Ammonium Iodide Catalyzed Selenolactonization of Unsaturated Acids

Article abstract of DOI:10.1055/s-0035-1560348

A convenient procedure is developed for the preparation of selenolactones from unsaturated acids and diselenides using a catalytic amount of ammonium iodide in combination with m-chloroperoxybenzoic acid as the oxidant. This catalytic ring-closing method

Full text of DOI:10.1055/s-0035-1560348

SYNTHESIS
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© Georg Thieme Verlag Stuttgart · New York
2016, 48, 57–64
paper
57
H. Shi et al.
Paper
Synthesis
Ammonium Iodide Catalyzed Selenolactonization of Unsaturated
Acids
Hongwei Shia
Chen Yua
Min Zhub
Jie Yan*a
O
NH4I (cat.), mCPBA
O
RSeSeR
+
SeR
CF3CH2OH, 5 h, r.t.
COOH
16 examples
up to 93% yield
a College of Chemical Engineering, Zhejiang University of Technology,
Hangzhou 310032, P. R. of China
jieyan87@zjut.edu.cn
b College of Biological and Environmental Sciences, Zhejiang Shuren
University, Hangzhou 310015, P. R. of China
Received: 26.06.2015
Accepted after revision: 05.09.2015
Published online: 24.09.2015
lide ion to an alkene and a decrease in stereoselectivity, an
alternative procedure for the formation of electrophilic
phenylselenium cations is via oxidation of cheaper and less
toxic diphenyl diselenide (Ph2Se2) with oxidants such as
ammonium peroxydisulfate, m-nitrobenzenesulfonyl per-
oxide, lead(IV) acetate [Pb(OAc)4], cerium(IV) ammonium
nitrate [CAN, Ce(NH4)2(NO3)6] and copper(II)[copper(I)]/
oxygen [Cu2+(Cu+)/O2] systems.8 However, the use of toxic
metal oxidants and the fact that some of these oxidations
need long reaction times or high reaction temperatures
have limited their applications.
DOI: 10.1055/s-0035-1560348; Art ID: ss-2015-h0403-op
Abstract A convenient procedure is developed for the preparation of
selenolactones from unsaturated acids and diselenides using a catalytic
amount of ammonium iodide in combination with m-chloroperoxyben-
zoic acid as the oxidant. This catalytic ring-closing method proceeds ef-
ficiently at room temperature under neutral conditions, and in short re-
action times, to afford the corresponding selenolactones in good yields.
Using the same reaction conditions, cyclic selenoethers and tellurocy-
clization products are prepared, thus extending the catalytic applica-
tion of inorganic iodides in organic synthesis.
Hypervalent iodine reagents, which are readily available
and easy to handle, demonstrate low toxicities and reactivi-
ties similar to those of heavy metal reagents, and can pro-
mote oxidative cleavage of the Se–Se bond of diphenyl
diselenide to generate a reactive electrophilic selenium spe-
cies,9 however, the catalytic utilization of hypervalent io-
dine reagents in organoselenium chemistry is not common.
In our recent research, we found that catalytic amounts of
inorganic iodides such as potassium iodide (KI) in combina-
tion with oxidants could be used instead of hypervalent io-
dine reagents, with similar results being obtained.10 Based
on this success, we have investigated a novel procedure for
the synthesis of selenolactones. Herein, we report a conve-
nient method for the selenolactonization of unsaturated
acids by employing ammonium iodide (NH4I) as the catalyst
and m-chloroperoxybenzoic acid (mCPBA) as the terminal
oxidant, resulting in the formation of the corresponding
selenolactones in good yields.
