Synthesis of β-Selenylated Cyclopentanones via Photoredox-Catalyzed Selenylation/Ring-Expansion Cascades of Alkenyl Cyclobutanols

Article abstract of DOI:10.1055/s-0037-1611841

A photoredox strategy to access β-selenated cyclic ketone derivatives through the coupling reaction of 1-(1-arylvinyl)cyclobutanols with diselenides under blue LED irradiation and an air atmosphere was developed. This reaction employs the easily accessibl

Full text of DOI:10.1055/s-0037-1611841

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© Georg Thieme Verlag Stuttgart · New York
2019, 30, A–E
letter
A
en
H. I. Jung, D. Y. Kim
Letter
Synlett
Synthesis of -Selenylated Cyclopentanones via Photoredox-Cata-
lyzed Selenylation/Ring-Expansion Cascades of Alkenyl Cyclobutanols
Hye Im Jung
Dae Young Kim*a
O
photocatalyst
(3 mol%)
0
0
0
0-0
0
0
2-
6
3
3
7-7
5
0
5
R1
OH
R1
R2SeSeR2
SeR2
MeCN, air, rt
blue LEDs
Department of Chemistry, Soonchunhyang University,
Asan, Chungnam 31538, Republic of Korea
dyoung@sch.ac.kr
15 examples
up to 94%
R1 = aryl, benzyl R2 = phenyl, benzyl
Received: 19.04.2019
Accepted after revision: 08.05.2019
Published online: 29.05.2019
a) Previous works7
O
DOI: 10.1055/s-0037-1611841; Art ID: st-2019-u0221-l
Ar
OH
[X.]
Ar
X
Abstract A photoredox strategy to access -selenated cyclic ketone
derivatives through the coupling reaction of 1-(1-arylvinyl)cyclobuta-
nols with diselenides under blue LED irradiation and an air atmosphere
was developed. This reaction employs the easily accessible and shelf-
stable diselenides as a selenium radical source, and the reaction has ad-
vantages of mild reaction conditions and broad substrate scope.
X : alkyl, aryl, acyl, CF3, CF2H, CH(CO2Et)2
CF2CO2Et, SCF3, N3, N(SO2Ph)2, SO2Ar
b) Previous our work7j
O
[RSe.]
OH
Ar
Ar
SeR
SeR
Key words selenylation, semipinacol rearrangement, 1,2-alkyl migra-
Electricity
tion, 1-(1-arylvinyl)cyclobutanols, photoredox reaction
c) This work
O
Organoselenium compounds have attracted consider-
able attention in pharmaceutical and material sciences due
to their biological and chemical properties.1 It can also be
used as a chemical intermediate for organic synthesis.2 The
widespread application of these compounds has led to in-
tensive efforts to develop novel and convenient synthetic
methods.3 Deselenide, a reagent that is easily accessible and
stable on the shelf, has emerged as a valuable selenium for-
mulation for synthesizing organic selenium compounds.
Various reactions of diselenides with alkene, boronic acid,
aromatics, and diazonium salt have been used to supply a
variety of organoselenium compounds.4
The radical-initiated addition reaction to alkenes pro-
vided a practical protocol for the difunctionalization of un-
activated alkenes with high chemoselectivity.5,6 Recently,
several groups reported radical additions and ring-expan-
sion cascades via semipinacol rearrangement of alkenyl al-
cohols with a variety of radicals, such as acyl, alkyl, amine,
aryl, azido, difluoromethyl, phenylsulfonyl, and trifluoro-
methyl radicals, for the synthesis of -functionalized car-
bonyl compounds (Scheme 1, a).7
[RSe.]
OH
Ar
Ar
Photoredox
catalysis
Scheme 1 Strategy for photoredox-catalyzed selenylation/ring-expan-
sion sequences
Over the last decade, the visible-light-mediated pho-
toredox catalysis has emerged as a powerful approach for
organic chemists to introduce the functional group to or-
ganic compounds because of its environmentally friendly
and practical properties.8 Very recently, we have reported
the electrochemical selenylation/ring-expansion sequences
of alkenyl cyclobutanols (Scheme 1, b).7j Although this
method has been achieved by this system, a more efficient,
mild, and environmentally benign approaches for the sele-
nylation/ring-expansion sequences of alkenyl alcohols are
highly desired. We envisioned transformation of alkenyl cy-
clobutanols to -selenated cyclopentanones by visible-
light-mediated photoredox-catalyzed selenylation/ring-ex-
pansion sequence via semipinacol rearrangement with
diselenides as selenium radical precursors (Scheme 1, c).
© Georg Thieme Verlag Stuttgart · New York — Synlett 2019, 30, A–E

