Ruthenium(II)-Catalyzed C?H Chalcogenation of Anilides

Article abstract of DOI:10.1002/adsc.201701147

Ruthenium-catalyzed C?H chalcogenations of anilides with readily available diselenides and disulfides have been achieved. Our strategy features ample substrate scope, affording the mono-ortho selenylated and thiolated anilides with complete site selectivity control and high catalytic efficacy. Detailed mechanistic studies provide strong support for a facile base-assisted internal electrophilic substitution (BIES) metalation event. (Figure presented.).

Full text of DOI:10.1002/adsc.201701147

Title: Ruthenium(II)-Catalyzed C−H Chalcogenation of Anilides
Authors: Wenbo Ma, Zhengyun Weng, Torben Rogge, Linghui Gu,
Jiafu Lin, Ai Peng, Xiang Luo , Xiaojun Gou, and Lutz
Ackermann
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10.1002/adsc.201701147
Advanced Synthesis & Catalysis
FULL PAPER
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Ruthenium(II)-Catalyzed C−H Chalcogenation of Anilides
Wenbo Ma,a,b* Zhengyun Weng,a,b Torben Rogge,c Linghui Gu,a,b Jiafu Lin,a,b
Ai Peng,a,b Xiang Luo,a,b Xiaojun Gou,a,b and Lutz Ackermannc*
a
Antibiotics Research and Re-evaluation Key Laboratory of Sichuan Province, Sichuan Industrial Institute of
Antibiotics, Chengdu University, Chengdu, P. R. China, 610052.
Key Laboratory of Medicinal and Edible Plants Resources Development of Sichuan Education Department, Sichuan
b
Industrial Institute of Antibiotics, Chengdu University, Chengdu, P. R. China, 610052
Fax: (+86)-(0)28-84333218; phone: (+86)-(0)28-84333218; E-mail: wenboma@hotmail.com
Institut fuer Organische und Biomolekulare Chemie Georg-August-Universitaet Tammannstrasse 2, 37077 Goettingen
c
(Germany) Fax: (+49)551-39-6777 E-mail: Lutz.Ackermann@chemie.uni-goettingen.de
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))
Abstract. Ruthenium-catalyzed C−H chalcogenations of strong support for
a
facile base-assisted internal
anilides with readily available diselenides and disulfides electrophilic substitution (BIES) metalation event.
have been achieved. Our strategy features ample substrate
scope, affording the mono-ortho selenylated and thiolated
anilides with complete site selectivity control and high
catalytic efficacy. Detailed mechanistic studies provide
Keywords: Selenylation; Thiolation; anilides; Ruthenium
catalyst; C−H activation.
by Ackermann, Nishihara, Shi, Li, and Zhang. While
these protocols provided efficient and convenient
route to access various chalcogenated arenes, there
are still some restrictions, such as long reaction time
as well as harsh reaction conditions that may limit
further applications. Especially, these previous
methods are limited to pyrimidine, oxime or other N-
containing directing groups, whereas the weakly-
coordinating[14] O- or S-directing groups have rarely
been reported (Scheme 1a).[15]
Anilides are useful building blocks in organic
synthesis, medicinal chemistry, natural products and
drug discovery. Importantly, acetanilide (antifebrin)
and its derivatives are valuable antipyretic and
analgesic drugs which are widely used in clinical
practice.[16] Given the structural utility, highly
efficient methods for transition metal-catalyzed C−H
functionalization with anilides have been devised in
recent years.[17]
Introduction
Diaryl sulfide and diaryl selenide scaffolds are
important structural motifs in a wide variety of
functional molecules, drug candidates and medicinal
chemistry because of their potential biological
activities.[1] For example, various organoselenium
and organosulfur compounds have been identified as
important therapeutic compounds ranging from
antiviral and anti-inflammatory to anticancer
agents.[2] Furthermore, they also have significant
applications to functional organic
fluorescent probes
material,[3]
and play an important role in
[4]
organic synthesis.[4g] The preparation of aryl selenides
therefore has attracted considerable interest in the
past decades. Compared with a large number of
synthetic methods of aryl selenides which are limited
to the coupling of prefunctionalized aryl substrates [5]
or electron-rich aryl compounds,[6] the transition-
metal-catalyzed C−Se and C−S formation via direct
C−H functionalization[7] represents a powerful and
reliable procedure due to its remarkable potential for
step economy and environmental sustainability.