Key words selenolactonization, selenolactone, diselenide, ammonium
iodide, catalytic addition
Lactonization plays an important role in modern organ-
ic synthesis, not only because lactones occur in nature in
great abundance and variety, but also represent a particu-
larly useful class of synthons.1 A significant number of lac-
tonizations involve the cyclization of unsaturated carboxyl-
ic acids initiated by suitable electrophilic reagents.2 As a re-
sult of their synthetic applicability,3,4 and biological
activities such as antitumor, antibacterial and other prop-
erties,5 organoselenium compounds have gained increased
importance in recent years. The introduction of organosele-
no groups into organic molecules to form C–Se bonds has
been widely studied, in which the use of selenenylating re-
agents [PhSeX (X = Br, Cl)] through electrophilic reactions is
the most common protocol.3 Since Campos and Petragnani
reported the first cyclization of unsaturated acids with ar-
ylselenium halides in 1960,6 selenolactonization reactions
have received sustained attention, and represent very reli-
able strategies in synthetic design.3a,b,7 Due to the moisture-
sensitive nature of phenylselenyl halides (PhSeX), and the
fact that nucleophilic halide anions are sometimes respon-
sible for undesirable processes such as addition of the ha-
Initially, we examined the selenolactonization of pent-
4-enoic acid (1a) with diphenyl diselenide (2a) in the pres-
ence of m-chloroperoxybenzoic acid as the oxidant and a
catalytic amount of potassium iodide in dichloromethane at
room temperature. It was found that simple stirring of a
mixture of potassium iodide (0.15 equiv), acid 1a (1.0
equiv), 2a (1.2 equiv) and m-chloroperoxybenzoic acid (0.6
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58
H. Shi et al.
Paper
Synthesis
equiv) in dichloromethane for six hours gave the expected
product, 5-phenylselenomethyl-2-tetrahydrofuranone (3a),
in 75% yield (Table 1, entry 1). In control experiments, the
desired product 3a was not detected in the absence of po-
tassium iodide (Table 1, entry 2) or without m-chloroper-
oxybenzoic acid (Table 1, entry 3). Next, the procedure for
the catalytic selenolactonization of 1a was optimized at
room temperature. The reaction was first evaluated in sev-
eral solvents giving the desired product in yields ranging
from 62–80%; of these, 2,2,2-trifluoroethanol (CF3CH2OH)
was selected as the most suitable (Table 1, entries 4–9).
Similar to potassium iodide, other iodine-containing cata-
lysts such as sodium iodide (NaI), ammonium iodide (NH4I),
copper(I) iodide (CuI) and tetraethylammonium iodide
(Et4NI) promoted the reaction, with ammonium iodide
demonstrating the best catalytic effect (Table 1, entries 9–
13). Compared with m-chloroperoxybenzoic acid, the use of
other oxidants such as Oxone®, sodium perborate tetrahy-
drate (NaBO3·4H2O), tert-butyl hydroperoxide (TBHP) and
hydrogen peroxide (H2O2) resulted in lower yields (Table 1,
entries 11 and 14–17). The amount of m-chloroperoxyben-
zoic acid was optimized with 0.55 equivalents proving to be
the best choice (Table 1, entries 11 and 18–20). The quanti-
ties of ammonium iodide and 2a were also evaluated, and it
was found that 0.1 equivalents and 1.2 equivalents, respec-
tively, were the most suitable (Table 1, entries 19 and 21–
Table 1 Optimization of the Selenolactonization of Pent-4-enoic Acid (1a) Catalyzed by Ammonium Iodide
O
O
I–, oxidant
solvent, r.t.
O
SePh
PhSeSePh
+
OH
1a
2a
3a
Entry
PhSeSePh (equiv)
Oxidant (equiv)
Iodide (equiv)
Solvent
Time (h)
Yield (%)a
1
2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.0
1.4
1.2
1.2
1.2
mCPBA (0.6)
mCPBA (0.6)
–
KI (0.15)
CH2Cl2
CH2Cl2
CH2Cl2
MeCN
EtOAc
EtOH
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
5
4
3
75
0
–
3
KI (0.15)
0
4
mCPBA (0.6)
mCPBA (0.6)
mCPBA (0.6)
mCPBA (0.6)
mCPBA (0.6)
mCPBA (0.6)
mCPBA (0.6)
mCPBA (0.6)
mCPBA (0.6)
mCPBA (0.6)
Oxone® (0.6)
NaBO3·4H2O (0.6)
TBHP (0.6)
KI (0.15)
76
76
62
78
78
80
82
91
83
60
80
78
34
35
84
93
83
93
88
80
93
93
88
81
5
KI (0.15)
6
KI (0.15)
7
KI (0.15)
AcOH
MeOH
8
KI (0.15)
9
KI (0.15)
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
CF3CH2OH
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
NaI (0.15)
NH4I (0.15)
CuI (0.15)
Et4NI (0.3)
NH4I (0.15)
NH4I (0.15)
NH4I (0.15)
NH4I (0.15)
NH4I (0.15)
NH4I (0.15)
NH4I (0.15)
NH4I (0.1)
NH4I (0.05)
NH4I (0.1)
NH4I (0.1)
NH4I (0.1)
NH4I (0.1)
NH4I (0.1)
H2O2 (0.6)
mCPBA (0.5)
mCPBA (0.55)
mCPBA (0.65)
mCPBA (0.55)
mCPBA (0.55)
mCPBA (0.55)
mCPBA (0.55)
mCPBA (0.55)
mCPBA (0.55)
mCPBA (0.55)
a Yield of isolated product.
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H. Shi et al.
