Reactions of gem-aryl-disubstituted methylenecyclopropanes with diaryl diselenide in the presence of iodosobenzene diacetate

Article abstract of DOI:10.1002/ejoc.200400644

The reaction of gem-aryl-disubstituted methylenecyclopropanes 1 with diaryl diselenide produced the corresponding ring-opened products 1,2-bis(arylselanyl) -3,3-diarylcyclobut-1-ene 4 in the presence of iodosobenzene diacetate in moderate-to-good yields u

Full text of DOI:10.1002/ejoc.200400644

FULL PAPER
Reactions of gem-Aryl-Disubstituted Methylenecyclopropanes with Diaryl
Diselenide in the Presence of Iodosobenzene Diacetate
[a]
[b]
[a]
Min Shi,* Bao-Yu Wang, and Jia Li
Keywords: Cyclobutyl cation / Iodosobenzene diacetate / MCPs / β-Proton elimination / Ring opening / Selenium
The reaction of gem-aryl-disubstituted methylenecyclopro- formation of 4 in the presence of MCPBA has also been ex-
panes 1 with diaryl diselenide produced the corresponding
amined.
ring-opened products 1,2-bis(arylselanyl)-3,3-diarylcyclobut-
1
-ene 4 in the presence of iodosobenzene diacetate in moder-
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2005)
ate-to-good yields under mild conditions. The further trans-
Introduction
clopropanes 1 with diaryl diselenides which give 1,2-bis(ar-
ylselanyl)-3,3-diarylcyclobut-1-enes 4 in the presence of
Methylenecyclopropanes (MCPs) 1 are highly strained
but readily accessible molecules that serve as useful building
blocks in organic synthesis. MCPs 1 undergo a variety of
ring-opening reactions because the relief of ring strain pro-
vides a potent thermodynamic driving force.[
Transition-metal (such as Pd, Rh, Ru, and Pt)-catalyzed
reactions of MCPs 1 with various reactants have attracted
iodosobenzene diacetate [PhI(OAc) ] in moderate-to-good
2
yields under mild conditions.
1]
Results and Discussion
We examined the reaction of MCP 1a with diphenyl dis-
[
2,3]
much attention.
In the field of Lewis acid catalyzed ring-
elenide in a variety of solvents in the presence of iodosoben-
opening reactions of MCPs 1, we have found that the ring
of MCPs 1 can be opened by alcohols and other nucleo-
philes in a novel manner to give the corresponding homoal-
[6]
zene diacetate at 35–40 °C. The results are summarized in
Table 1. It can be seen that the nature of the solvent signifi-
cantly affected the reaction products. In acetonitrile, 1,2-
dichloroethane (DCE), and dichloromethane (DCM), 1,2-
bis(phenylselanyl)-3,3-diphenylcyclobut-1-ene 4a was ob-
tained as the major product in 60, 73, and 60% isolated
yields, respectively, (Table 1, entries 1, 4, and 5). In THF, β-
hydroxyalkyl phenyl selenide 5a, derived from ambient
water, was obtained as the major product in 43% yield
along with (cyclobut-1-enylselanyl)benzene 2a in 12% and
[
4]
lylic derivatives in good yields under mild conditions. Pre-
viously, we reported that the reaction of gem-aryl-disubsti-
tuted methylenecyclopropanes 1 with phenylsulfenyl chlo-
ride or phenylselanyl chloride gives (cyclobut-1-enylsul-
fanyl)benzene or (cyclobut-1-enylselanyl)benzene 2 along
with ring-opened product 3 in good total yields at 0 °C in
various solvents (Scheme 1).[ In this paper we wish to re-
port the reactions of gem-aryl-disubstituted methylenecy-
5]
4a in 10% yields (Table 1, entry 2). In toluene, 2a was
formed as the major product in 40% yield along with 4a
and 5a in 10 and 30% yields, respectively (Table 1, entry 3).
With other organic oxidants such as PhI[OC(O)CF ] , 2,3-
3
2
dichloro-5,6-dicyanobenzoquinone (DDQ), chloramines-
[
7]
[6b]
T, and (NH ) S O
under identical conditions, either
4
2
2
8
no reaction occurred or 4a was formed in low yields. Met-
allic oxidants such as Cu(OAc) , Co(acac) , MnO , and
2
2
2
Scheme 1
FeCl showed no catalytic activities in this reaction. By
3
using [Mn(OAc) ]·2H O and Ag O as oxidants, 2a was ob-
tained in 50 and 52% yields, respectively (Scheme 2). With
[
a]
3
2
2
Shanghai Institute of Organic Chemistry, Chinese Academy of
Sciences,
3
54 Fenglin Lu, Shanghai 200032, China
ceric ammonium nitrate (CAN) as the oxidant in meth-
Fax: +86-21-64166128
E-mail: mshi@pub.sioc.ac.cn
[8]
anol, β-methoxyalkyl phenyl selenide 6a was exclusively
[
b]
Department of Chemistry, School of Science and Technology, formed in good yield (Scheme 2).
Yanbian University,
Yanji, Jilin Province 133002, China
Supporting information for this article is available on the
WWW under http://www.eurjoc.org or from the author.
On the basis of the above results, 4a was obtained in
good yield with iodosobenzene diacetate as the oxidant in
DCE at 35–40 °C. In order to suppress the formation of
Eur. J. Org. Chem. 2005, 759–765
DOI: 10.1002/ejoc.200400644
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759

M. Shi, B. Wang, J. Li
FULL PAPER
Table 1. Reaction of MCP 1a with diphenyl diselenide in the pres- in moderate-to-good yields without the formation of 5. For
ence of iodosobenzene diacetate in a variety of solvents
MCPs 1e–g bearing an electron-donating group on the ben-
zene ring, these reactions produced the ring-opened pro-
ducts 7 (acetates) in 10–27% yields (Table 2, entries 5–7,
and Figure 1).
Table 2. Reaction of MCPs 1 with diphenyl diselenide in the pres-
ence of iodosobenzene diacetate in DCE with 4-Å molecular sieves
[
(
4
a] Isolated yields; from 1a (0.3 mmol, 1 equiv.), C
0.33 mmol, 1.1 equiv.), C I(OAc)
(0.66 mmol, 2.2 equiv.), and (0.33 mmol, 1.1 equiv.), C
-Å molecular sieves (300 mg).
