(Pentamethylcyclopentadienyl)cobalt(III)-Catalyzed Direct Trifluoromethylthiolation of Arenes via C?H Activation

Article abstract of DOI:10.1002/adsc.201700066

The direct trifluoromethylthiolation of arenes was realized via (pentamethylcyclopentadienyl)cobalt(III)-catalyzed C(sp²)-H activation and coupling with AgSCF₃ under the assistance of a directing group. The reaction features redox-neutrality, mild conditions, broad substrate scope, and good functional group tolerance. Preliminary mechanistic studies have been conducted. (Figure presented.).

Full text of DOI:10.1002/adsc.201700066

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DOI: 10.1002/adsc.201700066
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(Pentamethylcyclopentadienyl)cobalt(III)-Catalyzed Direct
Trifluoromethylthiolation of Arenes via CÀH Activation
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Xu-Ge Liu,a Qingjiang Li,a and Honggen Wanga,*
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School of Pharmaceutical Sciences, Sun Yat-sen University, Guangzhou 510006, People’s Republic of China
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Fax: (+86)-20-3994-3000; e-mail: wanghg3@mail.sysu.edu.cn
Received: January 18, 2017; Revised: February 23, 2017; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201700066
Abstract: The direct trifluoromethylthiolation of
arenes was realized via (pentamethylcyclopentadie-
nyl)cobalt(III)-catalyzed C(sp2)-H activation and
coupling with AgSCF3 under the assistance of a
directing group. The reaction features redox-neu-
trality, mild conditions, broad substrate scope, and
good functional group tolerance. Preliminary mech-
anistic studies have been conducted.
Keywords: CÀH activation; cobalt; silver; arene
trifluoromethylthiolation
31 With the strong electron-withdrawing effect and high
32 lipophilicity properties,[1] the trifluoromethylthio
33 group (SCF3) has been recognized as a privileged
34 functional group in agrochemical and pharmaceuticals,
35 as exemplified by the wide occurrence of ArSCF3
36 components in a number of pesticides and drugs.[2] In
37 addition, SCF3 could serve as a precursor for the
38 preparation of trifluoromethyl sulfoxides and sulfones,
39 thus demonstrating its important synthetic values.[3]
40 ArSCF3 compounds have been traditionally accessed
41 from the halogen-fluorine exchange reactions of the
42 corresponding trihalomethylthio ethers.[4,5] An alter-
43 native strategy is the trifluoromethylations of sulfur-
44 containing functionalities such as thiols,[6] thiocya-
Scheme 1. Examples of the synthesis of ArSCF3 via CÀH
activation.
45 nates[7] and disulfdes.[8] Recent advances have demon- CÀH bonds under the catalysis of noble palladium
46 strated that metal-catalyzed cross-coupling of pre- catalyst by using various trifluomethylthiolating re-
47 activated arenes with diverse SCF3 sources provided a agents (Scheme 1b).[11] Li reported Rh(III)-catalyzed
48 reliable and powerful synthetic strategy.[9] In addition, selective trifluoromethylthiolation of indoles at the 2-
49 the uncatalyzed direct trifluoromethylthiolation of position under the assistance of a directing group
50 Grignard or organolithium reagents has also been (Scheme 1b).[12] To meet the criteria of sustainable
51 reported (Scheme 1a).[10]
chemistry, there is a growing interest in base metal
Over the past decades, transition-metal catalyzed catalysis. In this regard, Daugulis and coworkers
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53 direct functionalization of unactivated CÀH bonds has successfully developed a copper-promoted trifluoro-
54 emerged as a simple but powerful strategy in modern mythlthiolation of benzamides, wherein toxic and
55 organic synthesis. For the construction of ArSCF3, the volatile CF3SSCF3 was employed as the SCF3 source
56 groups of Shen, Huang, and Liu independently (Scheme 1b).[13] It should be noted that for electron-
57 realized the direct trifluoromythlthiolation of aryl
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rich arenes, the Friedel–Crafts type direct trifluorome- lowered the yield (entries 3–5). The use of a base
thylthiolation was also feasible.[14]
additive was found to be beneficial (entries 6–9), with
Pioneered by Kanai,[15] high-valent Cp*Co(III) NaOPiv·H2O giving the best result (65%, entry 9).