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Synthesis
24). Using the optimized conditions, the reaction proceed-
ed smoothly and was complete after five hours (Table 1, en-
tries 21 and 25–27). Based on this extensive screening pro-
cess, we arrived at the optimum reaction conditions
(Scheme 1).
substituent, 2-methylpent-4-enoic acid (1c) typically gave
mixtures of five-membered diastereoisomers 3c and 3i,
both in 93% yields (Table 2, entries 3 and 9), and the trans to
cis ratios of 3c and 3i were both approximately 1:1.11 On
similar treatment of trans-hex-3-enoic acid (1d) (a β,γ-un-
saturated acid), γ-butyrolactones 3d and 3j (Table 2, entries
4 and 10), and not the predicted four-membered products,
were obtained, which indicates that five-membered lac-
tones are preferred over the corresponding four-membered
products in this selenolactonization. When hept-6-enoic
acid (1e) was treated with 2a and 2b, the corresponding
seven-membered selenolactones 3e and 3k were obtained
in moderate 53% and 46% yields, respectively (Table 2, en-
tries 5 and 11).
O
NH4I, mCPBA
O
+
RSeSeR
SeR
CF3CH2OH, 5 h, r.t.
COOH
1
2
3
Scheme 1 The selenolactonization of unsaturated acids catalyzed by
NH4I
Next, the catalytic selenolactonizations of unsaturated
acids 1 (1.0 equiv) with diselenides 2 (1.2 equiv), m-chloro-
peroxybenzoic acid (0.55 equiv) and ammonium iodide (0.1
equiv) in 2,2,2-trifluoroethanol at room temperature for
five hours were investigated. The corresponding selenolac-
tones 3 were obtained and the results are summarized in
Table 2. The selenolactonizations proceeded efficiently, af-
fording the corresponding five-membered and six-mem-
bered selenolactones in good to excellent yields (Table 2,
entries 1–4, 6–10 and 12). Compared with five-membered
lactones 3a and 3g, the yields of the corresponding six-
membered selenolactones 3b and 3h were lower (Table 2,
entries 1, 2, 7 and 8). Owing to the influence of the methyl
To further explore the efficiency and generality of our
methodology, pent-4-en-1-ol (1g), as a representative un-
saturated alcohol, was investigated under the same reaction
conditions. We found that it reacted easily with diselenides
2a and 2b to furnish the five-membered selenoethers 3m
and 3n in excellent yields (Table 2, entries 13 and 14).
When diphenyl ditelluride (2c) was used, the tellurocy-
clization proceeded with pentenoic acid 1a and pentenol 1g
in the presence of ammonium iodide to give the expected
tellurocyclization products 3o and 3p in 51% and 65%
yields, respectively. Gratifyingly, this finding extends the
application of our methodology.
Table 2 Results of the Selenolactonization of Unsaturated Acids Catalyzed by Ammonium Iodide
Entry
1
Unsaturated acid
Dichalcogen
Product
Yield (%)a
93
O
O
O
O
PhSeSePh
2a
SePh
SePh
OH
O
3a
1a
O
2
3
2a
2a
82
93
OH
1b
3b
O
O
O
SePh
OH
O
(cis/trans)-3c
1c
O
O
4
5
2a
2a
67
53
OH
1d
SePh
(trans)-3d
O
O
O
SePh
OH
1e
3e
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H. Shi et al.
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Synthesis
Table 2 (continued)
Entry
Unsaturated acid
Dichalcogen
Product
Yield (%)a
SePh
OH
O
O
1f
1a
O
6
2a
86
(trans)-3f
O
O
(BnSe)2
2b
7
8
82
76
SeBn
SeBn
3g
O
O
O
1b
1c
2b
2b
3h
O
SeBn
9
93
76
(cis/trans)-3i
O
O
10
1d
2b
SeBn
(trans)-3j
O
O
SeBn
SeBn
11
12
1e
1f
2b
2b
46
78
3k
O
O
(trans)-3l
O
OH
13
14
15
16
2a
2b
97
89
51
65
SePh
1g
1g
3m
O
SeBn
3n
O
O
PhTeTePh
2c
1a
1g
TePh
3o
O
2c
TePh
3p
a Yield of isolated product.
A proposed catalytic mechanism for the selenolacton-
ization of pentenoic acid 1a is shown in Scheme 2. Initially,
ammonium iodide is oxidized by m-chloroperoxybenzoic
acid to give hypoiodous acid A, which reacts smoothly with
diselenide 2 to form the active intermediate B, followed by
rapid cleavage of the Se–Se bond.10,12 The in situ generated
active electrophilic selenium species then reacts with pen-
tenoic acid 1a to produce the unstable cyclic intermediate
C, and after intramolecular substitution via an SN2 mecha-
nism, the desired product 3 is obtained. During the cycle,
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H. Shi et al.
