Nickel-Catalyzed Intramolecular Decarbonylative Coupling of Aryl Selenol Esters

Article abstract of DOI:10.1002/adsc.202001611

This report describes a method for Ni-catalyzed intramolecular decarbonylative coupling, which enables the conversion of areneselenol esters to diaryl selenides. The inexpensive and readily available catalyst can be employed under mild reaction conditions for the construction of structurally diverse diaryl selenides, including heterocyclic and natural product derivatives. (Figure presented.).

Full text of DOI:10.1002/adsc.202001611

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DOI: 10.1002/adsc.202001611
Nickel-Catalyzed Intramolecular Decarbonylative Coupling of
Aryl Selenol Esters
Jin-Hua Bai,+a Xiu-Juan Qi,+b Wei Sun,a Tian-Yang Yu,a,* and Peng-Fei Xuc,*
a
Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education,
College of Chemistry & Materials Science, Northwest University, Xi’an 710069, People’s Republic of China
E-mail: yuty@nwu.edu.cn
School of materials science and engineering, Southwest University of Science and Technology, Mianyang 621010,
b
People’s Republic of China
c
College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, People’s Republic of China
E-mail: xupf@lzu.edu.cn
+
These authors contribute equally to this work.
Manuscript received: December 30, 2020; Revised manuscript received: February 16, 2021;
Version of record online: Februar 25, 2021
Supporting information for this article is available on the WWW under https://doi.org/10.1002/adsc.202001611
attention.[20–33] This process offers several advantages
over conventional cross-couplings. First, carboxylic
Abstract: This report describes a method for Ni-
catalyzed intramolecular decarbonylative coupling,
acids and their derivatives are often more readily
which enables the conversion of areneselenol esters
available and less expensive than their aryl halide
to diaryl selenides. The inexpensive and readily
counterparts. Second, this process helps reduce the
available catalyst can be employed under mild
amount of harmful toxic waste (CO as the major side
reaction conditions for the construction of structur-
product). Finally, this reaction proceeds in the absence
ally diverse diaryl selenides, including heterocyclic
of nucleophiles.
and natural product derivatives.
Significant effort has also been devoted to the
transition-metal-catalyzed decarbonylative intramolec-
ular couplings of ketones, esters, and other carboxylic
acid derivatives to form CÀ C and C-heteroatom
Keywords: Nickel catalysis; Decarbonylation; Dia-
ryl selenides; Seleno esters; Extrusion strategy
bonds.[34–49] Herein, we report our findings on an
alternate synthetic route to diaryl selenides via the
nickel-catalyzed intramolecular decarbonylative cou-
Selenium is known as a fundamental element in life pling of selenoesters (Scheme 1).
sciences. Organoselenides, particularly arylselenides,
have attracted considerable attention as key reagents in
organic synthesis; moreover, they possess unique
photoelectric properties and important biological activ-
ities (Figure 1).[1–5] Arylselenides also play pivotal
roles in catalysis, fluorescence analysis, and synthesis
of functional organic materials. This point has moti-
vated the report of different methodologies to synthe-
size these compounds.
Diarylselenides are most commonly prepared via
transition-metal-catalyzed coupling of aryl halides,
aryl silanes, or aryl boronic acids with phenylselenyl
chloride, diphenyl diselenide, or phenylselenyl tribu-
tyltin reagents.[6–19]
Recently, the transition-metal-catalyzed intramolec-
ular decarbonylative coupling of naturally abundant
carboxylic acid derivatives has attracted increased
Figure 1. Examples of diarylselenides as core structure for
organic electronic material, photosensitizers and biological
molecules.
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Table 1. Opimization of the reaction conditions.[a]
Entry Catalyst
Ligand
Base
Yield
(%)[b]
1
2
3
4
5
6
7
8
Ni(acac)2
NiI2
NiCl2
Ni(OAc)2
NiCl2(dppe)
Ni(cod)2
Ni(cod)2
NiCl2
dppe
dppe
dppe
dppe
–
dppe
dppe
dppp
dppm
Na2CO3 50
Na2CO3 67
Na2CO3 90
Na2CO3 78
Na2CO3 85
Na2CO3 90
–
90
Na2CO3 85
Na2CO3 30
9
NiCl2
Scheme 1. Ni-Catalyzed decarbonylation of selenoesters.
10
11
12
13
14[c]
15[d]
16
17
18[e]
NiCl2
NiCl2
NiCl2
NiCl2
NiCl2
NiCl2
–
1,10-phenanthroline Na2CO3 27
dppe
dppe
dppe
dppe
dppe
dppe
–
NaOH
Et3N
–
Na2CO3 trace
Na2CO3 40
Na2CO3 <5
Na2CO3 30
Na2CO3 60
45
15
13
At the outset of our studies, we noted one literature
reports of metal-mediated decarbonylation of arenese-
lenol esters.[50] However, the example employed stoi-
chiometric quantities of Ni complex with a narrow
scope of unfunctionalized substrates. To explore the
proposed intramolecular decarbonylative coupling, Se-
phenyl benzoselenoate 1a was chosen as the model
substrate. The reaction proceeded smoothly in the
presence of catalytic amounts of Ni (acac)2 and dppe to
provide the desired product 2a and the hydrolysis of
selenoesters was not detected (Table 1, entry 1). This
result encouraged us to attempt further optimization,
and we assessed the efficiency of a variety of Ni
catalysts. NiCl2 was found to be more effective than
NiI2, Ni(acac)2, Ni(OAc)2 and NiCl2(dppe) (Table 1,
entries 1–5). Ni(cod)2 also showed high catalytic
activity (Table 1, entry 6). However, from the view-
point of practical operation, NiCl2 was the better
option. Next, a range of ligands (dppp, dppm, and
NiCl2
NiCl2
dppe
[a] Standard conditions: 1a (0.1 mmol), catalyst (0.01 mmol),
