Electrochemical oxidative cyclization of olefinic carbonyls with diselenides

Article abstract of DOI:10.1039/c9gc02665g

The tandem cyclization of olefinic carbonyls with easily accessible diselenides facilitated by electrochemical oxidation has been successfully developed, which provides an environmentally friendly method for the construction of C-Se and C-O bonds simultaneously. A series of seleno dihydrofurans and seleno oxazolines, bearing fragile heterocycles, subtle C-I bonds and supernumerary vinyl groups, were forged using this elegant chelation strategy. Neither metal catalysts nor external chemical oxidants are required to promote this transformation.

Full text of DOI:10.1039/c9gc02665g

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DOI: 10.1039/C9GC02665G
Journal Name
COMMUNICATION
Electrochemical Oxidative Cyclization of Olefinic Carbonyls with
Diselenides
Zhipeng Guan,a Yunkun Wang,a Huamin Wang,a Yange Huang,a Siyuan Wang,a Hongding Tang*,a
Received 00th January 20xx,
Accepted 00th January 20xx
Heng Zhang*,a Aiwen Lei*,a
DOI: 10.1039/x0xx00000x
www.rsc.org/
The tandem cyclization of olefinic carbonyls with easily accessible a more effective and sustainable method to construct
diselenides facilitated by electrochemical oxidation has been dihydrofuran derivatives using olefinic carbonyl compounds.
OMe
O
successfully developed, which provides an environmentally friendly
manner for the construction of C−Se and C-O bonds simultaneously.
O
NC
H
O
OMe
HO
A series of seleno dihydrofurans and seleno oxazolines, bearing
fragile heterocycles, subtle C-I bond and supernumerary vinyl
groups, were forged with this elegant chelation strategy. Neither
metal catalysts nor external chemical oxidants is required to
promote this transformation.
a)
O
O
Cy
N
H
H
Dendritic extension activities
Anti-cancer activity
O
NH3
SePh
Se
O
The dihydrofurans are important structural skeletons in a wide
range of natural products, as well key structural motifs in
organic synthesis such as aromatization, Heck reaction, ring
opening of the reactive enol ether moiety, etc.1 In the view of
the drug design, dihydrofurans were also displayed to act as
potential lead compounds (Scheme 1, a).2 Thus, a variety of
synthetic methods have been developed for the construction of
this core moiety by building of C-O bonds.3 Among the various
synthetic routes, oxidative cyclization of 1,3-dicarbonyl
compounds with alkenes provided an excellent access for the
synthesis of dihydrofurans owing to the acidic α-H of carbonyls
and electronegativity of the oxygen atom of carbonyls.4 In
addition, tandem cyclization of the olefinic carbonyl compounds
has been utilized as an effective approach to introduce
functional groups into the dihydrofuran skeletons.5 Recently,
relevant developments have been independently reported by
Guo, Li, Liu et al.5c-5g Despite the progress achieved in this area,
these above methods required excess oxidants, chemical
additives and/or expensive metal catalysts, which not only limit
the potential application to a certain extent but also bring about
the possible metal residual that is adverse for the further
application. Therefore, it is necessary and appealing to develop
b)
O
MeO
Glutathione peroxidase-like activity
-lyase activity
c) Electrooxidative tandem cyclization of olefinic carbonyl with diselenides
O
R
O
C
Pt
R1SeSeR1
+
R
SeR1
GWE
metal-free
exogenous-oxidant-free
up to 93% yield
EWG
Scheme
1 The application and synthesis of dihydrofurans/
organoselenium compounds
The introduction of selenium atoms into organic molecules
has attracted much attention in pharmaceutical, agrochemical
and material industries because of the special biological and
chemical properties (Scheme 1, b).6 Due to the wide
applications of selenium-containing organic compounds,
continuous endeavors have been made to develop efficient
synthetic methods to access these molecules.7 Especially, the
construction of C-Se bonds has become a research hotspot in
the last decade. In addition, the seleno group could be
manipulated readily under suitable conditions owing to its
versatile functionality.8 Compared with other selenium-
reagents (PhSeBr, PhSeCl, PhthSe, etc), diselenides are a kind of
easily accessible and operatable selenium-reagents in organic
synthesis, which provide a good choice for C-Se bonds
formation.