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Synthesis
Se
R
R
Se
I
2
Se
R
R
Se
O
( I+ )
B
NH4OI
A
OH
1a
mCBA
R
O
O
NH4O–
SeR
Se
Se
I
R
3
NH4OH
O
O
H
NH4I (I–)
C
mCPBA
1a
Scheme 2 Proposed mechanism for the selenolactonization of unsaturated acids catalyzed by NH4I
another active intermediate, an arylselenium iodide (Ar-
SeI),13 can further transfer a second equivalent of electro-
philic selenium to the pentenoic acid.
IR (KBr): 3055, 1773, 1170, 740, 692 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 7.56–7.54 (m, 2 H), 7.30–7.28 (m, 3 H),
4.66 (dd, J = 7.2, 4.9 Hz, 1 H), 3.29 (dd, J = 12.9, 4.9 Hz, 1 H), 3.02 (dd,
J = 12.9, 7.9 Hz, 1 H), 2.63–2.47 (m, 2 H), 2.46–2.33 (m, 1 H), 1.99–1.93
(m, 1 H).
13C NMR (125 MHz, CDCl3): δ = 176.3, 133.2, 129.3, 128.9, 127.6, 79.3,
31.9, 28.7, 27.6.
In summary, we have developed a convenient catalytic
procedure for the preparation of selenolactones from un-
saturated acids and diselenides in the presence of a catalyt-
ic amount of ammonium iodide at room temperature. This
selenolactonization has several advantages including mild
reaction conditions and a simple procedure. The process is
also suitable for the preparation of cyclic selenoethers and
tellurocyclization products, thereby extending the catalytic
application of inorganic iodides in organic synthesis.
MS (ESI): m/z (%) = 256 (7.5) [M]+.
6-Phenylselenomethyl-2-tetrahydropyranone (3b)14
Yield: 89 mg (82%); pale yellow oil.
IR (KBr): 3055, 2951, 1734, 1242, 739, 692 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 7.53–7.51 (m, 2 H), 7.28–7.26 (m, 3 H),
4.45–4.42 (m, 1 H), 3.25 (dd, J = 12.9, 4.9 Hz, 1 H), 3.02 (dd, J = 13.0,
7.8 Hz, 1 H), 2.62–2.50 (m, 1 H), 2.47–2.43 (m, 1 H), 2.16–2.12 (m, 1
H), 1.91–1.88 (m, 1 H), 1.83–1.79 (m, 1 H), 1.59–1.54 (m, 1 H).
13C NMR (125 MHz, CDCl3): δ = 170.9, 132.8, 129.4, 129.2, 127.4, 79.7,
32.2, 29.3, 27.3, 18.3.
Unsaturated acids (1a–f), pent-4-en-1-ol (1g), diselenides (2a,b), di-
phenyl ditelluride (2c), mCPBA, and NH4I were commercially avail-
able. Petroleum ether (PE) refers to the fraction boiling in the 60–90 °C
range. Preparative TLC was performed using silica gel plates (20 cm × 20
cm) prepared in-house using GF-254 silica gel. IR spectra were ob-
tained using a Thermo-Nicolet 6700 instrument. 1H NMR and 13C
NMR spectra were recorded on a Bruker AVANCE III (500 MHz) spec-
trometer. Mass spectra were determined using Waters-GCT Premier,
Thermo-DECAX-60000 LCQ Deca XP and Thermo-ITQ 1100 mass
spectrometers.
MS (ESI): m/z (%) = 270 (12.5) [M]+.
3-Methyl-5-phenylselenomethyl-2-tetrahydrofuranone (3c)11
Yield: 100 mg (93%); pale yellow oil.
IR (KBr): 3056, 2973, 1771, 1179, 739, 692 cm–1
.
1H NMR (500 MHz, CDCl3): δ (trans/cis) = 7.55–7.52 (m, 2 H, cis/trans),
7.29–7.27 (m, 3 H, cis/trans), 4.67–4.63 (m, 1 H, trans), 4.51–4.46 (m,
1 H, cis), 3.30 (dd, J = 12.8, 5.2 Hz, 1 H, cis), 3.25–3.20 (m, 1 H, trans),
3.03–2.99 (m, 1 H, cis), 3.00–2.97 (m, 1 H, trans), 2.78–2.70 (m, 1 H,
trans), 2.67–2.57 (m, 1 H, cis/trans), 2.27–2.25 (m, 1 H, trans), 2.05–
2.02 (m, 1 H, cis), 1.59–1.54 (m, 1 H, cis), 1.26 (s, 3 H, cis), 1.25 (s, 3 H,
trans).
