The reaction of mono-aryl substituted methylenecyclobutanes with diphenyl diselenide in the presence of iodosobenzene diacetate and H2O

Article abstract of DOI:10.1016/j.tet.2008.11.052

The mono-aryl substituted methylenecyclobutanes undergo an interesting reaction with diphenyl diselenide in the presence of iodosobenzene diacetate and H₂O at 40 °C in 1,2-dichloroethane to give the corresponding aryl-(1-phenylselanylcyclobutyl

Full text of DOI:10.1016/j.tet.2008.11.052

Tetrahedron 65 (2009) 798–801
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The reaction of mono-aryl substituted methylenecyclobutanes with diphenyl
diselenide in the presence of iodosobenzene diacetate and H2O
*
Min Jiang, Min Shi
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai 200032, China
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 8 October 2008
Received in revised form 18 November 2008
Accepted 19 November 2008
Available online 24 November 2008
The mono-aryl substituted methylenecyclobutanes undergo an interesting reaction with diphenyl di-
selenide in the presence of iodosobenzene diacetate and H2O at 40 ꢀC in 1,2-dichloroethane to give the
corresponding aryl-(1-phenylselanylcyclobutyl)methanones in moderate to good yields within 30 h. A
plausible reaction mechanism has been discussed on the basis of the control and 18O-labeling
experiments.
Ó 2008 Elsevier Ltd. All rights reserved.
Keywords:
Mono-aryl substituted
methylenecyclobutanes
Diphenyl diselenide
Iodobenzene diacetate
Aryl-(1-phenylselanylcyclobutyl)-
methanones
1. Introduction
2. Results and discussion
Organoselenium compounds have become attractive synthetic
targets because of their unique chemo-, regio-, and stereo-
selectivities in organic synthesis and their useful biological activi-
ties.1 Furthermore, organoselenium compounds can also be used as
precursor for the introduction of a wide variety of functional groups
by selenoxide syn-elimination2 and [2,3]-sigmatropic rearrange-
ment,3 thus avoiding protection group chemistry.4 Previously, our
group reported the reaction of gem-aryl disubstituted methyl-
enecyclopropanes (MCPs) with diphenyl diselenide to give the
corresponding 1,2-bis(arylselanyl)-3,3-diarylcyclobut-1-ene, afour-
membered ring, along with a ring-opened product in the presence of
iodosobenzene diacetate [PhI(OAc)2] in moderate to good yields
under mild conditions (Scheme 1)5 as well as the reaction of vinyl-
idenecyclopropanes with diphenyl diselenide catalyzed by iodoso-
benzene diacetate to produce the corresponding addition products
in good yields.6 In this paper, we wish to report that the mono-aryl
substituted methylenecyclobutanes (MCBs)7 can react with
diphenyl diselenide in the presence of iodosobenzene diacetate and
H2O at 40 ꢀC in 1,2-dichloroethane (DCE) to give the corresponding
aryl-(1-phenylselanylcyclobutyl)methanones in moderate to good
yields rather than the ring-expanded or ring-opened products.
At first, we investigated the reaction of mono-aryl substituted
methylenecyclobutane 1a with diphenyl diselenide in the presence
of iodosobenzene diacetate and H2O to develop the optimal
conditions.8 The results of these experiments are summarized in
Table 1. Using mono-aryl substituted MCB(1a, 1.0 equiv) with
PhSeSePh (2, 1.0 equiv), PhI(OAc)2 (3, 2.0 equiv), and H2O
(1.0 equiv) in DCE at 40 ꢀC, 4a was produced in 71% yield after 30 h
under ambient atmosphere (Table 1, entry 1). When the tempera-
ture was changed to room temperature (20 ꢀC), the corresponding
product 4a was produced in trace (Table 1, entry 2). Raising the
reaction temperature to 60 ꢀC afforded 4a in 20% yield (Table 1,
entry 3). Changing the ratio of 1a/2/3/H2O to 1:1:1:1 or 1:1.5:3:1
provided 4a in 35% and 26% yield, respectively (Table 1, entries 4
and 5). Thus, the ratio of 1:1:2:1 for 1a/2/3/H2O is the best one for
this reaction to give 4a in 71% yield in DCE at 40 ꢀC (Table 1, entries
1–5). Further examination of solvent effects revealed that DCE was
the best one for this transformation (Table 1, entries 9–14). In tet-
rahydrofuran (THF), acetonitrile (CH3CN), and toluene, 4a was
obtained in 47%, 35%, and 52% yield at 40 ꢀC after 30 h, respectively
PhSe
R1
R1
SePh
+
PhI(OAc)2
DCE, 4A MS
R1
OAc
R2
+
PhSeSePh
R2
R2
SePh
* Corresponding author.
