Palladium-Catalyzed Distal C?H Selenylation of 2-Aryl Acetamides with Diselenides and Selenyl Chlorides

Article abstract of DOI:10.1002/adsc.202000948

A convenient and effective method of palladium-catalyzed C?H selenylation of the 2-aryl acetamides assisted with removable 8-aminoquinoline with readily available diselenides and selenyl chlorides has been developed. This selenylation reaction is scalable and tolerates a wide range of functional groups, providing a straightforward way of the preparing unsymmetrical diaryl selenides and dibenzoselene-pinone. Preliminary mechanistic studies indicated that a single-electron transfer type mechanism and facile C?H metalation are operative. (Figure presented.).

Full text of DOI:10.1002/adsc.202000948

Title: Palladium-Catalyzed Distal C–H Selenylation of Aryl
Aceticamides with Diselenides and Selenyl Chlorides
Authors: Meicui He, Linghui Gu, Yuqiang Tan, Yang Wang, Yuchi
Wang, Chunran Zhang, and Wenbo Ma
This manuscript has been accepted after peer review and appears as an
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content of this Accepted Article.
To be cited as: Adv. Synth. Catal. 10.1002/adsc.202000948
Link to VoR: https://doi.org/10.1002/adsc.202000948

Advanced Synthesis & Catalysis
10.1002/adsc.202000948
FULL PAPER
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Palladium-Catalyzed Distal C–H Selenylation of 2-Aryl
Acetamides with Diselenides and Selenyl Chlorides
a
a#
a
a
a
a
Meicui He , Linghui Gu , Yuqiang Tan , Yang Wang , Yuchi Wang , Chunran Zhang
a
and Wenbo Ma *
a
Antibiotics Research and Re-evaluation Key Laboratory of Sichuan Province, Sichuan Industrial Institute of
Antibiotics, Chengdu University, People’s Republic of China, 610052.
Fax: (+86)-(0)28-84333218; phone: (+86)-(0)28-84333218; e-mail: wenboma@hotmail.com
#
These authors contributed equally to this work.
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: A convenient and effective method of palladium- pinone. Preliminary mechanistic studies indicated that a
catalyzed C–H selenylation of the 2-aryl acetamides assisted single-electron transfer type mechanism and facile C–H
with removable 8-aminoquinoline with readily available metalation are operative.
diselenides and selenyl chlorides has been developed. This Keywords:
Palladium catalyst; C–H selenylation;
selenylation reaction is scalable and tolerates a wide range of Removable directing group; 2-Aryl acetamides; Single-
functional groups, providing a straightforward way of the electron transfer.
preparing unsymmetrical diaryl selenides and dibenzoselene-
Introduction
Unsymmetrical diaryl chalcogenide scaffolds are
useful building blocks that frequently appear in many
drug candidates and natural products.[1] For example,
aryl chalcogenide derivatives displayed promising
bioactivities ranging from antitumor, antioxidant, anti-
inflammatory, antibacterial, antiviral activities.
[2]
(
Figure 1).
In addition, aryl chalcogenide
compounds have extensive applications in functional
materials, organic catalysis, synthetic chemistry and
[3]
fluorescent probes. Thus, the preparation of organic
molecules containing diaryl chalcogenide motifs has
received considerable interest in recent years.
Traditional methods to access unsymmetrical diaryl
sulfides and diaryl selenides mainly rely on cross-
coupling reactions of pre-functionalized staring
materials or direct electrophilic substitutions of
Figure 1. Representative related bioactive molecules.
electron-rich
aromatic
compounds
with
[4]
thiols/disulfides or diselenides. Moreover, most of
these reactions are performed under harsh or strongly-
basic reaction conditions and resulted in a narrow
substrate scope. Therefore, a general, rapid, and highly
regioselective method for the construction of C−Se
and C−S bonds is highly desirable.
In the past few decades, transition metal-catalyzed
directed C−H chalcogenation has emerged as a
powerful and effective strategy for the construction of
S- or Se-containing structures in pharmaceuticals and
materials due to its remarkable potential for step
[5]
economy and environmental sustainability. These
catalytic reactions usually require directing groups
1
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Advanced Synthesis & Catalysis
10.1002/adsc.202000948
pre-installed in the starting materials to govern the
reactivity and regioselectivity. In this context, lots of
efforts has been made to develop diverse directing
[6]
groups, which enable the successful transformation.