13C NMR (125 MHz, CDCl3): δ (trans/cis) = 179.3, 178.7, 133.14,
133.08, 129.30, 129.26, 128.9, 128.8, 127.6, 127.5, 77.1, 76.9, 37.1,
35.9, 34.9, 33.9, 31.8, 31.7, 15.9, 15.0.
Selenolactonization; General Procedure
Alkenoic acid 1 (0.4 mmol), diselenide 2 (0.24 mmol), NH4I (0.04
mmol) and mCPBA (0.22 mmol) were added successively to a reaction
vessel containing CF3CH2OH (1.5 mL). The resulting suspension was
stirred vigorously at r.t. for 5 h. Upon completion, the reaction mix-
ture was quenched by the addition of sat. aq Na2S2O3 (2 mL) solution,
and made basic by the addition of sat. aq Na2CO3 (8 mL) solution and
then H2O (5 mL). The mixture was extracted with CH2Cl2 (3 × 5 mL)
and the combined organic phase dried over anhydrous Na2SO4, fil-
tered, and concentrated under reduced pressure. The residue was pu-
rified on a silica gel plate (PE–EtOAc, 2:1) to furnish the correspond-
ing selenolactone 3.
MS (ESI): m/z (%) = 270 (4.3) [M]+.
5-Ethyl-4-phenylselenomethyl-2-tetrahydrofuranone (3d)15
5-Phenylselenomethyl-2-tetrahydrofuranone (3a)8h
Yield: 72 mg (67%); pale yellow oil.
IR (KBr): 3057, 2969, 1779, 1183, 741, 693 cm–1
.
Yield: 95 mg (93%); pale yellow oil.
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H. Shi et al.
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Synthesis
1H NMR (500 MHz, CDCl3): δ = 7.59–7.56 (m, 2 H), 7.39–7.32 (m, 3 H),
4.34 (dt, J = 11.7, 4.2 Hz, 1 H), 3.53–3.49 (m, 1 H), 2.94 (dd, J = 18.1, 8.5
Hz, 1 H), 2.59 (dd, J = 18.1, 8.6 Hz, 1 H), 1.82–1.80 (m, 1 H), 1.67–1.62
(m, 1 H), 1.00 (t, J = 7.4 Hz, 3 H).
13C NMR (125 MHz, CDCl3): δ = 174.5, 135.9, 129.5, 128.9, 126.3, 87.1,
38.6, 36.4, 26.8, 9.6.
5-Benzylselenomethyl-3-methyl-2-tetrahydrofuranone (3i)
Yield: 106 mg (93%); pale yellow oil.
IR (KBr): 3027, 2933, 1770, 1178, 761, 699 cm–1
.
1H NMR (500 MHz, CDCl3): δ (trans/cis) = 7.32–7.28 (m, 4 H, cis/trans),
7.25–7.20 (m, 1 H, cis/trans), 4.60–4.55 (m, 1 H, trans), 4.45–4.41 (m,
1 H, cis), 3.87 (s, 2 H, cis), 3.86 (s, 2 H, trans), 2.80–2.62 (m, 3 H,
cis/trans), 2.52–2.47 (m, 1 H, cis), 2.20–2.12 (m, 1 H, trans), 1.99–1.94
(m, 1 H, trans), 1.57–1.48 (m, 1 H, cis), 1.27–1.24 (m, 3 H, cis/trans).
13C NMR (125 MHz, CDCl3): δ (trans/cis) = 179.5, 178.8, 138.7, 138.6,
128.9, 128.52, 128.50, 128.4, 126.93, 126.90, 77.8, 77.5, 36.9, 35.8,
35.1, 34.0, 28.07, 28.05, 27.4, 15.9, 15.0.
MS (ESI): m/z (%) = 270 (60.2) [M]+.
7-Phenylselenomethyl-2-oxepanone (3e)14
Yield: 60 mg (53%); pale yellow oil.
IR (neat): 3055, 2935, 1731, 1171, 738, 692 cm–1
.
MS (ESI): m/z (%) = 284 (5.9) [M]+.
HRMS: m/z [M]+ calcd for C13H16O2Se: 284.0316; found: 284.0306.
1H NMR (500 MHz, CDCl3): δ = 7.55–7.52 (m, 2 H), 7.30–7.27 (m, 3 H),
4.37–4.32 (m, 1 H), 3.25 (dd, J = 12.8, 6.0 Hz, 1 H), 2.97 (dd, J = 12.8,
7.2 Hz, 1 H), 2.72–2.61 (m, 1 H), 2.51 (dd, J = 7.8, 5.8 Hz, 1 H), 2.20 (d,
J = 14.6 Hz, 1 H), 1.99–1.90 (m, 2 H), 1.70–1.50 (m, 3 H).