6
H
5
SeSeC
6
H
5
[a] Isolated yields; from 1 (0.3 mmol, 1 equiv.), C
6 5 6 5
H SeSeC H
I(OAc) (0.66 mmol, 2.2 equiv.), and
H
5
2
6
H
5
2
6
4-Å molecular sieves (300 mg). [b] Acetates 7 were formed as by-
products (Figure 1).
Figure 1
The structures of the reaction products were determined
1
13
by H and C NMR spectroscopy and HRMS or microa-
nalysis (see the Supporting Information). The configuration
of the double bond in compound 7b was determined by
NOESY spectroscopy (see the Supporting Information).
The crystal structure of the four-membered ring product 4a
Scheme 2
byproduct 5a, we added 4-Å molecular sieves (300 mg for was identified by X-ray diffraction and is shown in Fig-
[
9]
0.3 mmol of MCPs 1) to the reaction solution to remove ure 2.
the ambient moisture in the reactions of a variety of MCPs
Since the structure of 1,2-bis(arylselanyl)-3,3-diarylcyclo-
1
with diphenyl diselenide in the presence of iodosobenzene but-1-enes 4 is novel for the organic chemist, we attempted
diacetate in DCE. Therefore, we carried out this reaction to synthesize this kind of compound by using other diaryl
by stirring MCP 1, PhSeSePh, 4-Å molecular sieves, and diselenides. In the reactions of MCPs 1 with bis(p-methyl-
DCE for 1 hour at room temperature and then iodosoben- phenyl) diselenide and bis(p-methoxyphenyl) diselenide[10]
zene diacetate was added. The reaction mixture was then in the presence of iodosobenzene diacetate, the correspond-
stirred for 20 hours at 35–40 °C. The results are summa- ing 1,2-bis(arylselanyl)-3,3-diarylcyclobut-1-enes 4 were ob-
rized in Table 2; in many cases, 1,2-bis(arylselanyl)-3,3-di- tained in similar yields under identical conditions. The re-
phenylcyclobut-1-enes 4 were obtained as the sole product sults are summarized in Table 3. With MCP 1e, this reac-
760
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Eur. J. Org. Chem. 2005, 759–765

2 2 6 5 2
Reactions of gem-Aryl-Disubstituted MCPs with Ar Se in the Presence of C H I(OAc)
FULL PAPER
ther react with electrophilic selenium species to produce the
cationic intermediate C which furnishes product 4, again by
β-proton elimination (Scheme 3). At this stage, we cannot
explain the formation of 7 from MCPs 1e–g. We believe
that the intermediate A is relatively stable owing to the elec-
tron-donating substituents on the benzene ring of MCPs
1
e–g. This long-lived species may have time to undergo nu-
–
cleophilic attack by OAc to give the ring-opened product
7
(Scheme 3).
Figure 2. ORTEP drawing of 4a
tion also produced the ring-opened acetate 7d as a bypro-
duct (Table 3, entry 8).
Table 3. Reaction of MCPs 1 with diaryl diselenides in the presence
of iodosobenzene diacetate in DCE with 4-Å molecular sieves
Scheme 3. A plausible reaction mechanism for the reaction of
MCPs 1 with diaryl diselenides in the presence of iodosobenzene
diacetate
Scheme 4
We confirmed that the reaction of 2a with diphenyl dis-
elenide gives 4a in the presence of iodosobenzene diacetate
a] Isolated yields; from 1 (0.3 mmol), ArSeSeAr (0.33 mmol, in excellent yield (Scheme 4). This result clearly suggests
[
1
6 5 2
.1 equiv.), C H I(OAc) (0.66 mmol, 2.2 equiv.), and 4-Å molecu-
that the reaction of 2 with the electrophilic selenium species
could indeed produce cationic intermediate C and the pro-
duct 4 under the same conditions.
lar sieves (300 mg). [b] Acetate 7d was formed as a byproduct (see
Exp. Sect.).
Compound 4a was further transformed on treatment
A plausible reaction mechanism for the formation of 4 is with m-chloroperbenzoic acid (MCPBA) in DCM
shown in Scheme 3. The hypervalent iodine reagent (Scheme 5). 4-Oxo-2,2-diphenyl-1-(phenylselanyl)cyclobutyl
[
PhI(OAc) ] oxidatively cleaves the Se–Se bond to generate 3-chlorobenzoate 8a was obtained in moderate yield. The
2
[
6b,11]
in situ a very reactive electrophilic selenium species.
This adds to the double bond of MCP 1 to give the cationic of 4a produces intermediate D
reaction mechanism is shown in Scheme 5. The oxidation
[
13]
which immediately gives
intermediate A. Rearrangement of the carbonium ion A intermediate E by selenoxide elimination. The reaction of
gives the ring-expanded cyclobutyl cation B which affords MCBA with intermediate E produces enol intermediate F
product 2 by β-proton elimination.[ Compound 2 can fur- which furnishes product 8a by isomerization.
12]
Eur. J. Org. Chem. 2005, 759–765
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761

M. Shi, B. Wang, J. Li
FULL PAPER
91 cm . 1H NMR (300 MHz, CDCl
–
1
, TMS): δ = 3.21 (s, 2 H,
6
3
CH
2
), 7.27–7.15 (m, 16 H, ArH), 7.49–7.39 ppm (m, 4 H, ArH).
, TMS): δ = 143.94, 142.14, 135.01,
33.61, 129.09, 129.06, 128.33, 128.10, 127.36, 126.36, 61.09,
1
3
C NMR (75 MHz, CDCl
3
1
5
2
+
+
1.11 ppm. EI-MS (%): m/z = 518 [M] (8.2), 361 [M – 157] (28.2),
80 [M – 238]+ (36.7), 203 [M – 315] (100). C28
+
H22Se (516.3943):
2
calcd. C 65.12, H 4.29; found: C 65.24, H 4.26%.
3,3-Bis(p-fluorophenyl)-1,2-bis(phenylselanyl)cyclobut-1-ene
(4b):
This compound was obtained as a white solid (129 mg, 78%), m.p.