As early as 2014, Nishihara and Li reported the first
palladium-catalyzed aryl C−H thiolation with diaryl
[7]
disulfides directed by pyridine group. Subsequently,
Law, Wong and Anbarasan further extended the
substrate scope with different chalcogenide reagents
[8]
under the palladium catalysis (Scheme 1a). Our
group then disclosed the selective ortho-thiolation and
selenylation of N-arylsulfonamides with disulfides and
diselenides via weak coordination.[9] Nishihara and
coworkers developed a palladium-catalyzed peri-
selective C−H chalcogenation of naphthylamines with
the assistance of picolinamide bidentate directing
groups.[ Inspired by this work, more recently, Xie’s
10]
3
group further achieved the γ-C(sp )−H chalcogenation
of alkylamines with diaryl disulfides and diselenide in
good yield (Scheme 1b).[11] Furthermore, Maiti’s
group reported palladium-catalyzed the more
3
challenging C(sp )−H chalcogenation with the
assistance of 8-aminoquinoline directing groups,
which provides a generally useful method for
structural modifications of α-amino acids (Scheme
c).[ Nevertheless, despite significant progress in
12]
1
2
3
palladium-catalyzed aryl C(sp )−H and aliphatic C(sp )
H chalcogenation, the distal ortho-chalcogenation of
−
Scheme 1 Directing group assisted palladium-catalyzed
C−H chalcogenations.
phenylacetic acid derivatives has been rarely reported
so far.
More recently, our group reported a ruthenium(II)-
2
catalyzed distal chalcogenation of aromatic C(sp )−H
bonds with diselenides and disulfides through weak
Results and Discussion
coordination.[
13]
However, these reactions require
excess diselenide or disulfide reagents and additional
additives for complete conversion. Furthermore, only
para- and meta-substituted 2-aryl acetamides and
electron-deficient diselenides were compatible with
this catalytic reaction. The more steric hindrance 2-
aryl acetamides and electron-efficient diselenide
substrates also remains a challenge. In continuation of
our work [ and those of others on the catalytic
synthesis of unsymmetrical diaryl selenides, herein,
we disclose the efficient palladium (II)-catalyzed
ortho-selenylations of synthetically useful aryl acetic
amide with readily available diaryl diselenides or
phenylselenyl chloride via distal C−H bond activation
process. (Scheme 1d)
Our exploration was commenced by examining the
reaction parameters for the envisioned direct C–H
selenylation of N-(quinolin-8-yl)-2-(o-tolyl)acetamide
(
1a) with diphenyl diselenide (2a) under palladium
catalysis. The desired product 3aa was obtained in
2% yield in the presence of 2 equiv. Ag CO in DMF
3
2
3
at 100 ℃without any additives (Entry 1, Table 1). The
addition of AgOTf significantly increased the yield to
14]
6
6%. Substituting TfOH as additive gave a
comparable yield of the desired product along with
1% side product 4aa under the standard conditions
Entry 3). To our delight, the combination of AgOTf
1
(
and TfOH as co-additives in this catalytic reaction
resulted in 80% of desired product. Further
experimental results on oxidant screening revealed
that Ag
silver salts such as AgOAc, Ag
dipotassium peroxymonosulfate
2
CO
3
gained the best performance, while other
O, AgOPiv and
resulted in
2
unsatisfactory yields. (Entries 6-10). Among various
representative solvents, including DMF, DMSO,
toluene, 1,4-dioxane, TFE, HFIP and trifluorotoluene,
DMF turned out to have better reactivity than others,
affording the selenylated product 3aa in 80 % yield,
2
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Advanced Synthesis & Catalysis
10.1002/adsc.202000948
while the other solvents led to inferior results.
Remarkably, reducing the amount of the diaryl
diselenide coupling partners to 1.2 equivalence, gave
the desired product 3aa in 94% yield along with 6%
side products 4aa (Entry 19). However, further
decreasing the diaryl diselenide loading to 1.0
equivalence significantly affected the chemical yield.
the bidentate directing group, a series of phenyl
acetamides (I−III) in which the 8-aminoquinoline
group was replaced by a different directing groups,
such as isopropylamine, 1-naphthylamine or 2-
aminopyridine-N-oxide were subjected to the
optimized reaction conditions. No selenylated
products were observed indicated that the 8-
aminoquinoline directing group was essential for this
transformation (Scheme 2).
Having established the optimal reaction conditions,
we set out to investigate the substrate scope of this
selenylation reaction by examining various benzamide
derivatives. As shown in Scheme 3, benzamides
bearing electron-donating groups such as -Me or -
OMe, on the ortho-position were selenylated smoothly,
providing the corresponding mono-selenylated
products in 94% and 45% yields (3aa and 3ba). The
(
Entry 20) Control experiments verified that the
selenylation reaction did not occur in the absence of
the palladium catalyst or silver oxidant. (Entries 11
and 21).