13C NMR (125 MHz, CDCl3): δ = 174.5, 133.1, 129.4, 129.3, 127.4, 79.8,
34.8, 34.0, 33.0, 28.1, 22.8.
4-Benzylseleno-5-ethyl-2-tetrahydrofuranone (3j)
Yield: 86 mg (76%); pale yellow oil.
IR (KBr): 3028, 2969, 1778, 1184, 759, 699 cm–1
.
MS (ESI): m/z (%) = 284 (11.3) [M]+.
1H NMR (500 MHz, CDCl3): δ = 7.36–7.28 (m, 4 H), 7.28–7.22 (m, 1 H),
4.27 (dt, J = 11.7, 3.9 Hz, 1 H), 3.90 (s, 2 H), 3.11 (dd, J = 16.3, 8.7 Hz, 1
H), 2.81 (dd, J = 18.0, 8.6 Hz, 1 H), 2.55 (dd, J = 18.1, 8.9 Hz, 1 H), 1.79–
1.67 (m, 1 H), 1.60–1.54 (m, 1 H), 0.98 (t, J = 7.4 Hz, 3 H).
6-(Phenylseleno)hexahydro-2H-cyclopenta[b]furan-2-one (3f)14
Yield: 97 mg (86%); pale yellow oil.
IR (KBr): 3055, 2958, 1774, 1176, 1006, 741, 692 cm–1
.
13C NMR (125 MHz, CDCl3): δ = 174.8, 138.0, 128.8, 128.7, 127.3, 87.3,
1H NMR (500 MHz, CDCl3): δ = 7.56–7.53 (m, 2 H), 7.31–7.29 (m, 3 H),
4.90 (d, J = 6.4 Hz, 1 H), 3.89 (d, J = 5.9 Hz, 1 H), 3.12–3.09 (m, 1 H),
2.82 (dd, J = 18.5, 10.0 Hz, 1 H), 2.34 (dd, J = 18.4, 2.4 Hz, 1 H), 2.28–
2.15 (m, 2 H), 1.87–1.82 (m, 1 H), 1.61–1.56 (m, 1 H).
37.5, 35.0, 27.9, 26.8, 9.7.
MS (ESI): m/z (%) = 284 (4.1) [M]+.
HRMS: m/z [M]+ calcd for C13H16O2Se: 284.0316; found: 284.0315.
13C NMR (125 MHz, CDCl3): δ = 176.7, 133.6, 129.3, 128.7, 127.8, 90.5,
46.2, 37.1, 35.9, 32.4, 30.1.
MS (ESI): m/z (%) = 282 (13.1) [M]+.
7-Benzylselenomethyl-2-oxepanone (3k)
Yield: 55 mg (46%); pale yellow oil.
IR (neat): 3026, 2933, 1731, 1172, 760, 699 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 7.36–7.26 (m, 4 H), 7.25–7.21 (m, 1 H),
4.07–4.01 (m, 1 H), 3.89 (d, J = 1.7 Hz, 2 H), 2.80 (dd, J = 13.1, 6.2 Hz, 1
H), 2.61 (dd, J = 13.1, 6.7 Hz, 2 H), 2.44–2.37 (m, 1 H), 2.03–1.98 (m, 1
H), 1.92–1.83 (m, 2 H), 1.61–1.49 (m, 2 H), 1.49–1.41 (m, 1 H).
5-Benzylselenomethyl-2-tetrahydrofuranone (3g)
Yield: 89 mg (82%); pale yellow oil.
IR (KBr): 3059, 3027, 2931, 1771, 1168, 760, 698 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 7.31–7.25 (m, 4 H), 7.25–7.21 (m, 1 H),
4.60 (dd, J = 7.0, 5.1 Hz, 1 H), 3.87 (s, 2 H), 2.76 (dd, J = 13.2, 5.0 Hz, 1
H), 2.69 (dd, J = 13.2, 6.7 Hz, 1 H), 2.61–2.45 (m, 2 H), 2.37–2.28 (m, 1
H), 1.96–1.87 (m, 1 H).
13C NMR (125 MHz, CDCl3): δ = 174.6, 139.3, 129.0, 128.5, 126.9, 80.6,
34.7, 34.1, 28.9, 28.4, 28.1, 22.8.
MS (ESI): m/z (%) = 298 (12.8) [M]+.
HRMS: m/z [M]+ calcd for C14H18O2Se: 298.0472; found: 298.0451.
13C NMR (125 MHz, CDCl3): δ = 176.5, 138.6, 128.9, 128.5, 126.9, 79.9,
28.6, 28.3, 28.0, 27.5.