9
1
9
5–97 °C. IR (KBr): ν˜ = 3057, 2962, 2925, 2852, 1941, 1878, 1756,
602, 1577, 1560, 1506, 1475, 1438, 1302, 1232, 1160, 1100, 1021,
–
1 1
30, 903, 830, 738, 690 cm . H NMR (300 MHz, CDCl
3
, TMS):
δ = 3.17 (s, 2 H, CH
H, ArH), 7.52–7.37 ppm (m, 4 H, ArH). C NMR (75 MHz,
CDCl , TMS): δ = 51.36, 59.91, 114.92 (d, JC,F = 21.2 Hz), 126.31,
27.55, 127.90, 128.26, 128.86 (d, JC,F = 8.3 Hz), 129.10, 129.16,
33.57, 135.07, 137.06, 139.48 (d, 3.0 Hz), 142.71,
61.37 ppm (d, JC,F = 244.7 Hz). EI-MS (%): m/z = 554 [M] , 397
2
), 6.95–6.89 (m, 4 H, ArH), 7.31–7.17 (m, 10
1
3
3
1
1
1
C,F
J =
+
Scheme 5
+
+
+
[
2
[
M – 157] (22.43), 316 [M – 238] (24.67), 240 [M – 314] (100.00),
+
+
20 [M – 334] (19.87). HRMS (MALDI): calcd. for C28
H
21
F
2
Se
2
+
M + 1] : 554.9936; found: 554.9944.
Conclusions
3,3-Bis(p-chlorophenyl)-1,2-bis(phenylselanyl)cyclobut-1-ene
(4c):
We have found that the reaction of gem-aryl-disubsti-
This compound was obtained as a yellow liquid (74 mg, 42%). IR
tuted MCPs 1 with diaryl diselenide in the presence of iodo- (KBr): ν˜ = 3056, 2924, 1952, 1893, 1577, 1558, 1489, 1475, 1438,
–
1 1
sobenzene diacetate produced the ring-opened products 4 1397, 1203, 1093, 1014, 821, 738, 690 cm . H NMR (300 MHz,
in moderate-to-good yields under mild conditions. This CDCl , TMS): δ = 3.15 (s, 2 H, CH ), 7.32–7.14 (m, 14 H, ArH),
.52–7.38 ppm (m, 4 H, ArH). C NMR (75 MHz, CDCl , TMS):
δ = 51.06, 60.03, 126.21, 127.62, 127.71, 128.30, 128.69, 129.14,
29.20, 132.37, 133.70, 135.10, 136.65, 141.95, 142.26, 142.90 ppm.
3
2
1
3
7
3
process provides a novel and efficient route for the synthesis
of 1,2-bis(phenylselanyl)-3,3-diphenylcyclobut-1-ene 4. The
further transformation of 4 to 4-oxo-2,2-diphenyl-1-(phe-
nylselanyl)cyclobutyl 3-chlorobenzoate (8) by the use of
MCPBA under mild conditions has also been disclosed. Ef-
forts are in progress to elucidate the mechanistic details of
this reaction and to disclose its scope and limitations.
1
+
+
EI-MS (%): m/z = 586 [M] (8.02), 429 [M – 157] (35.43), 349
+
+
+
[M – 237] (20.92), 314 [M – 272] (25.98), 272 [M – 314] (46.22),
+
202 [M
–
384] (100.00). HRMS (MALDI): calcd. for
+
+
C
28
H20Cl
2
Se
2
Na [M + 23] : 608.9165; found: 608.9196.
3
-(o-Chlorophenyl)-3-phenyl-1,2-bis(phenylselanyl)cyclobut-1-ene (4d):
This compound was obtained as a yellow liquid (114 mg, 69%). IR
KBr): ν˜ = 3056, 3028, 2927, 1941, 1871, 1800, 1599, 1577, 1559,
493, 1475, 1437, 1196, 1063, 1031, 1021, 915, 892, 754, 738,
(
1
Experimental Section
1
–1 1
General Remarks: H NMR spectra were recorded on a 300 MHz
691 cm . H NMR (300 MHz, CDCl , TMS): δ = 3.08 (d, J =
3
spectrometer in CDCl
3
using tetramethylsilane as the internal stan-
13.5 Hz, 1 H, CH ), 3.63 (d, J = 13.5 Hz, 1 H, CH ), 7.08–7.04 (m,
2
2
dard. Infrared spectra were measured on a Perkin–Elmer 983 spec-
trometer. Mass spectra were recorded on a HP-5989 instrument
and HRMS on a Finnigan MA mass spectrometer. Satisfactory
2 H, ArH), 7.36–7.14 (m, 14 H, ArH), 7.52–7.37 (m, 2 H, ArH),
1
3
7.80–7.77 ppm (m, 1 H, ArH). C NMR (75 MHz, CDCl , TMS):
3
+
δ = 50.43, 61.12, 126.18, 126.32, 126.40, 127.45, 128.16, 128.19,
CHN microanalyses were obtained using a Carlo–Erba 1106 ana-
lyzer. Melting points (uncorrected) were recorded with a Yanagim-
oto micro melting point apparatus. All reactions were monitored by
TLC using Huanghai GF254 silica-gel-coated plates. Flash column
chromatography was carried out using 300–400 mesh silica gel.
129.04 (2C), 129.18 (2C), 129.41, 130.35, 133.63, 134.09, 134.96,
138.04, 141.38, 141.51, 142.24, 142.55 ppm. EI-MS (%):
m/z = 552 [M]+ (2.98), 517 [M – 35] (1.84), 395 [M – 157] (7.83),
+
+
279 [M – 273]+ (21.71), 238 [M – 314]+ (70.29), 202 [M – 350]
+
+
+
(100.00). HRMS (MALDI): calcd. for C H ClSe [M + 1] :
2
8
22
2
5
52.9735; found: 552.9748.
General Procedure for the Reactions of MCPs 1 with Diphenyl Dis-
elenide in the Presence of Iodosobenzene Diacetate: Under argon,a
mixture of MCP 1 (0.3 mmol), PhSeSePh (0.33 mmol), and 4-Å
molecular sieves (300 mg) were added to DCE (2 mL). The reaction
mixture was stirred for 1 hour at room temperature and then iodo-
sobenzene diacetate (0.66 mmol) was added and the reaction mix-
ture was stirred for a further 20 hours at 35–40 °C. The solvent was
removed under reduced pressure and the residue was purified by
column chromatography on silica gel using petroleum/ethyl acetate
3,3-Bis(p-methylphenyl)-1,2-bis(phenylselanyl)cyclobut-1-ene (4e):
This compound was obtained as a yellow liquid (82 mg, 50%). IR
(
KBr): ν˜ = 3054, 3020, 2921, 2865, 1945, 1897, 1788, 1577, 1559,
–1
1
1
510, 1475, 1438, 1187, 1021, 900, 812, 737, 690 cm . H NMR
, TMS): δ = 2.30 (s, 6 H, CH ), 3.19 (s, 2 H,
), 7.49–7.43 (m, 4 H, ArH), 7.67–7.15 (m, 10 H, ArH), 7.07–
(300 MHz, CDCl
3
3
CH
2
13
7
2
1
3
.04 ppm (m, 4 H, ArH). C NMR (75 MHz, CDCl , TMS): δ =
1.00 (2C), 51.26, 60.67, 126.23, 126.75, 127.24, 128.00, 128.44,
28.77, 129.02, 129.04, 133.60, 134.94, 135.82, 137.75, 141.15,
(
300:1) as eluent to give the products.