complexes have been extensively investigated as cost- Performing the reaction under N2 atmosphere gave
effective catalysts for various CÀH functionalization lower yield (44%, entry 10), indicating that molecular
reactions.[16] The advantages are apparent in terms of oxygen might serve as an oxidant. Interestingly,
cost, toxicity, and in certain case, intriguing reactivity. however, under O2 atmosphere, a yield of only 15%
We have recently disclosed that Cp*Co(III) species is was obtained (entry 11). Other cobalt catalysts such as
an effective catalyst for the coupling between aryl or Co(OAc)2, Co(acac)2, Co(acac)3, CoBr2, and CoCl2
10 alkenyl CÀH bonds with carbenoids, CO, or alkynes.[17] were all ineffective (entries 12–16). Besides,
11 Herein, we report our realization of a Cp*Co(III)- [Cp*RhCl2]2 and [Cp*IrCl2]2, the heavier congeners of
12 catalyzed direct ortho-selective mono-trifluorome- [Cp*CoI2]2, also showed no activity under our opti-
13 thylthiolation reaction of arenes using AgSCF3 as a mized conditions (entries 17 and 18).
14 readily available reagent (Scheme 1c).[18]
15
We initiated our studies by examining the coupling
Table 2. Cp*Co(III)-catalyzed Trifluoromethylthiolation of
Aryl CÀH BondsThe SCF3 group in compound 2s should not
be “bold”. Please help us correst it.
16 of 2-phenypyridine (1a) with AgSCF3 in the presence
17 of a Cp*Co(III) catalyst (Table 1). The desired
18 trifluoromethylthiolation product 2a was obtained in
19 20% yield in the presence of Cp*Co(CO)I2(10 mol%)
20 in DCE at 1008C under air (Table 1, entry 1).
21 [Cp*CoI2]2 showed superior reactivity, giving an in-
22 creased yield of 45% (entry 2). Replacing DCE with
23 other solvents such as MeOH, DMF and toluene
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Table 1. Optimization of the reaction conditions.[a]
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entry Catalyst
(mol %)
solvent Additive
yield
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(20 mol %) (%)[b]
1
Cp*Co(CO)I2
DCE
DCE
–
–
20
(10)
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[Cp*CoI2]2 (5)
[Cp*CoI2]2 (5)
[Cp*CoI2]2 (5)
[Cp*CoI2]2 (5)
[Cp*CoI2]2 (5)
[Cp*CoI2]2 (5)
[Cp*CoI2]2 (5)
[Cp*CoI2]2 (5)
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trace
0
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MeOH –
DMF
–
toluene –
DCE Na2CO3
DCE KOAc
DCE CsOPiv
DCE NaOPiv·H2 65
O
DCE NaOPiv·H2O 44
DCE NaOPiv·H2O 15
DCE NaOPiv·H2O 0
DCE NaOPiv·H2O 0
DCE NaOPiv·H2O 0
DCE NaOPiv·H2O 0
DCE NaOPiv·H2O 0
DCE NaOPiv·H2O 0
DCE NaOPiv·H2O 0
10[c] [Cp*CoI2]2 (5)
11[d] [Cp*CoI2]2 (5)
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Co(OAc)2 (10)
Co(acac)2 (10)
Co(acac)3 (10)
CoBr2 (10)
CoCl2 (10)
[Cp*RhCl2]2 (5)
[Cp*IrCl2]2 (5)
Reaction conditions: 1 (0.2mmol), [Cp*CoI2]2 (5 mol%),
NaOPiv·H2O (20 mol%), DCE (0.2 M), 100oC, isolated
[a] Reaction conditions: 1a (0.2 mmol), AgSCF3(0.4 mmol),
yield.
catalyst, solvent (1 mL), 100oC under air, 24 h.
[a] DCM as solvent.
[b] Isolated yield based on 1a. under N2.
c
[c] under O2.