a Engineering Research Center of Organosilicon Compounds & Materials, Ministry of
Education, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan,
430072, P.R. China
Electronic Supplementary Information (ESI) available: [details of any supplementary
information available should be included here]. See DOI: 10.1039/x0xx00000x
In recent years, electrochemical synthesis has been widely
recognized as a sustainable and environmentally benign
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
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synthetic tool in synthetic chemistry.9 Electrochemistry offers a platinum sheet with graphite rod or iron plate ledVtioewdAertcicrleeOansleinde
DOI: 10.1039/C9GC02665G
direct means of generating active intermediate, which is yields obviously (Table 1, entries 9-10). When the reaction was
superior than the classical chemical process. A lot of reports opened to air, the yield was nearly reduced by half (Table 1,
have been made on cross-coupling and difunctionalization of entry 11). Control experiments indicated that no conversion
alkenes by electrochemistry.10 Given that the importance of occurred without electricity (Table 1, entry 12).
O
R
selenium-containing
compounds
in
pharmaceutical,
O
nBu4NBF4, (0.1 mmol),
R
+
PhSeSePh
0.3 mmol
HOAc (100 L), MeCN (12 mL)
agrochemical and material industries, we report herein an
electrochemical oxidative cyclization of olefinic carbonyls with
diselenide toward C−Se and C-O bonds formation. A series of
functionalized dihydrofurans and oxazolines were synthesized
in the absence of metal catalysts and external oxidants (Scheme
1, c).
SePh
GWE
EWG
10 mA, 2.5 h, 0 ℃,N2
,
0.3 mmol
R
O
O
SePh
R = 4-F, 3aa, 90%; R = H, 3ba, 91%; R = 4-Me, 3ca, 56%;
R = 4-OMe, 3da, 56%; R = 3-Me, 3ea, 69%
Table 1. Optimization of the Electrochemical Oxidative Cyclizationa
R
F
O
O
Ph
Ph
Ph
Ph
Ph
Me
OMe
O
O
OEt
O
O
O
O
Ph
Ph
Ph
SePh Ph
SePh
nBu4NBF4, (0.1 mmol),
SePh
SePh
HOAc (100 L), MeCN (12 mL)
O
O
O
O
SePh
O
3ga, 71%
3ia, 55%
3fa, 78%
3ha, 68%
+
PhSeSePh
10 mA, 2.5 h, 0℃,N2,
F
O
Ph
Ph
Ph
Me
Ph
2a
O
O
Ph
O
SePh
Me
Me
SePh
O
F
1a
Ph
Ph
Ph
SePh
SePh
Ph
F
3aa 90% isolated yield
O
O
O
O
3la, 26%
3ja, 70%
3ka, 37%
3ma, 52%
entry
variation from standard conditions
yield (%)b
Ph
Me
O
Ph
O
Ph
Ts
O
O
1
2
3
4
no HOAc
86
0
Me
+
SePh
Ph
SePh
MeOH (12mL)
SePh
SePh
NC
Me
3na
O
3na
O
MeCN/H2O (11 mL/1 mL)
MeCN/HFIP (11 mL/1 mL)
0
88% (2.6:1)
Me
3oa, 76%
3pa, 50%
0
Ph
Me
O
O
O
O
5
6
7
8
PhSeSePh (0.2mmol)
71
68
88
23
tBuO
EtO
EtO
SePh
SePh MeO
SePh
30℃
SePh
O
O
nBu4NPF6, (0.1 mmol),
TBAI (0.1mmol)
3ra, 41%
3sa, 78%
O
O
3ta, 82%
3qa, 65%
Me
Ph
Ph
Ph
O
O
O
O
9
C(+)/Fe(-)
C(+)/C(-)
68
56
53
0
Me
SePh
Ph
SePh
SeCH2Ph
SeMe
10
11
12
3ua, 93%
3ac, 50%
O
O
3va, 93%
3ab, 60%
O
O
Air
a
n
no electric current
Standard conditions: 1 (0.3 mmol), 2 (0.3 mmol), Bu4NBF4
a
n
(0.25 mmol), MeCN (12 mL), HOAc (100 μL), C anode, Pt cathode,
undivided cell, constant current = 10 mA (janode = 4.4 mA/cm2),
0 oC, N2, 2.5 h.