MS (ESI): m/z (%) = 270 (4.4) [M]+.
HRMS: m/z [M]+ calcd for C12H14O2Se: 270.0159; found: 270.0143.
6-(Benzylseleno)hexahydro-2H-cyclopenta[b]furan-2-one (3l)
Yield: 92 mg (78%); pale yellow oil.
IR (KBr): 3026, 2956, 1776, 1174, 1003, 761, 699 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 7.33–7.27 (m, 4 H), 7.26–7.22 (m, 1 H),
4.89 (d, J = 6.4 Hz, 1 H), 3.89 (d, J = 2.0 Hz, 2 H), 3.42–3.38 (m, 1 H),
3.10–2.98 (m, 1 H), 2.82 (dd, J = 18.4, 10.1 Hz, 1 H), 2.32 (dd, J = 18.4,
2.6 Hz, 1 H), 2.19–2.11 (m, 2 H), 1.74 (dd, J = 6.8, 3.4 Hz, 1 H), 1.58–
1.49 (m, 1 H).
13C NMR (125 MHz, CDCl3): δ = 176.8, 138.6, 128.8, 128.6, 127.0, 91.2,
42.9, 37.2, 35.8, 32.6, 30.8, 28.0.
6-Benzylselenomethyl-2-tetrahydropyranone (3h)
Yield: 86 mg (76%); pale yellow oil.
IR (KBr): 3059, 3026, 2931, 1733, 1242, 760, 699 cm–1
1H NMR (500 MHz, CDCl3): δ = 7.32–7.29 (m, 4 H), 7.25–7.21 (m, 1 H),
4.40–4.27 (m, 1 H), 3.88 (s, 2 H), 2.76 (dd, J = 13.1, 5.1 Hz, 1 H), 2.67
(dd, J = 13.1, 7.0 Hz, 1 H), 2.60–2.51 (m, 1 H), 2.48–2.43 (m, 1 H),
2.04–1.96 (m, 1 H), 1.92–1.87 (m, 1 H), 1.83–1.75 (m, 1 H), 1.62–1.51
(m, 1 H).
.
MS (ESI): m/z (%) = 296 (9.9) [M]+.
HRMS: m/z [M]+ calcd for C14H16O2Se: 296.0316; found: 296.0310.
13C NMR (125 MHz, CDCl3): δ = 171.0, 138.8, 129.0, 128.5, 126.9, 80.3,
29.3, 28.3, 28.0, 27.5, 18.3.
MS (ESI): m/z (%) = 284 (8.3) [M]+.
HRMS: m/z [M]+ calcd for C13H16O2Se: 284.0316; found: 284.0311.
2-Phenylselenomethyltetrahydrofuran (3m)8h
Yield: 94 mg (97%); colorless viscous oil.
IR (KBr): 3055, 2971, 1579, 1478, 1058, 736, 691 cm–1
.
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1H NMR (500 MHz, CDCl3): δ = 7.56–7.49 (m, 2 H), 7.30–7.21 (m, 3 H),
4.15–4.06 (m, 1 H), 3.90–3.82 (m, 1 H), 3.78 (dd, J = 14.2, 7.8 Hz, 1 H),
3.14 (dd, J = 12.2, 5.8 Hz, 1 H), 3.03–2.97 (m, 1 H), 2.13–2.04 (m, 1 H),
1.97–1.86 (m, 2 H), 1.69–1.60 (m, 1 H).
13C NMR (125 MHz, CDCl3): δ = 132.6, 130.4, 129.0, 126.8, 78.3, 68.3,
33.0, 31.5, 25.9.
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MS (ESI): m/z (%) = 242 (27.9) [M]+.
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227, 1. (b) Erkekoglu, P.; Rachidi, W.; Yuzugullu, O. G.; Giray, B.;
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Hininger-Favier, I.; Roussel, A.-M.; Favier, A.; Hincal, F. Environ.
Toxicol. 2014, 29, 98. (f) Wallace, K.; Kelsey, K. T.; Schned, A.;
Morris, J. S.; Andrew, A. S.; Karagas, M. R. Cancer Prev. Res. 2009,
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2-Benzylselenomethyltetrahydrofuran (3n)
Yield: 91 mg (89%); colorless viscous oil.
IR (KBr): 3026, 2969, 1494, 1057, 759, 697 cm–1
1H NMR (500 MHz, CDCl3): δ = 7.33–7.26 (m, 4 H), 7.25–7.21 (m, 1 H),
4.06–4.01 (m, 1 H), 3.93–3.87 (m, 1 H), 3.87–3.83 (m, 2 H), 3.81–3.74
(m, 1 H), 2.68 (dd, J = 12.4, 6.0 Hz, 1 H), 2.62 (dd, J = 12.4, 6.4 Hz, 1 H),
2.10–1.98 (m, 1 H), 1.97–1.85 (m, 2 H), 1.63–1.53 (m, 1 H).