,3-Diphenyl-1,2-bis(phenylselanyl)cyclobut-1-ene (4a): This com-
pound was obtained as a colorless solid (114 mg, 74%), m.p. 76–
+
+
3
141.49 ppm. EI-MS (%): m/z = 546 [M] , 426 [M – 120] (2.86),
389 [M – 157]+ (17.66), 232 [M – 314] (85.33), 208 [M – 338]
+
+
+
7
1
8 °C. IR (KBr): ν˜ = 3056, 3021, 2965, 2952, 1945, 1871, 1800, (100.00), 193 [M – 353] (50.68). HRMS (MALDI): calcd. for
+
+
577, 1559, 1492, 1475, 1438, 1201, 1067, 1021, 893, 758, 737,
62
C
30
H26Se
2
Na [M + 23] : 569.0257; found: 569.0230.
7
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2 2 6 5 2
Reactions of gem-Aryl-Disubstituted MCPs with Ar Se in the Presence of C H I(OAc)
FULL PAPER
Se+ [M + 1] : 483.1069;
+
3,3-Bis(p-methoxyphenyl)-1,2-bis(phenylselanyl)cyclobut-1-ene (4f): HRMS (MALDI): calcd. for C26
H
27
O
4
This compound was obtained as a yellow liquid (73 mg, 42%). IR found: 483.1061.
(
KBr): ν˜ = 3055, 2998, 2954, 2833, 2052, 1937, 1874, 1606, 1577,
509, 1475, 1438, 1299, 1248, 1177, 1034, 1022, 828, 738, 690 cm .
(
Z)-4-Phenyl-4-(p-methoxyphenyl)-3-(phenylselanyl)but-3-enyl Ace-
–
1
1
tate (7b-Z): This compound was obtained as a yellow liquid (25 mg,
1
H NMR (300 MHz, CDCl
), 6.8–6.77 (m, 4 H, ArH), 7.27–7.16 (m, 10 H, ArH),
.50–7.42 ppm (m, 4 H, ArH). 13C NMR (75 MHz, CDCl
, TMS):
δ = 51.50, 55.21 (2C), 60.09, 113.40, 113.41, 126.74, 127.31, 128.03,
3 2
, TMS): δ = 3.17 (s, 2 H, CH ), 3.77
1
1
1
0%). IR (KBr): ν˜ = 3055, 3028, 2954, 2835, 2056, 1951, 1881,
(s, 6 H, CH
3
737, 1605, 1576, 1508, 1475, 1439, 1382, 1245, 1173, 1107,
7
3
–
1 1
034 cm . H NMR (300 MHz, CDCl
), 2.67 (t, J = 6.6 Hz, 2 H, CH ), 3.80 (s, 3 H, OCH
J = 6.6 Hz, 2 H, CH ), 6.87–6.84 (m, 2 H, ArH), 7.31–7.12 (m, 10
H, ArH), 7.60–7.47 ppm (m, 2 H, ArH). EI-MS: m/z = 452 [M]
3
, TMS): δ = 1.70 (s, 3 H,
CH
3
2
3
), 4.17 (t,
1
1
3
28.42, 129.05, 129.07, 133.49, 134.93, 136.38, 137.96, 141.51,
+
+
2
57.94 ppm. EI-MS (%): m/z = 578 [M] , 421 [M – 157] (25.42),
+
40 [M – 238]+ (5.24), 312 [M – 266] (6.81), 264 [M – 314]+
+
+
+
+
(31.6), 392 [M – 60] (19.22), 311 [M – 141] (31.32), 235 [M – 217]
+
(100.00), 249 [M – 329] (20.89). HRMS (MALDI): calcd. for
100.00), 220 [M – 232] (40.17), 204 [M – 248]+ (38.44), 197 [M –
+
(
2
+
+
C
30 27 2 2
H O Se [M + 1] : 579.0336; found: 579.0354.
55] (53.62), 178 [M – 274]+ (34.70), 149 [M – 303] (59.26).
+
+
+
+
3
(
-(p-Methoxyphenyl)-3-phenyl-1,2-bis(phenylselanyl)cyclobut-1-ene
4g): This compound was obtained as a white liquid (66 mg, 40%).
IR (KBr): ν˜ = 3055, 2957, 2928, 2833, 1945, 1878, 1797, 1606, 1577,
25 25 3
HRMS (MALDI): calcd. for C H O Se [M + 1] : 453.0963;
found: 453.0947.
–
1
(E)-4-Phenyl-4-(p-methoxyphenyl)-3-(phenylselanyl)but-3-enyl Ace-
tate (7b-E): This compound was obtained as a yellow liquid (33 mg,
1
1
509, 1475, 1438, 1298, 1248, 1179, 1033, 1022, 827, 738, 691 cm .
1
H NMR (300 MHz, CDCl
s, 3 H, CH ), 6.80–6.77 (m, 2 H, ArH), 7.27–7.17 (m, 14 H, ArH),
.50–7.42 ppm (m, 3 H, ArH). 13C NMR (75 MHz, CDCl
, TMS):
δ = 51.31, 55.20, 60.60, 113.42, 126.30, 126.67, 127.33 (2C), 128.06,
3 2
, TMS): δ = 3.20 (s, 2 H, CH ), 3.77
7%). IR (KBr): ν˜ = 3055, 3029, 2997, 2835, 2042, 1955, 1881,
(
7
3
–
1
1738, 1605, 1577, 1508, 1475, 1439, 1382, 1245, 1173, 1034 cm .