Standard conditions: 1a (0.3 mmol), 2a (0.3 mmol), Bu4NBF4
(0.25 mmol), MeCN (12 mL), HOAc (100 μL), C anode, Pt cathode,
undivided cell, constant current = 10 mA (janode = 4.4 mA/cm2),
0 oC, N2, 2.5 h. b 19FNMR yield, 1-fluoro-3-methylbenzene as an
internal standard.
Scheme 2. Scope of the Olefinic Carbonyls with Diselenidesa
With the optimized conditions in hand, we turned to explore
the substrate scope of the tandem cyclization reactions in
Scheme 2. Symmetric olefinic carbonyls bearing electron-
withdrawing groups or electron-donating groups on the
para/meta position of the phenyl ring could react smoothly with
diphenyl diselenide to afford the corresponding dihydrofuran
compounds in moderate to good yields (3aa-3ea). It is
noteworthy that γ-substituted (Ph, Me, CO2Et, CO2Me)
symmetric olefinic carbonyls could also be transformed to the
target products in satisfactory yields (3fa-3ia). Subsequently,
we continued to investigate the effects of δ-substituted
substrates under standard conditions. Obviously, the steric
hindrance has a great influence on this transformation (3ja-3la).
To our delight, olefinic carbonyls containing γ, δ-disubstituted
groups, could also react with 1,2-diphenyldiselane to generate
the target molecule in 52% yield (3ma). Inspired by the above
results, we attempted to expand this method using
unsymmetric olefinic carbonyls. 2-allyl-1-phenylbutane-1,3-
dione could reacted with 2a, furnishing 2.6:1 separable mixture
with excellent yield (3na and 3n'a). Unsymmetric olefinic
carbonyls, α-substituted group (CN, CO2Et, Ts) instead of acyl
group, worked in 50-76% yields (3oa-3qa). In addition, alkyl
Initially, we commenced the electrochemical oxidative
cyclization
reaction
by
using
2-allyl-1,3-bis(4-
fluorophenyl)propane-1,3-dione (1a) with diphenyl diselenide
(2a) as model substrates in an undivided electrolytic cell.
Encouragingly, utilizing nBu4NBF4 as the supporting electrolyte,
HOAc as additive and acetonitrile as solvent, (4-fluorophenyl)(2-
(4-fluorophenyl)-5-((phenylselanyl)methyl)-4,5-dihydrofuran-
3-yl)methanone (3aa) could been obtained in 90% isolated yield
with graphite rod anode and platinum sheet cathode (Table 1).
The yield of the desired product decreased slightly in the
absence of HOAc (Table 1, entry 1). The reaction was completely
inhibited under other solvents with the formation of side
products (Table 1, entries 2-4). When the amount of diphenyl
diselenide was reduced from 0.3 mmol to 0.2 mmol, only 71%
yield could be obtained (Table 1, entry 5). It was remarkable
that only 68% yield was got when the reaction was conducted
at 30 oC (Table 1, entry 6). As to the other supporting
n
electrolytes, Bu4NPF6 showed a similar reactivity compared
n
with Bu4NBF4, while product 3aa was formed in diminished
yield when TBAI was used instead of nBu4NBF4 (Table 1, entries
7-8). Subsequently, various cathodes were examined. Replacing
2 | J. Name., 2012, 00, 1-3
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O
Ph
nBu4NBF4, (1 mmol)
substances such as 1r-1u were amenable in the current reaction
system, and the corresponding dihydrofurans were obtained in
moderate to good yields (3ra-3ua). A surprisingly high isolated
yield was obtained using 2-allylcyclohexane-1,3-dione 1v as a
substrate (3va). Next, two diverse diselenides were employed
as substrates to explore the scope of this reaction. It is
noteworthy that dimethyl diselenides and dibenzyl diselenides
were also good reaction candidates and furnished the target
product in acceptable yields (3ab and 3ac).