Considering the versatile bioactivities of arylselenium
and arylsulfur anilides, and in continuation of our
recent silver-mediated C−H chalcogenations of
pyrazones,[18] we herein report an efficient ruthenium-
catalyzed C−H chalcogenations of anilides with
easily available diselenides and disulfides under mild
reaction conditions by weak coordination (Scheme
1b).
Recently, numerous approaches to C−S or C−Se bond
formation through chelation-assisted direct C−H
thiolation
and
selenation
catalyzed
by
palladium(II),[8]
rhodium(III),[9]
ruthenium,[10]
nickel,[11] cobalt,[12] or copper[13] have been explored
1
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10.1002/adsc.201701147
Advanced Synthesis & Catalysis
Table 1. Optimization of ruthenium-catalyzed C−H
selenylationa
Entry Additive 1 Additive 2
Solvent
Yield[b]
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
AgSbF6
AgSbF6
AgSbF6
AgSbF6
AgSbF6
AgSbF6
AgSbF6
AgSbF6
AgSbF6
AgSbF6
AgSbF6
AgSbF6
AgBF4
KPF6
AgOTf
AgOTf
AgOTf
AgOTf
AgOTf
AgOTf
AgOTf
AgOTf
AgOTf
Cu(OTf)2
CH3SO3H
CF3SO3H
AgOTf
AgOTf
AgOTf
AgOTf
Cu(OTf)2
Cu(OTf)2
----
DCE
tAmOH
dioxane
DMF
DMSO
CH3CN
HFIP
toluene
o-xylene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
10
trace
34
trace
trace
15
trace
84
76
85
trace
37
89
55
Scheme 1. Transition-metal-catalyzed C−H chalcogenation
of arenes
HOAc
trace
trace
91
CsOAc
AgBF4
----
AgBF4
AgBF4
AgBF4
63
Results and Discussion
trace
77[c]
64[d]
Optimization studies
Cu(OTf)2
Cu(OTf)2
At the outset of our studies, we probed the effect
exerted by various additives, and solvents on the
oxidative C−H selenylation using N-phenylacetamide
(1a) and 1,2-diphenyldiselane (2a) as the substrates at
100 ºC for 24 h. Preliminary studies indicated silver(I)
acetate to be the most effective terminal oxidant
(Table S-1 in the Supporting Information). Solvent
optimization (Table 1, entries 1–9) showed that
toluene was the ideal solvent, while other reaction
media gave significantly lower yields. Among a
variety of additives, AgBF4 and Cu(OTf)2 proved to
be optimal (entries 10–17), respectively, which
furnished the desired product 3aa in 91% yield.
Importantly, the triflate ion is crucial for this
transformation.[17b] The yield decreased significantly
without AgBF4 additive, which indicated that the
AgBF4 might facilitate the formation of the active
ruthenium catalyst species. Control experiments
verified that in the absence of [{RuCl2(p-cymene)}2]
or when [{RuCl2(p-cymene)}2] was replaced by
palladium catalysts, the desired product 3aa was
obtained only in minor quantities (Table S-1 in the
Supporting Information).
a) Reaction conditions: 1a (0.25 mmol), 2a (2.0 equiv, 0.50
mmol), [RuCl2(p-cymene)]2 (5 mol%), solvent (2.0 ml),
24 h, under Ar. b) Isolated yields. 80 ºC. 2.5 mol%
c)
d)
[{RuCl2(p-cymene)}2].
Subsequently, we evaluated the effect of the N-
substituent of the anilides 1 for the C–H selenylation
(Scheme 2). Interestingly, the acetyl group appeared
to be more effective as compared to more sterically
hindered analogues 1b or the aryl substituted anilide
1c under the current reaction conditions. The more
electron-withdrawing substituted amide 1d did not
provide the desired selenylated product. Further
studies indicated that the tertiary amide 1e failed to
enable the reaction, highlighting the key importance
of the acidic N–H moiety (Scheme 2).
