluoromethylthiolated product
was unambiguously confirmed by X-ray analysis, which also
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10.1002/ejoc.201800451
European Journal of Organic Chemistry
COMMUNICATION
matches with the literature report[9a] (Scheme 3). Interestingly,
the developed method was successfully extended to the
selective ortho-trifluoromethylthiolation of N-arylpyrazoles
employing 3f as trifluoromethylthiolating reagent. Thus, using
3,5-dimethylpyrazole as directing group, trifluoromethylated
arenes 2s-2w were achieved in moderate to good yield. Bulky 3-
methyl-5-phenyl also successfully directed trifluoromethylation to
furnish 2t in 43% yield.
phenylpyridine 1a' under the optimized conditions with 3e for 5 h
afforded the mixture of 2a and 2a' in 23% yield and the 65% of
1a' recovered (Scheme 5a). Kinetic isotopic effect observed for
this reaction is 0.13, which suggests that the initial metallation
through C-H bond functionalization is reversible and not the rate-
determining step. This is further supported by the reaction of 1a'
in the absence of 3e under the optimized conditions with
palladium acetate, where significant amount of loss of deuterium
was observed. Subsequently, the stable palladacycle 6 was
synthesized and stoichiometric reaction was performed under
the optimized conditions. Thus, the trifluoromethylthiolation of
palladacycle 6 with 3e in TFAA at 130 °C furnished the product
2a in 15% yield along protodemetallation to 1a in 33% yield. On
the other hand, more reactive trifluoromethylthiolating reagent 3f
at 120 °C gave the product 2a in 37% yield. These observations
revealed that 1) palladacycle 6 like intermediate might be formed
in the catalytic cycle, 2) the reductive elimination to product 2 is
possibly the slow and rate determining step and 3) also support
the reversible metallation and protodemetallation.
DG
DG
Pd(OAc)2 (5 mol%)
3e (1.5 equiv.)
R
R
H
SCF3
2
1
TFA, 130 °C, 12 h
Me
F
Me
N
N
N
OMe
N
SCF3
SCF3
2n: 42%†
SCF3
2l: 77%
SCF3
2m: 65%
2k: 84%
N
N
N
N
SCF3
2r: 63%†
N
a)
SCF3
SCF3
2q: 31%†
H/D
2o: 66%‡
Pd(OAc)2 (5 mol%)
2p: 65%
SCF3
1a'
(65% recovered)
N
N
+
3e (1.5 equiv.)
Me
Me
Me
D
SCF3
2a/2a': 23%
TFA, 130 °C, 5 h
1a'
Me
Me
Me
KIE = 0.13
N
N
N
N
N
N
b)
c)
SCF3 Me
2s: 55%†
SCF3 iPr
2t: 52%†
SCF3
2u: 23%†
Pd(OAc)2 (5 mol%)
TFA, 130 °C, 12 h
N
N
D
H/D
1a/1a': 88%
Me
Me
Ph
1a'
Me
Me
Me
N
N
N
N
N
N
N
MeO
SCF3 Br
2v: 30%†‡
SCF3 Me
2w: 44%†‡
SCF3
2x: 43%†
3, TFA
Pd
N
N
+
2
temp, 6 h
O
Ac
SCF3
1a
2a
Scheme 3. Palladium catalyzed trifluoromethylthiolation: Scope and limitation
6
15%
37%
33%
48%
3e at 130 °C:
3f at 120 °C:
of directing group. Reaction of all the pyrazole derivatives were performed with
†
‡
10 mol% of Pd(OAc)2. Reaction was performed 1.1 equiv. of 3f at 120 °C.
1H NMR yield.
Scheme 5. Mechanistic investigation.
Synthetic utility of the present transformation was
demonstrated through oxidative conversion to sulfoxide 4 and
sulfone 5, which are shown to have unique physiochemical
properties. Oxidation of 2a with trichloroisocyanuric acid and
water at room temperature furnished the sulfoxide 4 in 98% yield.
On the other hand, using strong oxidation conditions, H5IO6 and
catalytic amount of CrO3, complete oxidation of 2a to sulfone 3
was observed in 95% yield.
Based on the preliminary mechanistic investigation and
literature precedence, the plausible mechanism for the present
trifluoromethylthiolation of arene C-H bond was postulated.
Palladium acetate in the presence of trifluoroacetic acid would
generate activated palladium species A, which on reaction with
arene 1 would furnish palladacycle B via chelation assisted
electrophilic metallation of arene C-H bond. Oxidative addition of
trifluoromethylthiolating reagent 3 to palladacycle B would afford
the Pd-intermediate C. Formation of product 2 from intermediate
C could be rationalized through reductive elimination and the
generation of palladium species D. Ligand exchange with TFAA
would complete the catalytic cycle and regenerate the active
palladium species A for the next cycle.
TCCA
(1.6 equiv.)
CH3CN/DCM
H2O, rt, 1 h
98%
H5IO6 (4 equiv.)
CrO3 (2 mol%)
CH3CN, rt, 8 h
95%
N
N
N
CF3
CF3
S
SCF3
S
4
2a
5
O O
O
Scheme 4. Synthetic applications.
Preliminary deuterium labeling and stoichiometric study were
performed to understand the possible mechanism of the present
trifluoromethylthiolation. Reaction of mono-deuteriated 2-
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10.1002/ejoc.201800451
European Journal of Organic Chemistry
COMMUNICATION
Pd(OAc)2
57, 1397-1409; f) S. Barata-Vallejo, S. Bonesi, A. Postigo, Org. Biomol.
Chem. 2016, 14, 7150-7182.
TFAA
AcOH
[3]
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DG
Ts
R
N
H
Pd(TFA)2
6
R
1
A
TFA
TFA
[4]
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Ts
R
DG
Pd
N
B
D
Pd(TFA)
TFA
R
R
Ts
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N
DG
SCF3
DG
3
Ts
R
SCF3
R
N
Pd
2
R
SCF3
C
[6]
Scheme 6. Plausible mechanism.
Conclusions
In summary, we have developed an efficient palladium catalyzed
trifluoromethylthiolation of chelation assisted C-H bond of arenes.
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The
reaction
utilizes
the
readily
accessible
trifluoromethylthiolating reagent and various directing group like
pyridine, pyrimidine, pyrazole, quinoline and isoquinoline. This
also allows the synthesis of various trifluoromethylthiolated
arenes in good to excellent yield. Synthetic application was
demonstrated through ready conversion to sulfoxide and sulfone.
Furthermore, preliminary mechanistic investigation was
performed to understand the in-sight of the reaction mechanism.
[8]
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We thank Indian Institute of Technology Madras (Project No.
CHY/16-17/840/RFIR/ANBA) for financial support. A.K. thanks
IIT Madras and M.C. thank Council of Scientific & Industrial
Research (CSIR) for a fellowship.
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Keywords: trifluoromethylthiolation • C-H bond functionalization
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10.1002/ejoc.201800451
European Journal of Organic Chemistry
COMMUNICATION
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COMMUNICATION
Trifluoromethylthiolation*
Arunachalam Kesavan, Manthena
Chaitanya and Pazhamalai Anbarasan*
Page No. – Page No.
Palladium Catalyzed
Palladium catalyzed trifluoromethylthiolation of chelation assisted C-H bond have
been accomplished employing readily accessible electrophilic
trifluoromethylthiolating reagent.
Trifluoromethylthiolation of Chelation
Assisted C-H bonds
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