O
View Article Online
10 mA, 25 h, 0℃,N2,
DOI: 10.1039/C9GC02665G
Ph
+
PhSeSePh
Ph
SePh
MeCN (120 mL), HOAc (1 mL)
O
Ph
O
2a 3 mmol
3ba 0.75g, 60% yield
1b 3 mmol
Ph
O
Br Br Ph
O
Ph
O
H2O2, THF
DABCO, DCM
H2O, NBS
O
3ba
O
Se Ph
O
Ph
7, 85 mg, 98% yield
SePh
6, 45 mg, 76% yield
O
Scheme 4. Gram-Scale Tandem Cyclization of 1b and Derivatization of
3ba
R
nBu4NBF4, (0.1 mmol),
O
PhSeSePh
0.15 mmol
+
R
N
H
MeCN (5 mL), CF3CH2OH (1 mL)
N
SePh
10 mA, 2 h, 0℃,N2,
0.3 mmol
To further demonstrate the potential application of this
electrochemical oxidative tandem cyclization, a gram scale
reaction was carried out. With the established electrochemical
strategy, the reaction could proceed smoothly and 3ba was
obtained in 60% yield. Furthermore, the versatility of 3ba was
also pursued. A ring opening process of 3ba led to the formation
of valuable α, α-dibromoketone compound 6 with NBS and
DABCO as the electrophilic halogen source and the catalyst,
respectively. In addition, selenoxide 7 was obtained via
oxidation using H2O2 in nearly quantitative yield.
R
Ph
Me
O
O
N
O
SePh
N
SePh
5ja, 50%
5ia, 65%
N
SePh
O
R = H, 5aa, 88%
O
R = 4-OMe, 5ba, 82%
R = 2-Me, 5ca, 74%
R = 4-F, 5da, 70%
R = 4-Br, 5ea, 58%
R = 3-Cl, 5fa, 49%
R = 4-I, 5ga, 79%
N
S
O
O
N
N
N
SePh
SePh
SePh
5ka, 72%
5la, 49%
5ma, 68%
R = 4-CF3, 5ha, 69%
Ph
O
O
Me
Ph
standard condition
0.6 mmol TEMPO
Cy
O
O
+
PhSeSePh
O
Ph
O
O
SePh
N
N
N
SePh
SePh
N
SePh
O
Ph
Ph
3ba only trace
SePh
2a
5na, 54%
5oa, 68%
5pa, 50%
5qa, 60%
1b
a
n
Scheme 5. Control Experiments
Standard conditions: 4 (0.3 mmol), 2a (0.3 mmol), Bu4NBF4
To explore the reaction mechanism, control experiments
were conducted under different conditions. Only trace amount
of the product was detected when 2 equiv. of TEMPO was
added (Scheme 5). On the other hand, the cyclic voltammetry
experiments of 2a. The oxidation and reduction peaks of 2a
could be observed at 1.8 V and -1.5 V vs. Ag/AgCl, respectively.
Therefore, the diphenyl diselenide 2a may be involved in both
oxidation and reduction processes in electrochemical
conditions. On the basis of aforementioned experimental
results and literature reports,7h-7j a proposed mechanism is
outlined in Scheme 6. Firstly, diphenyl diselenide is reduced at
cathode to give an anion radical intermediate I, which is further
decomposed to give phenylselenium radical and phenyl
selenium anion. Thereafter, phenylselenium radical is captured
by alkenyl of 1b to form alkyl radical II, which is further oxidized
at anode. The fast ring closing followed by nucleophilic attack of
the oxygen atom of carbonyl, as well as deprotonation furnish
to the formation of desired product (path a). Alternatively, the
pathway in which 1b reacts with phenylselenium radical to form
the alkyl radical II, could not be completely ruled out (path b).
(0.1 mmol), MeCN (5 mL), CF3CH2OH (1 mL), C anode, Pt cathode,
undivided cell, constant current = 10 mA (janode = 4.4 mA/cm2),
0 oC, N2, 2 h.