Scheme 1. Reactions of gem-aryl disubstituted methylenecyclopropanes with diaryl
E-mail address: mshi@mail.sioc.ac.cn (M. Shi).
diselenide in the presence of iodosobenzene diacetate.
0040-4020/$ – see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2008.11.052

M. Jiang, M. Shi / Tetrahedron 65 (2009) 798–801
799
Table 1
produced complex product mixtures without the formation of
4k, suggesting that an aromatic group is required in this trans-
formation (Table 2, entry 10).
Optimized reaction conditions of MCB 1a with PhSeSePh in the presence of
PhI(OAc)2
O
To further clarify the scope and limitations of this trans-
formation, the reactions of MCBs 1l, 1m, alkene 5, and methyl-
enecyclopentane 6 with diphenyl diselenide in the presence of
iodosobenzene diacetate and H2O have been also examined under
identical conditions. However, we found that either none of the
corresponding product was formed or complex product mixtures
were obtained after 30 h under the standard conditions, indicating
that the four-membered cyclobutane ring, an aromatic ring, and
a hydrogen atom in MCBs are essential for this reaction (Scheme 2).
p-ClC6H4
PhI(OAc)2 (3), H2O
solvent, temp, 30 h
p-ClC6H4
PhSe
+
PhSeSePh
H
2
1a
4a
Entrya
1a/2/3/H2O
Solvent
Temp (ꢀC)
Yieldb of 4a (%)
1
1:1:2:1
1:1:2:1
1:1:2:1
1:1:1:1
1:1.5:3:1
1:1:2:1
1:1:2:1
1:1:2:1
1:1:2:1
1:1:2:1
DCE
DCE
40
rt
71
Trace
20
35
26
47
52
35
25
2
3
4
5
6
7
8
9
10
DCE
DCE
DCE
THF
Toluene
CH3CN
CH2Cl2
Et2O
60
40
40
40
40
40
30
30
C6H5
NR
C6H5
1l
20
p-BrC6H4
a
Reaction conditions: 1a (0.3 mmol),
2
(0.3 mmol),
3
(0.6 mmol), solvent
NR
(2.0 mL), and H2O (0.3 mmol); and the reactions were carried out at various
temperatures.
1m
PhSeSePh, PhI(OAc)2, H2O
b
Isolated yields.
DCE, 40 °C, 30 h
C6H5
(Table 1, entries 6–8). In dichloromethane or ether at 30 ꢀC, 4a was
formed in only 25% and 20% yield, respectively (Table 1, entries 9
and 10).