2
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10.1002/adsc.201701147
Advanced Synthesis & Catalysis
Scheme 2. Effect exerted by the N-substituent
With the optimized reaction conditions in hand, we
probed the versatility of the C−H selenylation with
respect to the differently substituted anilide 1
(Scheme 3). Substrates bearing electron-rich and
electron-deficient groups on the para position reacted
with 1,2-diphenyldiselane 2a smoothly with excellent
positional selectivity, while electron-rich substrates
showed better reactivity (3fa-3ha). Importantly,
useful functional groups, such as chloro, bromo and
iodo were well tolerated under the ruthenium
catalysis regime, which could provide a versatile
synthetic handle for further functionalization of the
thus obtained products. It is noteworthy that the N-
(4-ethoxyphenyl)acetamide (1h), a typical NSAID,
proved to be a suitable substrate as well, delivering
the pharmaceutically and synthetically useful 3ha.
The ortho-substituted substrate 1m also reacted
efficiently, and gave the desired product in 61%
isolated yield. The site-selectivity of the C–H
functionalization with meta-substituted anilides (1n,
1o and 1q) was largely controlled by steric
interactions, thus delivering the mono-selenylated
products in 71% (3na), 70% (3oa) and 73% (3qa)
yields, respectively. In contrast, the substrate 1p
produced mono-selenylation on the more steric
hindrance position as the main product.
As
anticipated, differently substituted diaryl disulfides
showed high compatibility under the ruthenium
catalysis manifold, furnishing the desired products
3ab-3ad with high levels of chemo and positional
selectivity. The dibenzyl diselenide coupling partner
was also tested in this reaction. However, even under
harsher reaction conditions only trace amounts of the
selenylated product was observed.
Scheme 3. Scope of the C−H selenylations of substituted
anilides 1
Encouraged by the viability of the approach for direct
C−Se bond formation, we thereafter examined the use
of diaryl disulfides (Scheme 4) in C−S bond
formation under otherwise identical reaction
conditions. Hence, the anilide 1 substituted with
3
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10.1002/adsc.201701147
Advanced Synthesis & Catalysis
either electron-attracting or electron-donating groups
reacted with the diaryl disulfides 4 smoothly and
gave the thiolated product 5 in good isolated yields.
For the meta-substituted anilides, the ruthenium(II)-
catalyzed C−H functionalization occurred at the less
sterically hindered position to give the mono-
thiolated products 5na and 5qa. The decorated
diphenyl disulfides 4c was also efficiently converted
and gave the desired product with excellent levels of
chemo selectivity.
substrate 1g was more reactive than the electron-
deficient one 1i, being hence indicative of a base-
assisted internal electrophilic-type substitution (BIES)
metalation event (Scheme 5). [19]
Scheme 5. Intermolecular competition between different
substituted anilides 1
To further understand the reaction mechanism,
experiments were conducted with isotopically labeled
CD3OD as the additive. The results of the H/D
scrambling on the re-isolated anilide substrate [D]n-
1a and the selenylated product [D]n-3aa indicated
that the facile C–H activation step is reversible in
nature (Scheme 6).
Scheme 4. C−H thionations of anilides 1
Scheme 6. H/D exchange reaction with aniline 1a
Given the high catalytic activity of the versatile
ruthenium(II) catalyst, we conducted mechanistic
studies to unravel its mode of action. Intermolecular
competition experiments between two differently
substituted anilides showed that the electron-rich
Furthermore, ruthenium-catalyzed C–H selenylation
with the isotopically labeled substrate [D5]-1a and the
parent substrate 1a revealed an intermolecular kinetic
4
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10.1002/adsc.201701147
Advanced Synthesis & Catalysis
1.95 (s, 3H). 13C NMR (100 MHz, CDCl3) δ = 168.3, 139.6,
137.5, 130.9, 130.7, 129.9, 129.6, 127.0, 124.7, 121.0,
118.3, 24.7. HR-MS(ESI) m/z calcd for: C14H14NOSe+
[M+H+] 292.0235 found 292.0230.
isotope effect (KIE) of kH/kD ≈ 1.4 in competition
experiment (Scheme 7), being again suggestive of a
BIES C–H metalation event.