Scheme 3. Scope of the Unsaturated Amides with Diselenides
Encouraged by the efficient tandem cyclization of olefinic
carbonyls to construct dihydrofurans, we next turned our
attention to expand this protocol to provide oxazolines using
unsaturated amides and 1,2-diphenyldiselane. To our delight, a
series of oxazolines were produced successfully under slightly
modified conditions, as shown in Scheme 3. N-allylamides
containing electron-rich aryl groups (Ph, 4-OMePh, 2-MePh,
Naph) could be employed easily to construct C−Se and C-O bond
with 1,2-diphenyldiselane, affording the corresponding seleno
oxazolines in moderate to excellent yields (5aa-5ca, 5ia). The
sensitive halogen groups, especially subtle C-I bond, were
compatible with this strategy (5ea-5ga). No obvious negative
effect was observed for the strong electron withdrawing group
substituted substrate (5ha). It is worth noting that the methyl
derivative containing a quaternary carbon center could be
obtained with acceptable yield (5ja). N-allylamides, with fragile
thiophene, furan and pyridine rings, also were well-tolerated to
furnish the corresponding cyclization products with moderate
yields (5ka-5ma). Gratifyingly, N-allyvinylamide and N-
allycinnamide were also good candidates, and could be
converted to the desired products with 68% and 54% yields,
respectively (5na and 5oa). Similarly, the desired products can
also be accessed from N-allyalkylamides (5pa and 5qa).
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Tamura, C. Tohda, N. Toyooka, H. Nemoto and Y. Matsuya,
O
View Article Online
DOI: 10.1039/C9GC02665G
Bioorg. Med. Chem., 2013, 21, 4459-4471.
-e-
-e-, -H+
Ph
SePh
PhSeSePh
3ba
1b
COPh
Ⅱ
3. (a) S. Son and G. C. Fu, J. Am. Chem. Soc., 2007, 129, 1046-1047.
(b) J.-L. Zhou, Y. Liang, C. Deng, H. Zhou, Z. Wang, X.-L. Sun, J.-C.
Zheng, Z.-X. Yu and Y. Tang, Angew. Chem. Int. Ed., 2011, 50,
7874-7878. (c) J.-L. Zhou, L.-J. Wang, H. Xu, X.-L. Sun and Y. Tang,
ACS Catal., 2013, 3, 685-688. (d) F.-L. Zhu, Y.-H. Wang, D.-Y.
Zhang, J. Xu and X.-P. Hu, Angew. Chem. Int. Ed., 2014, 53,
10223-10227. (e) A. Guđmundsson, K. P. J. Gustafson, B. K. Mai,
B. Yang, F. Himo and J.-E. Backvall, ACS Catal., 2018, 8, 12-16. (f)
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Merino and J. L. Vicario, Angew. Chem. Int. Ed., 2018, 57, 8225–
8229.
+2e-
2H+
O
H2
(path b)
O
-e-, -H+
PhSe
Ph
Ph
SePh
3ba
COPh
COPh
Ⅱ
1b
+e-
PhSeSePh
PhSeSePh
Ⅰ
PhSe
+
PhSe
(path a)
2a
Scheme 6. Proposed Reaction Mechanism
4. (a) J.-i. Yoshida, K. Sakaguchi and S. Isoe, Tetrahedron Lett.,
1986, 27, 6075-6078. (b) E. Baciocchi and R. Ruzziconi, J. Org.
Chem., 1991, 56, 4772-4778. (c) H. Yi, Z. Liao, G. Zhang, G. Zhang,
C. Fan, X. Zhang, E. E. Bunel, C.-W. Pao, J.-F. Lee and A. Lei,
Chem. - Eur. J., 2015, 21, 18925-18929. (d) S. Tang, K. Liu, Y.
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2016, 52, 6817-6820. (g) J. Lou, Q. Wang, K. Wu, P. Wu and Z.
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Liang, Y. Pan, and A. Lei, ChemElectroChem, 2019, 6, 3383–3386.
Conclusions
In summary, we have developed an economical and practical
methodology for C−Se and C-O bonds forming via
electrochemical oxidative tandem cyclization. An array of
seleno dihydrofurans and oxazolines were obtained successfully
in moderate to excellent yields. Importantly, the gram scale
experiment and the easy following derivatization demonstrate
the potential application of this protocol in pharmaceutical and
synthetic research.
Acknowledgements
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This work was supported by the National Natural Science
Foundation of China (21520102003) and the Hubei Province
Natural Science Foundation of China (2017CFA010). The
Program of Introducing Talents of Discipline to Universities of
China (111 Program) is also appreciated.
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