ligand (0.01 mmol), base (0.15 mmol), dioxane (0.5 mL), at
°
160 C in sealed tube, 12 h.
[b] Isolated yields.
[c] At room temperature.
[d]
°
At 120 C.
[e] NiCl2 (5 mol%) and dppe (5 mol%) were used.
dppe=1,2-Bis(diphenylphosphino)ethane;
dppp=1,3-Bis(diphenylphosphino) propane;
dppm=Bis(diphenylphosphino)methane.
1,10-phenanthroline) was tested and found to be less variety of functional groups such as methyl chloride
effective than dppe (Table 1, entries 8–10). Bases were (2b), fluoride (2c), nitrile (2d), ester (2e), and ether
also screened, and Na2CO3 was found to be the optimal (2f–2i) groups. Substrates with a substituent at the
choice (Table 1, entries 11, 12). We also attempted to meta- and ortho-position also worked well to give the
lower the reaction temperature; unfortunately, the corresponding products (2h, 2i). Furthermore, this
yields decreased sharply at low temperatures (Table 1, protocol could be extended to heterocyclic (2j–2l) and
entries 14 and 15). Control experiments showed that polyaromatic (2n) substrates, providing the desired
both the phosphine and Ni-complex played pivotal products in moderate to good yields. Next, the scope
roles in this reaction (Table 1, entries 16 and 17). of the Se-derived fragment was examined (Table 2).
Finally, the loading of catalyst was investigated; Substrates containing para-, meta-, and ortho-meth-
however, reducing the catalyst loading gave a lower oxyl groups (2o–2q) afforded the corresponding
yield (Table1, entry 18).
selenides in good yields. Electron-withdrawing groups
With the optimized reaction conditions in hand, we such as fluoro (2r) and trifluoromethyl (2s) were well
next investigated the substrate scope of the nickel- tolerated under the catalytic conditions. However, no
catalyzed intramolecular decarbonylative coupling of products were detected when alkyl or alkenyl selenol
selenoesters. Selenoesters bearing electron-donating as esters were used under the standard conditions(2v–
well as electron-withdrawing groups reacted smoothly 2x).
to provide diaryl selenides 2 in good yields. The
Diversification of natural products or drugs meets
reaction also showed excellent compatibility with a the increasing demand in biochemical and pharmaceut-
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Table 2. Substrate Scope.[a]
Scheme 2. Diversification of natural product derivatives.
Ni(cod)2 was used instead of NiCl2 in the catalytic
system, the yields were much improved.
To further highlight the utility of this novel method,
a sequential reaction was designed for the synthesis of
the organic functional material PSePCz, which could
be used to fabricate sensing systems for H2O2 and
2,4,6-trinitrotoluene (TNT).[51] As shown in Scheme 3,
PSePCz was easily accessible from readily available
carboxylic acids in three steps.
In summary, we have developed a practical decar-
bonylative diaryl selenide synthesis from aryl sele-
noesters via Ni catalysis. As opposed to the traditional
diaryl selenide syntheses, this protocol is characterized
by high atom efficiency; it can be executed with
readily available carboxylic acids as coupling precur-
sors, and only small amounts of harmful toxic wastes
are generated. By virtue of its high chemoselectivity,
our protocol holds promise for application in the
discovery of biological Se-containing lead compounds,
preparation of Se-containing medicinal compounds,
and synthesis of functional organic materials. Related
studies are underway in our laboratory.
[a] Reaction conditions: 1 (0.1 mmol), NiCl2 (0.01 mmol), dppe
(0.01 mmol), Na2CO3 (0.15 mmol), dioxane (0.5 mL), at
°
160 C in sealed tube. Isolated yields.
[b] 1.0 mmol scale.
Experimental Section
General Procedure for the Synthesis of Selenoether 2. In a
glovebox, substrate 1 (0.1 mmol) was added to a solution of
ical communities. These modification strategies could
provide functionalized analogs with enhanced bio-
logical activities or improved therapeutic capabilities
compared to their natural counterparts. In order to
verify the applicability and universality of this protocol
a complex structural system, the diversification of
natural product derivatives was implemented. Sele-
noesters derived from estrone and epiandrosterone
were subjected to the optimized reaction conditions.
As shown in Scheme 2, this reaction offers a general
method for introducing the selenide group into a
natural product or its derivative, while the ester moiety
acts as a functional handle for further modification.
For these substrates, only trace amount of products
could be obtained under standard conditions. When
Scheme 3. Synthesis of PSePCz.
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NiCl2 (0.01 mmol), dppe (0.01 mmol) and Na2CO3 (0.15 mmol)
in 1,4-dioxane (0.5 mL). Then the vessel was sealed and
removed from glovebox. The contents of the vial were then
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stirred at 160 C for 12 h. The reaction was cooled to room
temperature, and the crude mixture was filtered through a pad
of silica gel. The filtrate was then concentrated in vacuo to give
a residue, which was purified by flash column chromatography
over silica gel to give product 2.
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Acknowledgements
Financial support for this work was provided by the National
Natural Science Foundation of China (NSFC 21901202),
Natural Science Basic Research Program of Shaanxi (2020JQ-
576) and China Postdoctoral Science Foundation
(2020 M673620XB).
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