Representative Procedure B: Ruthenium(II)-Catalyzed
C–H Thiolation with Substituted N-phenylacetamide 1:
A suspension of N-phenylacetamide (1a) (33.8 mg, 0.25
mmol), 1,2-diphenyldisulfane (4b) (109 mg, 0.50 mmol),
[RuCl2(p-cymene)]2 (7.6 mg, 5.0 mol%), AgBF4 (10.0 mg,
20 mol%), Cu(OTf)2 (19 mg, 20 mol%) and AgOAc (83
mg 2.0 equiv) in toluene (2.0 mL) was stirred under argon
at 100 °C for 24 h. At ambient temperature, the reaction
mixture was diluted with H2O (10 mL) and extracted with
EtOAc (3 x 25 mL). The combined organic layers were
dried over Na2SO4. After filtration and evaporation of the
solvents in vacuo, the crude product was purified by
column chromatography on silica gel (Hexane/EtOAc:
4/1→2/1) to yield 5ab (46 mg, 76%) as a brown solid. M.
p = 88–90 °C. 1H NMR (600 MHz) δ = 8.43 (d, J = 8.2 Hz,
1H), 8.20 (s, 1H), 7.57 (dd, J = 10.9, 4.9 Hz, 1H), 7.47–
7.41 (m, 1H), 7.25–7.22 (m, 2H), 7.17 (t, J = 7.4 Hz, 1H),
7.13–7.10 (m, 1H), 7.08 (d, J = 7.5 Hz, 2H), 2.04 (s, 3H).
13C NMR (150 MHz) δ = 168.5, 140.0, 136.5, 135.8, 131.0,
129.4, 127.3, 126.4, 124.5, 121.0, 120.0, 24.9. HR-MS
(ESI) m/z calcd for: C14H14NOS+ [M+H+] 244.0791 found
244.0790.
Scheme 7. Kinetic isotope effect studies
Conclusion
In summary, we have developed a highly efficient C–
H chalcogenation for the challenging preparation of
selenylated
and
thiolated
anilides
though
ruthenium(II)-catalyzed C–H activation. A wide
range of substrates could be employed for the
versatile C–H functionalization, setting the stage for
the C–H selenylations and thiolations with excellent
chemo- and positional-selectivity as well as high
functional group tolerance. The C–H activation
strategy provides step-economical access to diversely
decorated anilides through facile BIES C–H cleavage.
Given the outstanding biological activities of
selectively substituted anilides, the positional
selective C–H functionalizations should prove
instrumental for medicinal chemistry and drug
discovery. Detailed studies on the reaction
mechanism, the pharmacological evaluation of the
thus obtained decorated anilides and further
development of direct chalcogenations are ongoing in
our laboratories, and will be reported in due course.
Acknowledgements
The authors wish to thank the National Natural Science
Foundation of China (Grant No. 21502010), the Antibiotics
Research and Re-evaluation Key Laboratory of Sichuan Province
(Grant No. ARRLKF15-03), Key Laboratory of Medicinal and
Edible Plants Resources Development of Sichuan Education
Department (Grant No. 10Y201708), the DFG (Gottfried-
Wilhelm-Leibniz award to LA), and Fundamental Research
Funds of the Chengdu University (2081915033).
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Representative Procedure A: Ruthenium(II)-Catalyzed
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1:
A suspension of N-phenylacetamide (1a) (34.2 mg, 0.25
mmol), 1,2-diphenyldiselane (2a) (157 mg, 0.50 mmol),
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mg 2.0 equiv) in toluene (2.0 mL) was stirred under argon
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column chromatography on silica gel (n-hexane/EtOAc:
4/1→2/1) to yield 3aa (67 mg, 91%) as a brown solid. M.
p = 78–80 °C. 1H NMR (400 MHz, CDCl3) δ = 8.30 (d, J =
8.1 Hz, 1H), 8.06 (s, 1H), 7.62 (d, J = 7.5 Hz, 1H), 7.37–
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10.1002/adsc.201701147
Advanced Synthesis & Catalysis
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FULL PAPER
Ruthenium(II)-Catalyzed C-H Chalcogenation of
Anilides
Adv. Synth. Catal. 2017, Volume, Page – Page
Wenbo Ma,a,b* Zhengyun Weng, a,b Torben Rogge,c
Linghui Gu,a,b Jiafu Lin, a,b Ai Peng, a,b Xiang Luo,
a,b
Xiaojun Goua,b and Lutz Ackermannc*
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