complex
H
5
p-ClC6H4
Under these optimal reaction conditions, we next carried out
the reactions of a variety of MCBs 1 with diphenyl diselenide
in the presence of H2O and iodosobenzene diacetate to examine
the scope and limitations. We found that the corresponding
products 4 were obtained in moderate to good yields within 30 h
in spite of MCBs 1 bearing electron-rich, electron-neutral, and
electron-poor substituents on the benzene rings (Table 2). For
mono-aryl substituted MCBs 1b–1f having an electron-poor
substituent at the para or meta position of benzene ring, the
corresponding products 4b–4f were obtained in 75%–82% yields
(Table 2, entries 1–5). But for mono-aryl substituted MCB 1g
having an electron-poor substituent at the ortho position of
benzene ring, the corresponding product 4g was obtained in
slightly lower yield (61%), presumably due to the steric reason
(Table 2, entry 6). Using MCBs 1h–1j bearing an electron-rich
substituent on the benzene ring as the substrates afforded the
corresponding products 4h–4j in 62%–68% yields under the
standard conditions (Table 2, entries 7–9). However, when using
mono-aliphatic substituted MCB 1k as the substrate, the reaction
complex
H
6
Scheme 2. Reaction of 1l, 1m, 5, 6 with diphenyl diselenide in the presence of iodo-
sobenzene diacetate and H2O.
The structures of all these products reported in this paper were
determined by 1H, 13C NMR spectroscopic data, HRMS, or micro-
analysis. In addition, these products can be easily transformed to
the corresponding cyclobutenyl methanones by oxidation.9
In order to clarify the reaction mechanism, H128O (18O content
97.7%) was used in the reaction of 1a with diphenyl diselenide and
iodosobenzene diacetate under the standard conditions. It was
found that the corresponding product 4a-18O was obtained in 75%
yield along with 58% of 18O content, indicating that the oxygen
atom is indeed derived from water (Scheme 3). The lower 18O
content of 4a (58%) is due to that the ambient moisture (H2O) takes
part into the reaction as well.
The reaction mechanism is outlined in Scheme 4 on the basis of
the 18O-labeling and control experiments. Initially, the diphenyl
diselenide was oxidized by iodosobenzene diacetate to generate
intermediate PhSeþ,10 which was added into substrate 1 to form
intermediate A.5,6,10 Then, alcohol B is formed by the nucleophilic
attack of water11 at the position a of intermediate A. Further oxi-
dization of alcohol B by iodosobenzene diacetate12 affords the
corresponding product 4. A hydrogen atom at position a can facil-
itate the nucleophilic attack by water as well as the subsequent
oxidation by PhI(OAc)2 to give a ketone. Moreover, the four-mem-
bered cyclobutane moiety and an aromatic ring in MCBs can sta-
bilize intermediate A, driving the reaction forward. Therefore, the
four-membered cyclobutane, an aromatic ring, and a hydrogen
atom in MCBs are essential for this reaction.
Table 2
Reaction of MCBs 1 with PhSeSePh in the presence of PhI(OAc)2 and H2O
O
R
PhI(OAc)2 (3), H2O
DCE, 40 °C, 30 h
R
+
PhSeSePh
PhSe
H
2
1
4
Entrya
MCBs (R)
Yieldb of 4 (%)
1
2
3
4
5
6
7
8
9
10
1b, (p-BrC6H4)
1c, (p-FC6H4)
1d, (m-ClC6H4)
1e, (m-BrC6H4)
1f, (m-NO2C6H4)
1g, (o-ClC6H4)
1h, (p-MeC6H4)
1i, (p-EtC6H4)
1j, (m-CH3C6H4)
1k, (C4H9)
4b, 78
4c, 75
4d, 78
4e, 77
4f, 82
4g, 61
4h, 68
4i, 65
4j, 62
4k, -
O
p-ClC6H4
PhI(OAc)2, H218O
p-ClC6H4
PhSe
+ PhSeSePh
DCE, 40 °C, 30 h
H
1a
a
4a-18O 75% (18O content: 58%)
Scheme 3. Isotopic labeling experiment using H128O under the reaction conditions.
Reaction conditions: 1 (0.3 mmol), 2 (0.3 mmol), 3 (0.6 mmol), DCE (2.0 mL), and
H2O (0.3 mmol); and the reactions were carried out at 40 ꢀC.
b
Isolated yields.

