New synthesis and cyclopropanation of α-phenylselanyl α,β-unsaturated ketones with non-stabilized phosphorus ylides

Article abstract of DOI:10.1016/j.tet.2008.07.025

A general method for the preparation of α-phenylselanyl enones is described. Phosphorus ylides react with these α-phenylselanyl enones in a 1,4-addition, leading to cyclopropanes and/or dihydrofurans, depending on the substitution pattern. This unusual reactivity is due to the phenylselanyl moiety, hindering the carbonyl of the enone and making it less prone to 1,2-additions or promoting conjugate addition by electronic effects.

Full text of DOI:10.1016/j.tet.2008.07.025

Tetrahedron 64 (2008) 9293–9304
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New synthesis and cyclopropanation of
a-phenylselanyl
a
,b
-unsaturated
ketones with non-stabilized phosphorus ylides
*
*
´
´
Sebastien Redon, Stephane Leleu, Xavier Pannecoucke, Xavier Franck , Francis Outurquin
Universite´ and INSA de Rouen-C.O.B.R.A.-I.R.C.O.F., UMR 6014 CNRS, 1, rue Tesnie`re, 76131 Mont-Saint-Aignan cedex, France
a r t i c l e i n f o
a b s t r a c t
Article history:
A general method for the preparation of a-phenylselanyl enones is described. Phosphorus ylides react
Received 27 May 2008
Received in revised form 7 July 2008
Accepted 9 July 2008
with these
a-phenylselanyl enones in a 1,4-addition, leading to cyclopropanes and/or dihydrofurans,
depending on the substitution pattern. This unusual reactivity is due to the phenylselanyl moiety, hin-
dering the carbonyl of the enone and making it less prone to 1,2-additions or promoting conjugate
addition by electronic effects.
Available online 15 July 2008
Ó 2008 Elsevier Ltd. All rights reserved.
Keywords:
Selenium
a
-Phenylselanyl enones
Cyclopropane
Dihydrofuran
Conjugated dienes
1. Introduction
then further converting enals into diverse enones by addition/oxi-
dation sequence (Scheme 1). Due to the high sensitivity of the se-
Organoselenium compounds are versatile reagents that can ei-
ther act as nucleophiles or electrophiles and can generate radicals
under mild conditions.1 Indeed, due to the weakness of the carbon–
selenium bond, it is easier to introduce, transform, or eliminate
lenium atom to oxidation, highly chemoselective oxidation
methods of allylic alcohols have to be used.
than sulfur. Among these compounds,
a-selanylated a,b-un-
2. Results and discussion
saturated aldehydes have been shown to be good precursors of
a
-
allenols, -allenamines or -allenyl chlorides after formation of the
corresponding diene (Wittig) and allylic rearrangement of the
selanylated moiety.2 Following our studies on such compounds, we
a
-Phenylselanyl a,b-unsaturated aldehydes 2 were prepared
following our recently published procedure2 and submitted to di-
verse alkyllithium reagents. The corresponding allyl alcohols 3–8
were obtained in good yields (57–88%) with methyl-, n-butyl-, and
aryl-lithium whereas secondary and tertiary alkyllithium reagents
(s-BuLi, t-BuLi) gave rise to lower yields (30–36%), as shown inTable 1.
Allyl alcohols were then converted into enones by chemoselective
oxidation, without affecting the selanylated moiety, by the mild
PhSeSePh/t-BuOOH procedure.8 Enones 9–14 were obtained in
good yields, except for those in which R1¼H, due to their relative
instability (Table 1). When starting enals were Z, substituted enones
were obtained mainly (>95%) as Z isomers, as determined by 1H
NMR (through NOE experiments when possible) and 77Se NMR
spectrometric analyses. Indeed, as previously shown, 77Se NMR is
an efficient tool for the determination of the geometry of enals and
dienes2 and we extend this method to enones. Comparison of 77Se
turned our attention to the preparation of a-selanylated a,b-un-
saturated ketones and studied their reactivity toward phosphorus
ylides. We now report on the surprising results that were obtained,
as cyclopropanes and sometimes dihydrofurans were formed in-
stead of the expected dienes.
Usually,
a
-phenylselanyl
a
,
b
-unsaturated ketones are prepared
-unsaturated ketones
-diazo-ketones
by
a
-selenenylation of the corresponding a,b
(PhSeX/amine3 or PhSeNR2/SiO24), by reaction of
a
with PhSeX,5 by oxidation of propargylic phenylselenoderivatives,6
or by trapping allenol- or enol-ethers by PhSeX.7 Nevertheless,
these methods are limited to non-hindered enones or non-aryl-
substituted b-positions in order to achieve good yields, or neces-
sitate the preparation of reactive intermediates. We therefore
envisioned introducing the selenium moiety at the enal stage and
chemical shifts (d ppm) of enones 9–14 with those of the starting Z-
enals 2b (77Se 261.0 ppm) and 2c (77Se 301.1 ppm) indicates that the
substitution of the aldehyde hydrogen with R2¼Me, n-Bu, s-Bu, t-
Bu, or Ph, respectively, generates a homogeneous deshielding of the
Se atom of about 35, 36, 45, 80, or 90 ppm, respectively (Table 2).
* Corresponding authors. Tel.: þ33 2 35522403; fax: þ33 2 35522959.
E-mail addresses: xavier.franck@insa-rouen.fr (X. Franck), francis.outurquin@
univ-rouen.fr (F. Outurquin).
0040-4020/$ – see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2008.07.025