3
1
H NMR (300 MHz, CDCl
t, J = 6.6 Hz, 2 H, CH ), 3.79 (s, 3 H, OCH
2 H, CH ), 6.87–6.83 (m, 2 H, ArH), 7.33–7.28 (m, 10 H, ArH),
3
, TMS): δ = 1.94 (s, 3 H, CH
3
), 2.63
(
2
3
), 4.15 (t, J = 6.6 Hz,
1
1
28.08, 128.36, 128.45, 129.04, 129.07, 133.51, 134.97, 136.11,
+
2
37.66, 141.83, 144.22, 157.97 ppm. EI-MS (%): m/z = 548 [M]
+
+
+
7.53–7.49 ppm (m, 2 H, ArH). EI-MS: m/z = 452 [M] (16.54), 392
(1.45), 391 [M – 157] (26.90), 310 [M – 238] (11.62), 234 [M –
[M – 60]+ (11.41), 312 [M – 140]+ (27.50), 235 [M – 217] (67.27),
+
+
+
3
14] (100.00), 189 [M – 359] (36.86). HRMS (MALDI): calcd.
220 [M – 232]+ (27.17), 157 [M – 295] (37.70), 149 [M – 303]
+
+
+
+
2
for C29H24OSe Na [M + 23] : 571.0050; found: 571.0061.
+
(
C
100.00), 135 [M – 317] (56.65). HRMS (MALDI): calcd. for
Diphenyl[1-(phenylselanyl)cyclopropyl]methanol (5a): This com-
pound was obtained as a white solid (43 mg, 40%), m.p. 94–95 °C.
IR (KBr): ν˜ = 3502, 3057, 3023, 1948, 1882, 1775, 1598, 1578, 1491,
+
+
25 25 3
H O Se [M + 1] : 453.0963; found: 453.0946.
4
,4-Bis(p-methylphenyl)-3-(phenylselanyl)but-3-enyl Acetate (7c):
–
1 1
This compound was obtained as a yellow liquid (16 mg, 13%). IR
(
1
1.95 (s, 3 H, CH ), 2.33 (s, 6 H, CH ), 2.63 (t, J = 6.6 Hz, 2 H,
CH
1
477, 1447, 1438, 1334, 1151, 1041, 1024, 756, 738, 703 cm . H
NMR (300 MHz, CDCl , TMS): δ = 0.95 (t, J = 6.0 Hz, 2 H, CH ),
.03 (t, J = 6.0 Hz, 2 H, CH ), 3.58 (s, 1 H, OH), 7.31–7.22 (m, 9 H,
ArH), 7.54–7.50 ppm (m, 6 H, ArH). C NMR (75 MHz, CDCl
TMS): δ = 13.96 (2C), 36.06, 82.12, 127.21, 127.32, 127.71, 127.72,
KBr): ν˜ = 3021, 2957, 2924, 2854, 1739, 1578, 1509, 1475, 1438,
3
2
–
1 1
3
240, 1035, 1022 cm . H NMR (300 MHz, CDCl , TMS): δ =
1
2
13
,
3
3
3
2
), 4.15 (t, J = 6.6 Hz, 2 H, CH
2
), 7.11–7.09 (m, 6 H, ArH),
+
7.28–7.26 (m, 4 H, ArH), 7.51–7.48 ppm (m, 3 H, ArH). EI-MS:
1
28.69, 128.96, 131.11, 133.29 ppm. EI-MS (%): m/z = 380 [M]
m/z = 450 [M , 14.83] (390 [M – 60]+ (9.25), 309 [M – 141]
+
+
+
+
+
+
(14.44), 363 [M – 17] (5.65), 198 [M – 182] (42.77), 183 [M – 197]
+
+
+
(13.69), 233 [M – 217] (100.00), 218 [M – 232] (70.17), 149 [M –
301] (96.68), 119 [M – 331] (51.89). HRMS (MALDI): calcd. for
C H O Se [M + 1] : 451.1171; found: 451.1189.
26 27 2
(48.65), 105 [M – 275] (100.00). HRMS (MALDI): calcd. for
+
+
20OSeNa+ [M + 23] : 403.0572; found: 403.0596.
+
C
22
H
+
+
Product 6a: This compound was obtained as a white liquid (97 mg,
8
1
7
=
2
2%). IR (KBr): ν˜ = 3056, 2978, 2938, 1948, 1897, 1819, 1578,
490, 1477, 1444, 1405, 1264, 1221, 1190, 1158, 1073, 1034, 765,
1,2-Bis(p-methylphenylselanyl)-3,3-diphenylcyclobut-1-ene (4h): This
compound was obtained as a yellow solid (70 mg, 43%), m.p.
–1 1
53, 704 cm . H NMR (300 MHz, CDCl
4.5, 6.9 Hz, 2 H, CH
.85 (s, 3 H, CH ), 6.39–6.36 (m, 2 H, ArH), 7.00–6.87 (m, 3 H,
ArH), 7.39–7.32 (m, 6 H, ArH), 7.66–7.63 ppm (m, 4 H, ArH). EI-
3
, TMS): δ = 0.95 (dd, J 115 °C. IR (KBr): ν˜ = 3067, 3022, 2911, 2852, 1941, 1889, 1797,
–
1
1
), 1.81 (dd, J = 4.5, 6.9 Hz, 2 H, CH
2
),
1597, 1486, 1438, 1202, 1028, 895, 758, 699 cm . H NMR
(300 MHz, CDCl , TMS): δ = 2.31 (s, 6 H, CH ), 3.17 (s, 2 H,
3
CH ,
), 7.00–7.39 ppm (m, 18 H, ArH). 13C NMR (75 MHz, CDCl
2
3
3
3
2
MS: m/z = 394 [M]+ (2.52), 281 [M – 113] (0.58), 237 [M – 157]
+
+
TMS): δ = 21.12, 21.14, 51.05, 60.89, 122.86, 124.38, 126.22,
+
+
(2.01), 205 [M – 189] (11.53), 197 [M – 197] (100.00). HRMS
127.37, 127.38, 128.02, 129.80, 129.84, 133.98, 135.15, 137.36,
+
+
+
(MALDI): calcd. for C23
H
23OSe [M + 1] : 395.0909; found:
138.09, 141.45, 144.04 ppm. EI-MS (%): m/z = 546 [M] , 373 [M –
+
+
+
395.0923.
173] (9.13), 342 [M – 204] (6.81), 296 [M – 250] (12.21), 279
+
+
[
M – 267] (11.99), 217 [M – 329] (5.10). HRMS (MALDI/DHB):
calcd. for C30H27Se [M + 1] : 547.0438; found: 547.0431.