800
M. Jiang, M. Shi / Tetrahedron 65 (2009) 798–801
138.8, 196.6; MS (EI) m/z (%): 350 (21.67) [Mþ], 322 (4.74), 211
(46.04), 193 (16.01), 139 (100.00), 130 (45.49), 111 (59.40), 75
(25.35); HRMS (EI) calcd for C17H15OClSe (Mþ) requires: 349.9977,
found: 349.9970.
PhI(OAc)2 + PhSeSePh
Ph
Se
+
Ar
Ar
H
PhSe+
Ar
a
H
b
HO
H
SePh
4.2.2. (4-Bromophenyl)(1-(phenylselanyl)cyclobutyl)-
methanone (4b)
H2O
A
1
B
A yellow oil; IR (CH2Cl2):
1437, 1394, 1275, 1247, 1071, 1010, 740, 691 cmꢁ1
(300 MHz, CDCl3, TMS): 1.85–1.89 (1H, m, CH2), 2.31–2.51 (3H, m,
n
3057, 2947, 1663, 1583, 1566, 1480,
1H NMR
O
;
PhI(OAc)2
d
Ar
CH2), 2.77–2.87 (2H, m, CH2), 7.22–7.27 (2H, m, ArH), 7.31–7.40 (3H,
PhSe
m, ArH), 7.54 (2H, d, J¼8.4 Hz, ArH), 7.76 (2H, d, J¼8.4 Hz, ArH); 13C
4
NMR (75 MHz, CDCl3, TMS):
d 16.2, 32.9, 53.2, 127.6, 127.9, 128.9,
Scheme 4. Proposed mechanism for the reaction of MCBs with diphenyl diselenide in
129.0, 131.1, 131.4, 132.5, 136.2, 196.8; MS (EI) m/z (%): 394 (42.68)
[Mþ], 366 (12.09), 239 (11.95), 211 (100.00), 209 (44.90), 182
(94.65), 158 (18.15), 76 (9.79); HRMS (EI) calcd for C17H15OBrSe
(Mþ) requires: 393.9471, found: 393.9471.
the presence of iodosobenzene diacetate and H2O.
3. Conclusion
In summary, we have disclosed an interesting reaction of mono-
aryl substituted methylenecyclobutanes with diphenyl diselenide
in the presence of iodosobenzene diacetate and H2O at 40 ꢀC in 1,2-
dichloroethane (DCE) to give the corresponding aryl-(1-phenyl-
selanylcyclobutyl)methanone derivatives in moderate yields.
A plausible reaction mechanism has been discussed on the basis
of the control and 18O-labeling experiments. The particular
four-membered cyclobutane ring plays a key role for this trans-
formation. The corresponding aryl-(1-phenylselanylcyclobutyl)-
methanones 4 may be useful intermediates in organic synthesis.
Efforts are in progress to further elucidate the mechanistic details of
this reaction and to determine its scope and limitations.
4.2.3. (4-Fluorophenyl)(1-(phenylselanyl)cyclobutyl)-
methanone (4c)
A colorless oil; IR (CH2Cl2):
1275, 1236, 1156, 849, 740, 691 cmꢁ1
TMS): 1.84–1.91 (1H, m, CH2), 2.32–2.51 (3H, m, CH2), 2.78–2.87
n
3072, 2927, 1663, 1598, 1505, 1437,
;
1H NMR (300 MHz, CDCl3,
d
(2H, m, CH2), 7.07 (2H, t, J¼9.0 Hz, ArH), 7.22–7.41 (5H, m, ArH), 7.63
(2H, dd, J¼9.0, 5.7 Hz, ArH); 13C NMR (75 MHz, CDCl3, TMS):
d 16.1,
33.0, 53.2, 115.2 (d, JC–F¼22.0 Hz), 128.0, 128.9, 129.0, 130.0, 132.1 (d,
JC–F¼8.9 Hz), 136.2, 165.1 (d, JC–F¼253.0 Hz), 196.5; MS (EI) m/z (%):
334 (17.01) [Mþ], 306 (4.74), 211 (31.12), 209 (15.89), 177 (11.16), 130
(29.44), 123 (100.00), 77 (16.04); HRMS (EI) calcd for C17H15OFSe
(Mþ) requires: 334.0272, found: 334.0273.