B
H. I. Jung, D. Y. Kim
Letter
Synlett
As part of a study for redox reaction and ring closure, we
have reported internal redox reactions9 and radical addi-
tions/ring-expansion sequences under mild conditions.7d–m
Herein, we report photoredox catalytic selenyla-
tion/ring-expansion cascades via semipinacol rearrange-
ment of alkenyl cyclobutanols. To determine optimized re-
action conditions for visible-light-mediated photoredox
catalytic selenylation/1,2-alkyl-migration sequences of
alkenyl cyclobutanol derivatives, we choose 1-[1-(4-me-
thoxyphenyl)vinyl] cyclobutanol (1c) and diphenyl disele-
nide (2a) as the model substrates. The reaction proceeded
in visible-light irradiation using blue LED (5 W, max = 455
nm) in acetonitrile with 5 mol% of photocatalyst. The reac-
tion was conducted with various organic and metal photo-
catalysts (Table 1, entries 1–9), among which a ruthenium
complex, Ru(bpy)3Cl2·6H2O, afforded the optimal result
(94% yield, Table 1, entry 8). An intensive screening revealed
that the reaction is best conducted in acetonitrile (Table 1,
entries 8 and 10–19). The reaction tolerates photocatalyst
loading down to 3 mol% without a decrease in yield (Table
1, entries 20 and 21). Using white or green LEDs to replace
blue LEDs led to a slight decrease in reaction yields (Table 1,
entries 22 and 23). The controlled experiments showed that
the reaction completely suppressed in the absence of pho-
tocatalyst or light source (Table 1, entries 24 and 25).
We turned our attention to study the substrate scope of
1-(1-arylvinyl)cyclobutanols 1 with diphenyl diselenide
(2a, Scheme 2). The reactions of cyclobutanol substrates
1a–h showed that a variety of functional groups were well
tolerated, including methyl, methoxy, fluoro, and chloro;
and the corresponding cyclopentanone products 3a–h were
obtained with 64–94% yields (Scheme 2). The electronic ef-
fect on the aryl of cyclobutanols 1 is important to the reac-
tivity of this selenylation and ring-expansion sequences:
cyclopentanones containing electron-donating-substituted
aryl groups had higher yields than those with electron-
withdrawing ones. The 2-naphthyl-substituted cyclobuta-
nol 1i provided the corresponding product 3i in 72% yield.
Notably, this radical selenylation/1,2-alkyl-migration reac-
tion with alkyl-substituted alkenyl cyclobutanol gave 61%
yield of corresponding product 3j under the optimized re-
action conditions. Next, dibenzyl diselenide (2b) was also
effective in the reaction, resulting in the corresponding
products 3k–o were obtained in moderate to high yields
(55–75%, Scheme 2).
Table 1 Optimization of Reaction Conditionsa
O
photocatalyst
(5 mol%)
O
OH
PhSeSePh
SePh
solvent, rt
O
blue LEDs
1c
2a
3c
Entry
Photocatalyst
Solvent
Time (h)
Yield (%)b
1
2
eosin Y
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
DMSO
DMF
12
16
16
12
16
12
12
11
11
22
22
21
21
21
24
21
11
22
21
14
14
21
21
24
24
24
37
46
24
29
30
41
45
94
37
trace
trace
trace
20
32
24
22
37
65
55
94
78
66
64
0
Na2eosin Y
3
eosin B
4
rhodamine B
5
rhodamine 6G
fac-Ir(ppy)3
6
7
F(Ir)picc
8
Ru(bpy)3Cl2·6H2O
Ru(bpy)3(PF6)2
Ru(bpy)3Cl2·6H2O
Ru(bpy)3Cl2·6H2O
Ru(bpy)3Cl2·6H2O
Ru(bpy)3Cl2·6H2O
Ru(bpy)3Cl2·6H2O
Ru(bpy)3Cl2·6H2O
Ru(bpy)3Cl2·6H2O
Ru(bpy)3Cl2·6H2O
Ru(bpy)3Cl2·6H2O
Ru(bpy)3Cl2·6H2O
Ru(bpy)3Cl2·6H2O
Ru(bpy)3Cl2·6H2O
Ru(bpy)3Cl2·6H2O
Ru(bpy)3Cl2·6H2O
–
9
10
11
12
13
14
15
16
17
18
19
20d
21e
22f
23g
24h
25i
26j
MeOH
H2O
Acetone
PhMe
EA
THF
DCM
DCE
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
Ru(bpy)3Cl2·6H2O
Ru(bpy)3Cl2·6H2O
0
The practical synthesis of -selenated cyclic ketones has
been achieved by the photoredox-catalyzed selenylation
and ring-expansion cascades of 1-(1-arylvinyl)cyclobutanol
derivatives with diselenides. Under the optimized reaction
conditions, 1-[1-(p-tolyl)vinyl]cyclobutanol (1b) with di-
phenyl diselenide (2a) afford the desired -selenated cyclo-
pentanone 3b with 81% yield (Scheme 3). It is noteworthy
that this cascade can also be conducted on gram scale.
To demonstrate the feasibility of this protocol, we de-
cided to further investigate synthetic utility of -selenated
cyclopentanones 3 through Dowd–Beckwith-type ring ex-
pansion to afford ring-enlarged cyclohexanone derivatives
25
a Reaction conditions: 1-[1-(4-methoxyphenyl)vinyl]cyclobutanol (1c, 0.1
mmol), diphenyl diselenide (2a, 0.06 mmol), photocatalyst, solvent (1 mL),
blue LEDs, room temperature under air.
b Isolated yields.
c F(Ir)pic = bis(3,5-difluoro-2-(2-pyridyl)phenyl-(2-carboxypyridyl) iridium (III).
d 3 mol% photocatalyst loading.
e 1 mol% photocatalyst loading.
f White LEDs instead of blue LEDs.
g Green LEDs instead of blue LEDs.
h Without photocatalyst.
i The reaction was performed in the dark.
j The reaction was performed under N2.
© Georg Thieme Verlag Stuttgart · New York — Synlett 2019, 30, A–E