Table 1. Optimization of various reaction parametersa
meta-substituted
benzamides
also
proceeded
efficiently at the less sterically encumbered C−H
bonds, affording the desired products in good yields
with excellent regioselectivity (3ca-3ea). Furthermore,
1-naphthyl- and 2-naphthyl- substituted substrates
reacted smoothly to give the corresponding products in
50% and 83% yields respectively (3fa and 3ga). The
1
h also participated in the reaction, however, the
Entry Oxidant
Additive
Solvent Yield%
yields were somewhat lower (3ha). Gratifyingly,
heterocyclic substrate 1i was also selenyated
efficiently and afford the desired product in 49%
isolated yield (3ia). However, the 3-substituted
thiophene substrate and more challenging alkenyl
C(sp )−H and aliphatic C(sp )−H bonds were not
compatible with the palladium catalysis regime (3ja-
3la). Note that attempts to activate heteroaryl,
naphthyl, and ortho-substituted aryl C−H bonds by the
previous report on ruthenium(III) catalyst assisted by
simple amide directing groups have, unfortunately,
met with limited success and only resulted in
3
aa/4aa
32/0
1
2
3
4
5
6
7
8
9
Ag
Ag
Ag
Ag
Ag
2
2
2
2
2
CO
CO
CO
CO
CO
3
3
3
3
3
---
AgOTf
TfOH
AgOTf+TfOH
AgOTf+TfOH
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
66/0
69/11
80/18
2
3
79/16b
AgOAc AgOTf+TfOH
Ag AgOTf+TfOH
AgOPiv AgOTf+TfOH
66/6
64/5
68/17
58/14
0/74
trace
--
2
O
K
2
S
2
O
8
AgOTf+TfOH
AgOTf+TfOH
AgOTf+TfOH
AgOTf+TfOH DMSO
AgOTf+TfOH Toluene
AgOTf+TfOH
AgOTf+TfOH dioxane
AgOTf+TfOH
AgOTf+TfOH
AgOTf+TfOH PhCF
1
0
1
2
3
4
5
6
7
8
9
0
1
CuBr
--
2
1
1
1
1
1
1
1
1
1
2
2
Ag
Ag
Ag
Ag
Ag
Ag
Ag
Ag
Ag
Ag
2
2
2
2
2
2
2
2
2
2
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
3
3
3
3
3
3
3
3
3
3
[13]
unsatisfactory yields.
--
DCE
20/5
trace
70/5
29/1
70/6
94/6c
TFE
HFIP
3
AgOTf+TfOH
AgOTf+TfOH
AgOTf+TfOH
DMF
DMF
DMF
d
48/6
e
--
a
Reaction conditions: 1a (0.20 mmol), 2a (0.40 mmol), PdCl
2
(10
mol %), Additive (20 mol %), TfOH (5 μL), solvent (2.0 mL),
b
c
d
1
2
00 ︒C , 24 h, under Ar. TfOH (10 μL). 1.2 equiv 2a. 1.0 equiv
a. without catalyst.
e
Scheme 2 Unreactive substrates
To clarify the necessity of the 8-aminoquioline as
3
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Advanced Synthesis & Catalysis
10.1002/adsc.202000948
Scheme 3 Palladium-catalyzed C−H selenylations with
different substituted 2-aryl acetamides.
Scheme 4. Investigation of diaryl diselenide scope.
Subsequently, a wide range of substituted diaryl
diselenides was evaluated under the optimized
reaction conditions. As depicted in Scheme 4, diaryl
diselenides bearing either electron-withdrawing
Encouraged by the successful distal selenylation
reaction with diaryl diselenide as coupling partners,
the more challenging phenylselenenyl chlorides (4)
[15]
were also tested under the palladium catalysis. As
anticipated, differently substituted 2-aryl acetamides
showed good reactivity, furnishing the desired
products 3aa−3ba and 3da−3ga with high levels of
positional selectivity. It is worth pointing out that the
meta-chloro substituted benzamide also proved to be a
suitable substrate in this selenylation, although only
give the selective mono-selenylated product in
moderate yields owing to incomplete conversion.
(
2b−2e, 2h-2j) or electron-donating groups (2f−2g) on
para-, meta- or ortho-position showed high reactivity
under the optimized conditions to give the selected
mono-selenylated products in medium to high yields.
Importantly, various functional groups such as
halogen and methoxyl were also well tolerated under
this palladium catalysis condition, giving the
possibility to further functionalize the selenylated
products. Notably, 1,2-di-p-tolyldisulfide could be
employed as a suitable coupling partner and afforded
the thiolated product 3ak in synthetically useful yield.
4
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Advanced Synthesis & Catalysis
10.1002/adsc.202000948
Scheme 5. Substrate scope of palladium-catalyzed
selenylation with phenylselenenyl chlorides.