2
4,4-Bis(p-methoxyphenyl)-3-(phenylselanyl)but-3-enyl Acetate (7a):
+
+
This compound was obtained as a yellow liquid (23 mg, 10%). IR
(
1
KBr): ν˜ = 3056, 2999, 2932, 2836, 2057, 1883, 1736, 1605, 1576, 3,3-Bis(p-fluorophenyl)-1,2-bis(p-methylphenylselanyl)cyclobut-1-ene
508, 1464, 1382, 1245, 1173, 1034 cm . H NMR (300 MHz, (4i): This compound was obtained as a yellow solid (100 mg, 58%),
–1
1
CDCl
CH ), 3.79 (s, 3 H, OCH
H, CH
.27–7.25 (m, 3 H, ArH), 7.50–7.47 ppm (m, 2 H, ArH). C NMR
, TMS): δ = 21.0, 33.6, 55.1, 55.2, 63.5, 113.2,
3
, TMS): δ = 1.94 (s, 3 H, CH
3
), 2.65 (t, J = 6.9 Hz, 2 H, m.p. 80 °C. IR (KBr): ν˜ = 2921, 2851, 1886, 1741, 1600, 1562, 1506,
–
1
2
3
), 3.80 (s, 3 H, OCH
3
), 4.15 (t, J = 6.9 Hz,
1489, 1462, 1301, 1232, 1160, 1100, 1015, 927, 903, 830, 724 cm .
1
2
7
(
2
), 6.85–6.81 (m, 4 H, ArH), 7.13–7.10 (m, 4 H, ArH),
H NMR (300 MHz, CDCl
(s, 2 H, CH
), 6.89–7.40 ppm (m, 16 H, ArH). 13C NMR (75 MHz,
CDCl , TMS): δ = 21.15, 21.16, 51.39, 59.78, 114.86 (d, JC,F
3 3
, TMS): δ = 2.32 (s, 6 H, CH ), 3.11
1
3
2
75 MHz, CDCl
3
3
=
1
1
13.6, 127.3, 127.7, 129.1, 130.4, 130.5, 130.6, 133.4, 134.2, 136.1,
21.0 Hz), 122.67, 128.93 (d, JC,F = 8.1 Hz), 129.89, 129.90, 129.97,
132.30, 134.11, 135.25, 137.74, 138.38, 139.53 (d, JC,F = 2.9 Hz),
142.09, 161.40 ppm (d, JC,F = 243.6 Hz). EI-MS (%): m/z = 582
+
47.7, 158.6, 158.8, 170.8 ppm. EI-MS: m/z = 482 [M] (3.32), 452
M – 30]+ (3.53), 341 [M – 141] (3.22), 312 [M – 170] (9.89), 242
+
+
[
[
+
+
+
[M] , 448 [M – 134] (12.65), 411 [M – 171]+ (16.47), 330 [M –
+
+
M – 240] (26.13), 149 [M – 333] (58.45), 135 [M – 347] (100.00).
www.eurjoc.org
Eur. J. Org. Chem. 2005, 759–765
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
763

M. Shi, B. Wang, J. Li
FULL PAPER
52]+ (34.08), 240 [M – 342] (100.00). HRMS (MALDI/DHB): 698 cm–1. 1H NMR (300 MHz, CDCl
+
, TMS): δ = 2.95 (d, J =
2
3
+
+
calcd. for C30
H
24
F
2
Se
2
Na [M + 23] : 605.0069; found: 605.0093.
13.2 Hz, 1 H, CH
CH
), 6.70–7.79 ppm (m, 17 H, ArH). 13C NMR (75 MHz, CDCl
TMS): δ = 29.66, 50.46, 55.21, 60.83, 114.62, 114.66, 114.78,
16.45, 117.85, 126.16, 126.19, 126.37, 128.07, 129.57, 130.25,
134.10, 136.53, 137.80, 141.16, 141.55, 141.62, 159.57, 159.84 ppm.
2 2
), 3.48 (d, J = 13.2 Hz, 1 H, CH ), 3.76 (s, 6 H,
3
3
,
3
1
4
1
-(o-Chlorophenyl)-1,2-bis(p-methylphenylselanyl)-3-phenylcyclobut-
-ene (4j): This compound was obtained as a yellow liquid (77 mg,
4%). IR (KBr): ν˜ = 3053, 3018, 2921, 2840, 1897, 1797, 1600,
1
–
1
1
489, 1444, 1296, 1275, 1180, 884, 753, 697 cm . H NMR
, TMS): δ = 2.30 (s, 6 H, CH ), 3.03 (d, J =
), 3.56 (d, J = 13.5 Hz, 1 H, CH ), 6.97–7.81 ppm
, TMS): δ = 21.16,
9.68, 50.45, 61.02, 122.72, 126.18, 126.22, 126.38, 128.08, 128.10,
29.54, 129.82, 129.85, 129.96, 130.29, 134.08, 134.11, 135.14,
37.51, 137.93, 138.26, 141.57, 141.63, 142.12 ppm. EI-MS (%): ene (4o): This compound was obtained as a yellow liquid (108 mg,
+
+
+
EI-MS (%): m/z = 612 [M] , 425 [M – 187] (6.59), 345 [M – 267]
(300 MHz, CDCl
3
3
100.00), 238 [M – 374] (26.19), 202 [M – 410]+ (80.98), 187 [M –
+
(
1
3.5 Hz, 1 H, CH
2
2
+
13
4 2 5 ] ( 8 1 . 3 3 ) . H R M S ( M A L D I / D H B ) : c a l c d . f o r
(m, 17 H, ArH). C NMR (75 MHz, CDCl
3
ClNa+ [M + 23] : 634.9766; found: 634.9795.
+
C
30
H
25
O
2
Se
2
2
1
1
1,2-Bis(p-methoxyphenylselanyl)-3,3-bis(p-methylphenyl)cyclobut-1-
+
+
+
m/z = 580 [M] (3.32), 409 [M – 171] (8.98), 340 [M – 240] (8.43), 60%). IR (KBr): ν˜ = 2998, 2922, 2835, 1957, 1886, 1590, 1572,
3
29 [M – 251]+ (63.20), 293 [M – 287] (22.52), 238 [M – 342]+
+
1490, 1460, 1439, 1173, 1030, 900, 823, 717, 632 cm . H NMR
(300 MHz, CDCl , TMS): δ = 2.31 (s, 6 H, CH ), 3.05 (s, 2 H,
CH ), 3.79 (s, 6 H, CH ), 6.74–7.44 ppm (m, 16 H, ArH).