C
H. I. Jung, D. Y. Kim
Letter
Synlett
O
Ru(bpy)3Cl2.6H2O
(3 mol%)
R
O
OH
R1
R1
R2SeSeR2
SeR2
O
MeCN, air, rt
blue LEDs
Bu3SnH, AIBN
2
1
3
SePh
PhMe, 100 °C, 5 h
O
R
3a, R = H
3b, R = Me
4a, R = H, 63% yield
4b, R = Me, 75% yield
O
O
O
Ph
SePh
Scheme 4 Dowd–Beckwith rearrangement of 3
SePh
SePh
3b
3a
3c
reducing yield of product was obtained (Table 1, entry 26).
This result indicates that the oxygen plays an important role
in the reaction. In addition, when 2,2,6,6-tetramethylpiper-
idin-1-yloxyl (TEMPO), as a radical inhibitor, was added
into the reaction, no desired product was detected (Scheme
5). This outcome was consistent with our hypothesis that a
radical pathway can be involved in this cascade reaction.
We propose the reaction mechanism as shown in Scheme 6
based on the results of the experiment and related litera-
ture.11 A photocatalyst Ru(bpy)3Cl2·6H2O is converted into
the excited state [Ru(bpy)3Cl2·6H2O]* under visible-light ir-
radiation. Energy-transfer process then occurs to diphenyl
diselenide (2a) and would generate ground-state
Ru(bpy)3Cl2·6H2O and selenium radicals I. After that, seleni-
um radical I react with 1-(1-phenylvinyl) cyclobutanol (1a)
to give carbon radical III, which is oxidized to cation inter-
mediate IV by oxygen (path a). The semipinacol rearrange-
ment through 1,2-alkyl migration of intermediate IV af-
fords the cyclopentanone 3a. Alternatively, radical I can also
be oxidized by oxygen to selenium cation II which react
with 1-(1-phenylvinyl) cyclobutanol (1a) to give corre-
sponding cation IV (path b).
21 h, 83% yield
19 h, 88% yield
Cl
14 h, 94% yield
F
O
O
O
SePh
SePh
SePh
3d
3f
3e
24 h, 74% yield
21 h, 83% yield
25 h, 73% yield
O
O
O
F
SePh
SePh
SePh
3i
3g
3h
25 h, 72% yield
25 h, 72% yield
25 h, 64% yield
Ph
O
O
O
Ph
SePh
SeBn
SeBn
3j
25 h, 61% yield
3k
3l
24 h, 72% yield
8 h, 65% yield
O
F
O
O
O
SeBn
SeBn
SeBn
O
Ru(bpy)3Cl2.6H2O
Ph
OH
3m
17 h, 75% yield
3n
3o
(3 mol%)
Ph
SePh
PhSeSePh
23 h, 68% yield
24 h, 55% yield
MeCN, air, rt
blue LEDs, 24 h
TEMPO (3 equiv)
Scheme 2 Substrate scope. Reaction conditions: allylic alcohol 1 (0.1
mmol), R2SeSeR2 2 (0.06 mmol), Ru(bpy)3Cl2·6H2O (3 mol), MeCN (1
mL), blue LEDs, room temperature under air. Isolated yields are given.
1a
2a
3a, trace
Scheme 5 Radical-trapping experiment
visible light
O
Ru(bpy)3Cl2.6H2O
OH
PC
PC
PhSeSePh
(3 mol%)
SePh
MeCN, air, rt
blue LEDs, 24 h
1b
(3 mmol)
2a
3b
(0.834 g, 81%)
O2
O2
path b
(1.8 mmol)
PhSe•
PhSe+
PhSe–SePh
Scheme 3 Gram-scale synthesis of 3b
2a
I
II
path a
1a
1a
4.10 The reaction of cyclopentanones 3 with Bu3SnH and
azobis(isobutyronitrile) (AIBN) affords high yields of ring-
enlarged cyclohexanones 4 in toluene at 100 °C for 5 hours
(Scheme 4).
PhSe
Ph
PhSe
Ph
O
Ph
OH
OH
+
SePh
– H+
O2
O2
In order to gain insight into the reaction mechanism,
some control experiments were performed. When the reac-
tion was carried out under anhydrous nitrogen, significantly
3a
IV
III
Scheme 6 Proposed reaction mechanism
© Georg Thieme Verlag Stuttgart · New York — Synlett 2019, 30, A–E