13C NMR (125 MHz, CDCl3): δ = 139.4, 128.9, 128.4, 126.6, 79.0, 68.2,
31.7, 28.9, 27.6, 25.9.
MS (ESI): m/z (%) = 256 (21.0) [M]+.
HRMS: m/z [M]+ calcd for C12H16OSe: 256.0366; found: 256.0343.
.
5-Phenyltelluromethyl-2-tetrahydrofuranone (3o)16
(6) Campos, M. M.; Petragnani, N. Chem. Ber. 1960, 93, 317.
(7) (a) Ranganathan, S.; Muraleedharan, K. M.; Vaish, N. K.;
Jayaraman, N. Tetrahedron 2004, 60, 5273. (b) Petragnani, N.;
Stefani, H. A.; Valduga, C. J. Tetrahedron 2001, 57, 1411.
(c) Freudendahl, D. M.; Santoro, S.; Shahzad, S. A.; Santi, C.;
Wirth, T. Angew. Chem. Int. Ed. 2009, 48, 8409.
Yield: 62 mg (51%); pale yellow oil.
IR (neat): 3052, 2929, 1774, 1169, 736, 692 cm–1
1H NMR (500 MHz, CDCl3): δ = 7.82–7.76 (m, 2 H), 7.34 (t, J = 7.5 Hz, 1
H), 7.29–7.20 (m, 2 H), 4.76–4.68 (m, 1 H), 3.29 (dd, J = 12.4, 4.7 Hz, 1
H), 3.03 (dd, J = 12.4, 8.5 Hz, 1 H), 2.60–2.52 (m, 2 H), 2.51–2.43 (m, 1
H), 1.96–1.82 (m, 1 H).
13C NMR (125 MHz, CDCl3): δ = 176.6, 138.9, 129.5, 128.3, 110.6, 81.1,
29.3, 29.1, 13.2.
MS (ESI): m/z (%) = 306 (7.5) [M]+.
.
(8) (a) Tiecco, M.; Testaferri, L.; Tingoli, M.; Bagnoli, L.; Marini, F.;
Santi, C.; Temperini, A. Gazz. Chim. Ital. 1996, 126, 635.
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1433. (c) Yoshshida, M.; Sasage, S.; Kawamura, K.; Suzuki, T.;
Kamigata, N. Bull. Chem. Soc. Jpn. 1991, 64, 416. (d) Trost, B. M.;
Ochiai, M.; McDougal, P. G. J. Am. Chem. Soc. 1978, 100, 7103.
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Lett. 1994, 35, 6525. (f) Miyoshi, N.; Ohno, Y.; Kondo, K.; Murai,
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Chem. 2006, 71, 7874. (h) Tingoli, M.; Diana, R.; Panunzi, B. Tet-
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Tingoli, M.; Bartoli, D.; Balducci, R. J. Org. Chem. 1990, 55, 429.
(9) (a) Tingoli, M.; Tiecco, M.; Chianelli, D.; Balducci, R.; Temperini,
A. J. Org. Chem. 1991, 56, 6809. (b) Tingoli, M.; Tiecco, M.;
Testaferri, L.; Balducci, R. Synlett 1993, 211. (c) Tingoli, M.;
Tiecco, M.; Testaferri, L.; Temperini, A. Chem. Commun. 1994,
1883. (d) Tingoli, M.; Tiecco, M.; Testaferri, L.; Temperini, A.
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2-Phenyltelluromethyltetrahydrofuran (3p)17
Yield: 76 mg (65%); colorless viscous oil.
IR (KBr): 3051, 2969, 1574 1475, 1052, 733, 692 cm–1
1H NMR (500 MHz, CDCl3): δ = 7.78–7.73 (m, 2 H), 7.30–7.25 (m, 1 H),
7.22–7.17 (m, 2 H), 4.20–4.09 (m, 1 H), 3.98–3.90 (m, 1 H), 3.82–3.74
(m, 1 H), 3.18–3.08 (m, 2 H), 2.09–2.02 (m, 1 H), 2.01–1.85 (m, 2 H),
1.65–1.54 (m, 1 H).
13C NMR (125 MHz, CDCl3): δ = 138.3, 129.1, 127.5, 111.8, 79.4, 68.4,
32.8, 26.2, 15.3.
MS (ESI): m/z (%) = 292 (11.2) [M]+.
.
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© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, 57–64