NMR (75 MHz, CDCl , TMS): δ = 21.00, 51.19, 55.23, 55.26,
0.24, 114.65, 116.85, 118.01, 127.34, 128.71, 135.42, 135.71,
36.53, 136.97, 137.35, 139.76, 141.29 ppm. EI-MS (%): m/z = 606
–1 1
+
(72.64), 202 [M – 378] (100.00). HRMS (MALDI/DHB): calcd.
3
3
+
+
13
for C30
H25ClSe
2
Na [M + 23] : 602.9867; found: 602.9896.
2
3
C
3
3
,3-Bis(p-methylphenyl)-1,2-bis(p-methylphenylselanyl)cyclobut-1-
6
1
[
y?oas [jy[lx?>ene (4k): This compound was obtained as a yellow
solid (114 mg, 66%), m.p. 129 °C. IR (KBr): ν˜ = 3019, 2920, 2850,
M] , 419 [M – 187] (24.34), 339 [M – 267]+ (59.77), 232 [M –
+
+
1
9
2
893, 1737, 1562, 1509, 1488, 1451, 1300, 1214, 1186, 1114, 1043,
374] (100.00), 215 [M – 391]+ (26.75), 202 [M – 404] (23.45).
+
+
–
1
1
34, 901, 803, 722 cm . H NMR (300 MHz, CDCl
.30 (s, 12 H, CH ), 3.13 (s, 2 H, CH ), 7.00–7.38 ppm (m, 16 H,
, TMS): δ = 20.70, 20.97, 21.00,
3
, TMS): δ =
+
+
HRMS (MALDI/DHB): calcd. for C32
629.0469; found: 629.0498.
30 2 2
H O Se Na [M + 23] :
3
2
ArH). 3C NMR (75 MHz, CDCl
1
3
2
1
1
4
(
(
1.13, 21.15, 21.18, 29.70, 29.74, 51.24, 70.47, 123.07, 127.30, 3-(p-Methoxphenylselanyl)-4,4-bis(p-methylphenyl)but-3-enyl Ace-
28.73, 129.76, 129.81, 129.84, 133.97, 134.01, 135.14, 135.74, tate (7d): This compound was obtained as a yellow liquid (17 mg,
+
37.37, 138.05, 140.30, 140.92 ppm. EI-MS (%): m/z = 574 [M] ,
5%). IR (KBr): ν˜ = 3021, 2960, 2921, 2851, 1957, 1904, 1844, 1794,
03 [M – 171]+ (9.95), 322 [M – 252] (19.24), 232 [M – 342]
+
+
1739, 1571, 1508, 1490, 1462, 1441, 1403, 1381, 1362, 1286, 1247,
+
+
–1
1
100.00), 215 [M – 359] (49.50), 202 [M – 372] (44.64). HRMS
1173, 1103, 1030, 945, 911, 819, 734, 596 cm
[M + 1] : 575.0751; found: (300 MHz, CDCl , TMS): δ = 2.30 (s, 12 H, CH ), 3.13 (s, 2 H,
CH
), 7.00–7.38 ppm (m, 16 H, ArH). 13C NMR (75 MHz, CDCl
TMS): δ = 20.70, 20.97, 21.00, 21.13, 21.15, 21.18, 29.70, 29.74,
. H NMR
+
+
MALDI/DHB): calcd. for C32
H31Se
2
3
3
5
75.0741.
2
3
,
1
,2-Bis(p-methoxyphenylselanyl)-3,3-diphenylcyclobut-1-ene (4l):
This compound was obtained as a yellow liquid (87 mg, 50%). IR
KBr): ν˜ = 3053, 2961, 2926, 2835, 1940, 1879, 1591, 1566, 1490,
5
1
1.24, 70.47, 123.07, 127.30, 128.73, 129.76, 129.81, 129.84, 133.97,
34.01, 135.14, 135.74, 137.37, 138.05, 140.30, 140.92 ppm. EI-MS
(
1
7
+
+
+
(
(
[
%): m/z = 480 [M] (21.49), 339 [M – 141] (43.80), 247 [M – 233]
456, 1443, 1287, 1247, 1173, 1102, 1030, 955, 909, 824, 733,
35.69), 233 [M – 247] (61.76), 218 [M – 262]+ (100.00), 203
+
–1 1
00 cm . H NMR (300 MHz, CDCl
), 3.81(s, 6 H, CH
), 6.77–7.48 ppm (m, 18 H, ArH). 13C NMR
75 MHz, CDCl , TMS): δ = 51.01, 55.17, 55.20, 60.55, 114.65,
3
, TMS): δ = 3.13 (s, 2 H,
M – 277]+ (52.19). HRMS (MALDI/DHB): calcd. for
CH
2
3
+
+
C
27 29 4
H O Se [M + 1] : 497.1226; found: 497.1216.
(
3
1
1
1
3
(
(
16.62, 116.64, 117.84, 126.22, 127.19, 127.60, 127.40, 127.70, 4-Oxo-2,2-diphenyl-1-(phenylselanyl)cyclobutyl 3-Chlorobenzoate
28.01, 136.50, 136.53, 136.93, 136.97, 140.27, 144.02, 159.58, (8a): This compound was obtained as a white liquid (40%). IR
+
+
˜
(KBr): ν = 3059, 2919, 2844, 1786, 1741, 1571, 1496, 1446, 1286,
59.75 ppm. EI-MS (%): m/z = 578 [M] , 391 [M – 187] (12.87),
74 [M – 204]+ (5.69), 311 [M – 267] (100.00), 279 [M – 299]
+
+
1249, 1118, 1072, 739, 697 cm–1
TMS): δ = 3.85 (d, J = 17.4 Hz, 1 H, CH ), 4.45 (d, J = 17.4 Hz,
.
H NMR (300 MHz, CDCl3,
1
+
+
8.47), 204 [M – 374] (57.98), 187 [M – 391] (47.22). HRMS
2
+
+
1 H, CH ), 7.1–7.08 (m, 4 H, ArH), 7.65–7.19 (m, 13 H, ArH),
MALDI/DHB): calcd. for C30
H
26
O
2
Se
2
Na [M + 23] : 601.0156;
2
1
3
found: 601.0163.