4. Experimental procedures
4.1. General methods
4.2.4. (4-Nitrophenyl)(1-(phenylselanyl)cyclobutyl)-
methanone (4d)
A white solid, mp 75–77 ꢀC; IR (CH2Cl2):
n
2964, 2932, 1682,
1606, 1417, 1252, 1222, 967, 779, 768, 744 cmꢁ1; 1H NMR (300 MHz,
CDCl3, TMS): 1.87–1.98 (1H, m, CH2), 2.39–2.59 (3H, m, CH2),
1H and 13C NMR spectra were recorded on a Bruker AM-300
spectrometer for solution in CDCl3 with tetramethylsilane (TMS) as
an internal standard; J-values are in hertz. Mass spectra were
recorded by EI methods and HRMS was measured on a Finnigan
MAþ mass spectrometer. CHN microanalyses were recorded on
a Carlo-Erba 1106 analyzer. Solvents were used without further
drying up. Commercially obtained reagents were used without
further purification. All reactions were monitored by TLC with
Huanghai GF254 silica gel coated plates. Flash column chromato-
graphy was carried out using 300–400 mesh silica gel at increased
pressure.
d
2.82–2.92 (2H, m, CH2), 7.22–7.27 (2H, m, ArH), 7.32–7.38 (3H, m,
ArH), 7.61 (1H, t, J¼8.1 Hz, ArH), 8.23 (1H, d, J¼6.6 Hz, ArH), 8.33–
8.37 (1H, m, ArH), 8.70 (1H, s, ArH); 13C NMR (75 MHz, CDCl3, TMS):
d
16.2, 32.6, 53.2, 124.3, 126.7, 127.6, 129.0, 129.2, 129.3, 135.0, 135.1,
136.1, 147.9, 195.2; MS (EI) m/z (%): 361 (41.63) [Mþ], 333 (13.40),
211 (69.97), 183 (29.71), 157 (30.04), 150 (100.00), 130 (64.73), 76
(55.51). Anal. Calcd for C17H15NO3Se: C, 56.68; N, 3.89; H, 4.20%.
Found: C, 56.31; N, 3.84; H, 4.20%.
4.2.5. (3-Chlorophenyl)(1-(phenylselanyl)cyclobutyl)-
methanone (4e)
4.2. General procedure
A colorless oil; IR (CH2Cl2):
1437, 1420, 1278, 1244, 1206, 1022, 804, 739, 673 cmꢁ1
(300 MHz, CDCl3, TMS): 1.81–1.91 (1H, m, CH2), 2.32–2.52 (3H, m,
n
3064, 2948, 2853, 1666, 1569, 1475,
;
1H NMR
Under argon atmosphere, methylenecyclobutanes (1, MCBs)
(0.3 mmol), PhSeSePh (2, 0.3 mmol), and PhI(OAc)2 (3, 0.6 mmol)
were added into an Schlenk tube. After adding 2.0 mL of dry DCE,
H2O (0.3 mmol) was added rapidly via a syringe. The reaction
mixture was stirred at 40 ꢀC for 30 h. Then, the solvent was re-
moved under reduced pressure and the residue was purified by
a flash column chromatography (SiO2) to give the corresponding
products 4 in moderate yields.
d
CH2), 2.77–2.86 (2H, m, CH2), 7.22–7.40 (6H, m, ArH), 7.46 (1H, d,
J¼8.7 Hz, ArH), 7.77 (1H, d, J¼8.7 Hz, ArH), 7.87 (1H, s, ArH); 13C
NMR (75 MHz, CDCl3, TMS):
d 16.2, 32.8, 53.2, 127.6, 127.9, 128.9,
129.1, 129.4, 129.5, 132.4, 134.4, 135.4, 136.2, 196.4; MS (EI) m/z (%):
350 (29.21) [Mþ], 322 (6.35), 211 (71.94), 209 (35.97), 183 (18.75),
157 (18.14), 139 (100.00), 77 (39.51); HRMS (EI) calcd for
C17H15OClSe (Mþ) requires: 349.9977, found: 349.9994.