D
H. I. Jung, D. Y. Kim
Letter
Synlett
In conclusion, we have developed a practical synthesis
of -selenated cyclopentanone derivatives 3 via photore-
dox-catalyzed selenylation and ring-expansion cascade of
alkenyl cyclobutanol derivatives 1 with diselenides.12,13 This
approach is environmentally friendly by using shelf-stable
diselenides as selenium radical source and visible light as
source of energy. This synthetic method affords a facile way
to prepare -selenated cyclopentanone derivatives.
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Funding Information
This research was supported by Basic Science Research Program
through the National Research Foundation of Korea (Grant-No. NRF-
2016-R1D1A1B03933723) and Soonchunhyang University Research
Fund.
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Supporting Information
Supporting information for this article is available online at
https://doi.org/10.1055/s-0037-1611841.
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© Georg Thieme Verlag Stuttgart · New York — Synlett 2019, 30, A–E

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(12) General Procedure for Photoredox Selenylation/Ring-Expan-
sion Sequences of Alkenyl Cyclobutanols
An oven-dried flask equipped with a magnetic stir bar was
charged with 1-(1-arylvinyl)cyclobutanols 1 (0.1 mmol), disele-
nide 2 (0.06 mmol), Ru(bpy)3Cl2·6H2O (2.2 mg, 3 mol), and ace-
tonitrile (1 mL) under air. The reaction mixture was stirred for
8–25 h under irradiation of blue LEDs (5 W, 455 nm). The reac-
tion mixture was concentrated under vacuum and purified by
chromatography on silica gel (ethyl acetate/n-hexane = 1:20) to
afford -selenated cyclic ketone derivatives 3.
(13) 2-Phenyl-2-[(phenylselanyl)methyl]cyclopentanone (3a)
Yield 83%; yellow oil. 1H NMR (400 MHz, CDCl3):  = 7.42–7.37
(m, 4 H), 7.34–7.30 (m, 2 H), 7.27–7.23 (m, 1 H), 7.21–7.18 (m, 3
H), 3.39 (d, J = 12 Hz, 1 H), 3.30 (d, J = 12.4 Hz, 1 H), 2.70–2.65
(m, 1 H), 2.40–2.20 (m, 3 H), 2.00–1.90 (m, 1 H), 1.84–1.73 (m, 1
H). 13C NMR (100 MHz, CDCl3):  = 217.9, 138.4, 132.6, 131.0,
128.9, 128.7, 127.4, 126.8, 126.7, 57.8, 37.8, 37.4, 33.6, 18.4.
HRMS (ESI): m/z calcd for C18H18OSe [M]+ : 330.0523; found:
330.0527.
(9) For a selection of our recent work on C–H activation, see:
(a) Kang, Y. K.; Kim, S. M.; Kim, D. Y. J. Am. Chem. Soc. 2010, 132,
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2014, 3, 399. (d) Kang, Y. K.; Kim, D. Y. Chem. Commun. 2014, 50,
222. (e) Suh, C. W.; Kim, D. Y. Org. Lett. 2014, 16, 5374. (f) Kwon,
© Georg Thieme Verlag Stuttgart · New York — Synlett 2019, 30, A–E