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With the establishment of the optimized conditions reversible and turn-over limiting. Previous studies
(Table 1, entry 9), the substrate scope was then have demonstrated that under oxidative reaction
investigated. As show in Table 2, a wide range of conditions, AgSCF3 could be transformed to CF3
2-arylpyridines bearing different substituents, regard- SSCF3, which may serve as an active trifluorome-
less of their electronic properties, underwent reaction thylthiolating reagent.[20] As a matter of fact, Daugulis
smoothly, giving the corresponding trifluoromethyl- and coworkers have employed CF3SSCF3 as an
thiolation product in 23–65% yields. Some commonly effective SCF3 source in copper catalyzed trifluorome-
encountered functional groups such as methoxy (2d, thylthiolation of arenes.[12] To probe whether CF3
2l, 2o, 2r, 2t), methylthio (2e), ester (2f), ketone SSCF3 is the active trifluoromethylthiolation in our
10 (2g), halogen (2h, 2m, 2o), were tolerated, thus giving system, 19F NMR analysis was conducted. Heat a
11 good opportunities for further functionalizations. Al- solution of AgSCF3 at 1008C under air with or w/o
12 cohols protected with acetyl (2i), MOM (2j) or TBS base led to only the detection of AgSCF3 (d=
13 (2k) survived under the reaction conditions. The 22.0 ppm) in solution. However, in the presence of
14 reaction of meta-substituted 2-phenypyridines gave [Cp*CoI2]2, a new signal corresponding to CF3SSCF3
15 the corresponding functionalized products at the less (d=46.8 ppm) started to be detected. The same signal,
16 congested position exclusively (2m, 2n). Unfortu- though in low intensity, could also be observed from
17 nately, an ortho-methoxy substituent hampered the the crude reaction mixture (Scheme 2c). However,
[20b,d,e]
18 reaction likely due to steric reasons (2o). Naphthalene when an independently prepared CF3SSCF3
was
19 (2r) and heteroaryl substrates including thiopene (2p) used in place of AgSCF3 in a catalytic reaction, no
20 and dibenzo[b,d]furan (2q) were also viable sub- formation of 2a was detected. It is likely that the
21 strates. To our delight, 2-pyrimidinyl was also an silver salt (AgSCF3) may act as an activator of the Co
22 effective directing group for this transformation.[19] In (III) catalyst or CF3SSCF3. Nevertheless, no formation
23 this case, DCM was found to be a superior solvent and of 2a was found in the presence of additional AgOAc
24 the corresponding trifluoromethylthiolation products or AgSbF6 (Scheme 2c). All these results seem to
25 could be obtained in moderate yields (2s 57%, 2t indicate that CF3SSCF3 was less likely to be an
26 60%).
Several reactions have been conducted to showcase
intermediate for this reaction.
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Based on the above mechanistic studies and
28 the utilities of the products. The oxidation of 2s with literature precedents, a reaction mechanism was
29 m-CPBA provided trifluoromethyl sulfoxide 3 in 88% tentatively proposed (Scheme 3). The active catalyst
30 yield (eq 1).[9g] The Cp*Ir(III)-catalyzed CÀH annula- Cp*Co(III)Ln (I) is generated from the reaction of
31 tion of 2a with alkyne 4 delivered the trifluorome- [Cp*CoI2]2 with AgSCF3 and/or NaOPiv·H2O. There-
32 thylthiolated pyrido[2,1-a]isoquinolin-5-ium 5 in 65% after, a turn-over limiting and reversible CÀH activa-
33 yield (eq 2).[17d] Moreover, the SCF3-functionalized tion takes places to give II. The transmetallation of
34 indolizine 6 was obtained from the reaction of 2a and thiolate anion from AgSCF3 to II furnishes III. Upon
35 ethyl oxoacetate, albeit in low yield (eq 3).[16s]
reductive elimination, the product is formed with the
concomitant formation of a Cp*Co(I) species, which is
then oxidized by Ag+ or molecular oxygen to regener-
ate the active catalyst.
In summary, the direct trifluoromethylthiolation of
arenes has been realized via Cp*Co(III)-catalyzed
CÀH activation and subsequent coupling with
AgSCF3. Mechanistic studies have been conducted
and a tentative reaction mechanism was proposed.
Given the significance of SCF3 group in medicinal and
synthetic organic chemistry, we expect that this
protocol may find applications.
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Experimental Section
To a 10 mL sealed tube, were added the corresponding
substrate (0.2 mmol), AgSCF3 (83.6 mg, 0.4 mmol),
[Cp*CoI2]2 (9.0 mg, 0.01 mmol), NaOPiv·H2O (5.8 mg,
0.04 mmol), and DCE (1.0 mL). The resulting reaction
mixture was allowed to stir at 1008C for 24 h. After cooling
down, the solvents were removed under reduced pressure
and the residue was purified by column chromatography on
50
To shed light on the reaction mechanism, mecha-
51 nistic studies were conducted. Subjection of 1a-d5 to
52 the standard conditions resulted in significant amount
53 of H/D exchange (around 50%) at the ortho positions
54 of both the product and recovered starting material
55 (Scheme 2a). In addition, a primary kinetic isotope
56 effect of kH/kD =2.2 was observed (Scheme 2b). These
57 results suggested that the CÀH activation step is
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silica gel (petroleum ether/ethyl acetate) to give the desired
products.
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Acknowledgements
Financial support by the National Natural Science Foundation
of China (Nos. 21472250 and 81402794), the Key Project of
Chinese National Programs for Fundamental Research and
Development (2016YFA0602900), the “1000-Youth Talents
Plan”, and the Start-up Grant from Sun Yat-sen University is
gratefully acknowledged.
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