4.2.1. (4-Chlorophenyl)(1-(phenylselanyl)cyclobutyl)-
4.2.6. (3-Bromophenyl)(1-(phenylselanyl)cyclobutyl)-
methanone (4a)
methanone (4f)
A colorless oil; IR (CH2Cl2):
1394, 1273, 1247, 1177, 1071, 1010, 740, 691 cmꢁ1
(300 MHz, CDCl3, TMS): 1.84–1.91 (1H, m, CH2), 2.31–2.51 (3H, m,
n
3057, 2947, 1633, 1583, 1479, 1437,
A colorless oil; IR (CH2Cl2):
1438, 1276, 1248, 1182, 1021, 740, 691 cmꢁ1
CDCl3, TMS): 1.82–1.92 (1H, m, CH2), 2.32–2.55 (3H, m, CH2), 2.77–
n
3056, 2948, 2860, 1662, 1572, 1477,
;
1H NMR
;
1H NMR (300 MHz,
d
d
CH2), 2.77–2.87 (2H, m, CH2), 7.22–7.27 (2H, m, ArH), 7.33–7.40 (5H,
2.84 (2H, m, CH2), 7.22–7.35 (5H, m, ArH), 7.40 (1H, d, J¼9.6 Hz,
m, ArH), 7.85 (2H, d, J¼8.7 Hz, ArH); 13C NMR (75 MHz, CDCl3,
ArH), 7.63 (1H, d, J¼9.0 Hz, ArH), 7.81 (1H, d, J¼9.0 Hz, ArH), 8.02
TMS):
d
16.2, 32.9, 53.2, 127.9, 128.4, 128.9, 129.0, 130.9, 132.0, 136.2,
(1H, s, ArH); 13C NMR (75 MHz, CDCl3, TMS):
d 16.2, 32.9, 53.2,

M. Jiang, M. Shi / Tetrahedron 65 (2009) 798–801
801
122.5, 127.9, 128.0, 129.0, 129.1, 129.6, 132.4, 135.3, 135.6, 136.2,
196.3; MS (EI) m/z (%): 394 (29.44) [Mþ], 366 (3.76), 239 (13.35), 211
(98.19), 209 (49.75), 183 (90.98), 157 (100.00), 77 (50.50); HRMS
(EI) calcd for C17H15OBrSe (Mþ) requires: 393.9471, found:
393.9484.
143.3,145.2,197.8; MS (EI) m/z (%): 330 (22.39) [Mþ], 302 (4.02), 211
(34.52), 173 (15.39), 130 (42.34), 119 (83.12), 91 (100.00), 77 (19.20);
HRMS (EI) calcd for C18H18OSe (Mþ) requires: 330.0523, found:
330.0510.
Acknowledgements
4.2.7. (2-Chlorophenyl)(1-(phenylselanyl)cyclobutyl)-
methanone (4g)
Financial support from the Shanghai Municipal Committee of
Science and Technology (06XD14005 and 08dj1400100-2), National
Basic Research Program of China (973)-2009CB825300, and the
National Natural Science Foundation of China (20872162,
20672127, and 20732008) are greatly acknowledged.