,3-Bis(p-fluorophenyl)-1,2-bis(p-methoxyphenylselanyl)cyclobut-1-
ene (4m): This compound was obtained as a yellow liquid (100 mg,
4%). IR (KBr): ν˜ = 2926, 2844, 1885, 1863, 1845, 1590, 1571,
505, 1453, 1287, 1239, 1169, 1102, 1028, 954, 932, 821, 725,
8.02–7.99 ppm (m, 2 H, ArH). C NMR (75 MHz, CDCl
3
, TMS):
δ = 54.10, 55.87, 96.02, 126.18, 127.03, 127.67, 127.71, 128.04,
3
1
1
28.51, 128.93 (2C), 129.00, 129.55, 129.64, 130.74, 133.46, 134.38,
36.99, 140.88, 142.40, 161.74, 193.48 ppm. EI-MS (%): m/z = 532
5
1
6
[
[
(
M] (0.32), 375 [M – 157] (17.36), 337 [M – 195]+ (3.13), 219
+
+
M – 313]+ (13.78), 207 [M – 325]+ (18.44), 180 [M – 352]
+
–
1 1
73 cm . H NMR (300 MHz, CDCl
), 3.79 (s, 6 H, CH ), 6.73–7.44 ppm (m, 16 H, ArH).
NMR (75 MHz, CDCl , TMS): δ = 51.39, 55.25, 55.28, 59.51,
14.71, 114.73, 114.84 (d, JC,F = 20.9 Hz), 116.42, 117.42, 128.95
d, JC,F = 7.9 Hz), 136.62, 136.82, 137.05, 139.60 (d, JC,F = 3.1 Hz),
40.83, 159.72, 159.90, 161.34 ppm (d, JC,F = 243.8 Hz). EI-MS
3
, TMS): δ = 3.03 (s, 2 H,
47.42), 139 [M – 393]+ (100.00). HRMS (MALDI): calcd. for
1
3
CH
2
3
C
C
29
H21ClO
3
SeNa+ [M + 23] : 555.0237; found: 555.0251.
+
3
Supporting Information Available (see also footnote on the first
1
(
1
(
3
(
1
13
page of this article): The H and C NMR spectra of the com-
pounds shown in Tables 1–3, Figure 1 and Schemes 2, 4, and 5.
+
+
+
%): m/z = 614 [M] , 446 [M – 168] (12.42), 427 [M – 151] (13.22),
47 [M – 231]+ (93.76), 219 [M – 359] (69.66), 187 [M – 391]+
+
Acknowledgments
+
100.00), 123 [M – 455] (67.84). HRMS (MALDI/DHB): calcd.
for C30H O Se F [M + 1] : 615.0094; found: 615.0124.
25 2 2 2
+
+
We thank the State Key Project of Basic Research (Project 973)
(No. G2000048007), the Chinese Academy of Sciences (KGCX2-
210-01), Shanghai Municipal Committee of Science and Technol-
3
-(o-Chlorophenyl)-1,2-bis(p-methoxyphenylselanyl)-3-phenylcyclo-
but-1-ene (4n): This compound was obtained as a yellow liquid
(68 mg, 37%). IR (KBr): ν˜ = 2925, 2836, 1964, 1879, 1638, 1591, ogy, and the National Natural Science Foundation of China for
1572, 1490, 1460, 1288, 1248, 1173, 1102, 1030, 955, 912, 824, 755, financial support (203900502, 20025206 and 20272069).
764 © 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.eurjoc.org
Eur. J. Org. Chem. 2005, 759–765

Reactions of gem-Aryl-Disubstituted MCPs with Ar
2
Se
2
6 5 2
in the Presence of C H I(OAc)
FULL PAPER
9
66; i) A. Brandi, S. Cicchi, F. M. Cordero, A. Goti, Chem.
Rev. 2003, 103, 1213–1269.
[
1] For the synthesis of MCPs, see: a) A. Brandi, A. Goti, Chem.
[
4] a) M. Shi, B. Xu, Org. Lett. 2002, 4, 2145–2148; b) M. Shi, Y.
Chen, B. Xu, J. Tang, Tetrahedron Lett. 2002, 43, 8019–8024;
c) G. L. N. Peron, J. Kitteringham, J. D. Kilburn, Tetrahedron
Lett. 2000, 41, 1615–1618; d) G. L. N. Peron, D. Norton, J.
Kitteringham, J. D. Kilburn, Tetrahedron Lett. 2001, 42, 347–
Rev. 1998, 98, 589–635; b) A. de Meijere (Ed.), Methods of Or-
ganic Chemistry: Carbocyclic Three-Membered Ring Com-
pounds(Houben-Weyl), Thieme, Stuttgart, 1996, vol. E 17a–c;
c) for a recent review, see: I. Nakamura, Y. Yamamoto, Adv.
Synth. Catal. 2002, 344, 111–129.
3
49; e) L. Patient, M. B. Berry, J. D. Kilburn, Tetrahedron Lett.
2003, 44, 1015–1017; f) B. Xu, M. Shi, Org. Lett. 2003, 5, 1415–
418; g) L.-X. Shao, M. Shi, Eur.J. Org. Chem. 2004, 426–430;
[2] Three types of ring-opening reaction of MCPs have been dis-
[
4a]
closed (see ref. ). For the ring opening of MCPs by type I,
see: a) D. H. Camacho, I. Nakamura, S. Saito, Y. Yamamoto,
Angew. Chem. Int. Ed. 1999, 38, 3365–3367; b) D. H. Camacho,
I. Nakamura, S. Saito, Y. Yamamoto, J. Org. Chem. 2001, 66,
1
h) A. T. Bottini, L. I. Cabral, Tetrahedron1978, 34, 3187–3194;
i) S. Kozhushkov, T. Spätch, T. Fiebig, B. Galland, M.-F. Ru-
asse, P. Xavier, Y. Apeloig, A. de Meijere, J. Org. Chem. 2002,
2
70–275; c) I. Nakamura, H. Itagaki, Y. Yamamoto, J. Org.
68, 4100–4114 and references cited therein.
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2
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mass 516.38,colorless, prismatic, triclinic, primitive lattice type,
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o
3
108.694(2), β = 111.511(2), γ = 96.036(2) , V = 854.5(2) Å ,
¯
3
space group P1, Z = 2, Dcalcd. = 1.504 g/cm , F000 = 516, Ri-
gaku AFC7R diffractometer, R = 0.0472, Rw = 0.1124. CCDC-
249186 contains the supplementary crystallographic data for
this paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via www.ccdc.cam.a-
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[13] It is conceivable that monoselenooxide D is formed as a result
of steric hindrance.
4
5
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Received September 13, 2004
Eur. J. Org. Chem. 2005, 759–765
www.eurjoc.org
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