To further demonstrate the practicality of this
palladium-catalyzed C−H selenylation, a gram-scale
reaction with 5.0 mmol of 1a and 2a was carried out,
and the selenylated product 3aa was delivered in a
slightly lower isolated yield of 85%. In addition, the 8-
aminoquinoline could be easily removed in the
o
presence of H
argon, to provide the corresponding ortho-selenylated
-arylacetic acids (5a-5d) in excellent yields. Notably,
2
SO
4
in 1,4-dioxane at 105 C under
2
the 8-aminoquinoline was also recovered in over 80%
yield. Furthermore, the thus obtained ortho-
selenylated 2-arylacetic acid was treated with TFA at
room temperature to give the biologically relevant
dibenzoselenepinone moiety 6 in 74% yield through an
intramolecular cyclization process. Finally, the
selenylated product 3aa could be selectively oxidized
to selenone 7 in the presence of hydrogen peroxide in
Scheme 6. Diversification of the selenylated products.
Considering the high catalytic activity of the robust
palladium catalyst, we conducted a set of control
experiments to gain insights into the reaction
mechanism. First, when the selenylation was
conducted with CD OD as cosolvent under the
3
standard reaction condition, around 36% deuterium
was incorporated at the ortho-position of recovered
starting material, thus indicating that the C−H bond
cleavage is reversible. (Scheme 7a) Furthermore, the
addition of typical radical scavenger (2,2,6,6-
tetramethylpiperidin-1-yl)oxidanyl (TEMPO) or 2,6-
di-tert-butyl-4-methylphenol (BHT) significantly
suppressed the catalyst’s efficacy and did not produce
the desired product (Scheme 7b), suggesting that a
single electron transfer (SET)‐ type mechanism likely
being in force here. A kinetic isotope effect (KIE) of
78% yield.
1.1 through intermolecular competitive C−H
selenylation of 1h and isotopically labeled [D ]-1h
5
with 2a implying that the C−H cleavage might not be
involved in the rate-determining step (Scheme 7c).
5
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Advanced Synthesis & Catalysis
10.1002/adsc.202000948
Scheme 8. Proposed catalytic cycle.
Conclusion
In conclusion, we have developed a novel and facile
method of palladium-catalyzed distal C−H
selenylations of 2-aryl acetic acid derivatives directed
by a removable 8-aminoquinolines bidentate auxiliary.
This protocol demonstrates scalable, excellent
regioselectivity and good functional group tolerance,
and delivered unsymmetrical diaryl selenides in good
yields (up to 94%). Considering the multi-bioactivity
of the diaryl diselenide and dibenzoselenepinone
derivatives, further applications of this strategy for the
preparation or diversification of complex molecules
and pharmaceuticals are currently in progress in our
laboratory
Scheme 7. Mechanistic Studies
Experimental Section
On the basis of experimental evidence discussed
A suspension of substituted N-(quinolin-8-yl)-2-(o-tolyl)-
acetamide (1) (1.0 equiv, 0.20 mmol), 1,2-diphenyldiselane
[12],[16]
above and previous literature reports
proposed a plausible mechanism outlined in Scheme
Initially, the activated palladium catalyst
we
(
(
(
(
2) (1.2 equiv, 0.24 mmol) or phenylselenenyl chloride (4a)
2.0 equiv, 0.4 mmol), PdCl (4 mg, 10 mol %), Ag CO
110 mg, 0.4 mmol), AgOTf (10 mg, 20 mol %) and HOTf
2
2
3
8.
coordinated to the N, N bidentate ligand to give a six
membered cyclopalladated intermediate A through a
reversible C−H bond activation process. Subsequent
oxidation by a selenyl radical generated palladium (III)
B, followed by reductive elimination to afford the
ortho-selenylated product. Besides, the intermediate A
could also coordinate with PhSeCl, followed by
nucleophilic displacement of the Cl by the Pd−C(aryl)
bond cleavage to give species E. Finally, reductive
elimination released the coupling product with the
regeneration of the active palladium catalyst in the
presence of silver oxidant.
5 μL) in DMF (2.0 mL) or mixture solvent (DMF:HFIP =
3
:1) was stirred under argon at 100 ℃ for 24 h. At ambient
temperature, the reaction mixture was quench with H O (10
mL) and extracted with EtOAc (3 x 25 mL). The combined
organic layers were dried over anhydrous Na SO . After
2
2
4
filtration and evaporation of the solvents in vacuo, the crude
product was purified by column chromatography on silica
gel (Petroleum ether/DCM: 2/1→1/1) to yield product 3.
Acknowledgements
The authors wish to thank the Sichuan Science and Technology
Program (Grant No. 2018JY0247), Antibiotics Research and
Re-evaluation Key Laboratory of Sichuan Province (Grant No.
ARRLKF-19-18) and Key Laboratory of Medicinal and Edible
Plants Resources Development of Sichuan Education
Department (Grant No. 10Y201708)
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