A colorless oil; IR (CH2Cl2):
1281, 1242,1050, 1022, 968, 898, 739, 691 cmꢁ1; 1H NMR (300 MHz,
CDCl3, TMS): 1.88–1.96 (1H, m, CH2), 2.12–2.24 (2H, m, CH2), 2.34–
n 3058, 2950, 2852, 1681, 1477, 1436,
d
2.43 (1H, m, CH2), 2.71–2.82 (2H, m, CH2), 7.21–7.44 (6H, m, ArH),
7.51 (2H, d, J¼8.4 Hz, ArH), 7.78 (1H, d, J¼9.0 Hz, ArH); 13C NMR
(75 MHz, CDCl3, TMS):
d 16.1, 32.1, 54.4, 126.2, 128.3, 128.9, 129.0,
Supplementary data
129.3, 130.4, 130.8, 131.5, 135.8, 137.4, 200.6; MS (EI) m/z (%): 350
(8.29) [Mþ], 315 (79.95), 287 (10.50), 211 (50.30), 183 (13.88), 157
(21.35), 139 (100.00), 77 (30.72); HRMS (EI) calcd for C17H15OClSe
(Mþ) requires: 349.9977, found: 349.9970.
1H and 13C NMR spectroscopic charts for compounds 4a–4j are
provided. This material is available free of charge via the Internet.
Supplementary data associated with this article can be found in the
online version, at doi:10.1016/j.tet.2008.11.052.
4.2.8. (p-Tolyl)(1-(phenylselanyl)cyclobutyl)methanone (4h)
A colorless oil; IR (CH2Cl2):
1391, 1246, 1219, 1121, 775, 696 cmꢁ1
TMS): 1.81–1.90 (1H, m, CH2), 2.31–2.49 (3H, m, CH2), 2.40 (3H, s,
n
3065, 2957, 2853, 1686, 1594, 1449,
References and notes
;
1H NMR (300 MHz, CDCl3,
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4. (a) Nicolaou, K. C.; Petasis, N. A. Selenium in Natural Products Synthesis; CIS:
Philadelphia, 1984; (b) Paulmier, C. Selenium Reagents and Intermediates in
Organic Synthesis; Pergamon: Oxford, 1986; (c) Patai, S.; Rappoport, Z. The
Chemistry of Organic Selenium and Tellurium Compounds; Wiley: New York, NY,
1986; Vol. 1; (d) Liotta, D. Organoselenium Chemistry; Wiley: New York, NY,
1987; (e) Krief, A.; Hevesi, L. Organoselenium Chemistry I; Springer: Berlin, 1988;
(f) Back, T. G. Organoselenium Chemistry: A Practical Approach; Oxford University
Press: Oxford, 1999; (g) Reich, H. J. Acc. Chem. Res. 1979, 12, 22–30; (h) Liotta, D.
Acc. Chem. Res. 1984, 17, 28–34; (i) Wirth, T. Topics in Current Chemistry;
Springer: Heidelberg, 2000; Vol. 208; (j) Mugesh, G.; Singh, H. B. Acc. Chem. Res.
2002, 35, 226–236.
d
CH3), 2.79–2.88 (2H, m, CH2), 7.20–7.35 (5H, m, ArH), 7.41 (2H, d,
J¼7.8 Hz, ArH), 7.82 (2H, d, J¼7.8 Hz, ArH); 13C NMR (75 MHz, CDCl3,
TMS):
d 16.2, 21.6, 33.1, 53.3, 128.3, 128.81, 128.84, 128.87, 129.6,
131.1, 136.1, 143.3, 197.7; MS (EI) m/z (%): 330 (19.21) [Mþ], 302
(4.74), 252 (6.19), 211 (39.99), 173 (23.83), 119 (100.00), 91 (75.29),
77 (22.51); HRMS (EI) calcd for C18H18OSe (Mþ) requires: 330.0523,
found: 330.0517.
4.2.9. (4-Ethylphenyl)(1-(phenylselanyl)cyclobutyl)methanone (4i)
A colorless oil; IR (CH2Cl2):
1436, 1281, 1242, 1208, 1050, 968, 898, 739, 691 cmꢁ1
(300 MHz, CDCl3, TMS):
n
3058, 1987, 2852, 1681, 1589, 1477,
;
1H NMR
d
1.26 (3H, t, J¼7.8 Hz, CH3), 1.83–1.87 (1H,
m, CH2), 2.33–2.46 (3H, m, CH2), 2.70 (2H, q, J¼7.8 Hz, CH2), 2.80–
2.87 (2H, m, CH2), 7.23–7.33 (5H, m, ArH), 7.42 (2H, d, J¼7.2 Hz,
ArH), 7.85 (2H, d, J¼7.2 Hz, ArH); 13C NMR (75 MHz, CDCl3, TMS):
5. Shi, M.; Wang, B.-Y.; Li, J. Eur. J. Org. Chem. 2005, 759–765.
6. Shi, M.; Lu, J.-M. Synlett 2005, 2352–2356.
d
15.1, 16.2, 28.9, 33.1, 53.3, 127.7, 128.3, 128.8, 128.9, 129.7, 131.3,
7. For the synthesis of MCBs, see: Brandi, A.; Goti, A. Chem. Rev. 1998, 98, 589–636.
8. It has been reported that treatment of diphenyl diselenide with iodosobenzene
diacetate produces an electrophilic selenenylating agent for double bonds. See:
(a) Tingoli, M.; Tiecco, M.; Testaferri, L.; Temperini, A. Synth. Commun. 1998, 28,
1769–1772; (b) Tiecco, M.; Tingoli, M.; Testaferri, L. Pure Appl. Chem. 1993, 65,
715–722 and references cited therein; (c) Miyoshi, N.; Takai, Y.; Murai, S.; So-
noda, N. Bull. Chem. Soc. Jpn. 1978, 51, 1265–1266; (d) Brugier, D.; Outurquin, F.;
Paulmier, C. J. Chem. Soc., Perkin Trans. 1 2001, 37–43.
9. Reich, H. J.; Renga, J. M.; Reich, I. L. J. Am. Chem. Soc. 1975, 97, 5434–5449.
10. Chen, D.-W.; Chen, Z.-C. Tetrahedron Lett. 1994, 41, 7637–7638.
11. The examples of water as nucleophilic reagent: (a) Kurz, J. L.; Lu, J. Y. J. Phys.
Chem. 1983, 87, 1444–1448; (b) Chi, D. Y.; Kim, D. W.; Hong, D. J.; Kim, H. S.
J. Org. Chem. 2004, 69, 3186–3189.
136.2, 149.4, 197.8; MS (EI) m/z (%): 344 (20.76) [Mþ], 314 (9.52), 211
(35.37), 187 (20.84), 171 (9.47), 157 (27.23), 133 (100.00), 77 (46.26);
HRMS (EI) calcd for C19H20OSe (Mþ) requires: 344.0679, found:
344.0689.
4.2.10. (m-Tolyl)(1-(phenylselanyl)cyclobutyl)methanone (4j)
A colorless oil; IR (CH2Cl2):
1391, 1246, 1219, 1121, 775, 696 cmꢁ1
TMS): 1.83–1.92 (1H, m, CH2), 2.32–2.51 (3H, m, CH2), 2.38 (3H, s,
n
3065, 2957, 2853, 1686, 1594, 1449,
;
1H NMR (300 MHz, CDCl3,
d
CH3), 2.79–2.88 (2H, m, CH2), 7.23–7.36 (5H, m, ArH), 7.42 (2H, d,
12. The oxidation of iodobenzene diacetate: (a) Swenton, J. S.; Callinan, A.; Chen, Y.;
Rohde, J. J.; Kerns, M. L.; Morrow, J. W. J. Org. Chem. 1996, 61, 1267–1274; (b)
Canesi, S.; Bouchu, D.; Ciufolini, M. A. Org. Lett. 2005, 7, 175–177.
J¼7.8 Hz, ArH), 7.70 (2H, s, ArH); 13C NMR (75 MHz, CDCl3, TMS):
d
16.2, 21.6, 33.1, 53.3, 121.0, 128.3, 128.8, 128.9, 129.6, 131.1, 136.1,