9294
S. Redon et al. / Tetrahedron 64 (2008) 9293–9304
R1
SePh
O
R1
SePh
OH
R1
R1
SePh
O
(3)
(2)
(1)
O
R2
3-8
R2
9-14
1
2
1a, R1=H
2a, R1=H
2b, R1=Me
2c, R1=Ph
3a-d, R2=Ph
9a-d, R2=Ph
1b, R1=Me
1c, R1=Ph
4c, R2=p-MeO-C6H4
5a-d, R2=Me
10c, R2=p-MeO-C6H4
11a-d, R2=Me
1d, R1=p-MeO-C6H4
2d, R1=p-MeO-C6H4
6a-c, R2=n-Bu
7b-c, R2=s-Bu
8b-c, R2=t-Bu
12a-c, R2=n-Bu
13b-c, R2=s-Bu
14b-c, R2=t-Bu
Scheme 1. Synthesis of
a
-phenylselanylenones 9–14. (1) (a) Morpholinobenzeneselenamide (MBSe), (b) SiO2; (2) R2Li, THF, ꢁ70 ꢀC; (3) PhSeSePh, t-BuOOH, 80 ꢀC.
Table 1
77Se of
d
a
-phenylselanyl enols 3–8 and
a
-phenylselanyl enones 9–14
R1
SePh
OH
R1
SePh
O
Entry
R1
R2
R2
R2
No.
Yield (%)
d
77Se
No.
Yield (%)
d
77Se
1
2
3
4
5
6
7
8
H
Me
Ph
Ph
Ph
Ph
Ph
3a9
3b
3c
3d
4c
60
81
88
85
73
58
88
83
84
57
75
66
36
30
36
31
390.1
269.3
323.4
313.2
327.5
381.0
254.7
311.3
301.4
379.6
252.0
310.9
250.9
306.9
9a12
9b4
54
88
89
91
80
54
85
89
85
390.8
342.8
404.5
385.4
409.9
413.1
295.8
337.3
325.2
9c11,13
9d
p-MeO–C6H4
Ph
H
Me
p-MeO–C6H4
Me
Me
Me
Me
n-Bu
n-Bu
n-Bu
s-Bu
s-Bu
t-Bu
t-Bu
10c
5a9,10
5b
5c11
5d
6a
6b
6c
7b
7c
11a6b,12,14
11b
Ph
11c15
11d
9
p-MeO–C6H4
H
10
11
12
13
14
15
16
12a
12b
12c
13b
13c
14b
14c
Me
Ph
Me
Ph
Me
Ph
76
88
86
89
90
89
296.9
337.4
304.4
349.7
338.0
388.2
8b
8c
Table 2
d
77Se of
a
-phenylselanyl enal 2 and
a
-phenylselanyl enones 9–14
77Se)
Enal (
d
77Se)
Enone (
d
Dd (ppm)
Enal (
d
77Se)
Enone (
d
77Se)
Dd (ppm)
Z-2b (261.0)
11b (295.8)
12b (297.0)
13b (304.4)
14b (338.0)
9b (342.8)
34.8
36
43.4
77
Z-2c (301.1)
11c (337.3)
12c (337.4)
13c (349.7)
14c (388.2)
9c (404.5)
36.2
36.3
48.6
87.1
81.8
103.4
With enones 9–14 in hand, we explored their reaction with
phosphorus ylides and started with enone 11b (R1¼Me, R2¼Me) as
highly hindered substrates in which 1,2-additions are not possible
or require hard conditions.16,17 The other methods involving nu-
cleophiles other than phosphorus ylides mainly include sulfur
ylides (Corey’s ylide), but also ammonium ylides, carbenes, diazo-
methane, and tellurium derivatives, and have been recently
reviewed.18
model substrate. Addition of 11b to
a solution of ethyl-
idenetriphenylphosphorane (R3¼Me, R4¼H) at rt in THF, surpris-
ingly, yielded cyclopropane 15 in 12% yield, 47% of PhSeSePh, and
no trace of the desired diene. After a brief survey of the reaction
conditions (time and temperature), we found that heating the
mixture at 50 ꢀC for 12 h was beneficial, increasing the yield in 15 to
65% (along with 15% of PhSeSePh); again, no diene was observed
(Scheme 2).
Cyclopropanations via 1,4-addition of phosphorus ylides to
enones have been known in the literature for many years, but have
never been developed because they generally occur only with
The addition of Corey’s ylides to
a-phenylthioenones has re-
cently been reported and allows the formation of cyclopropanes or
dihydrofurans, depending on both the substituents on the enone
and on the oxidation level of the sulfur atom (sulfur, sulfoxide, or
sulfone).19 The advantage of phosphorus ylides lays in the fact that
more substituted cyclopropanes can in principle be obtained if
alkylphosphorus ylides are used. We thus turned our attention to
the cyclopropanation of
a-phenylselanyl enones using different
phosphorus ylides (Scheme 3, Table 3).
With R1¼Me, cyclopropanes 15–20 and 41–42 are the exclusive
products, regardless of R2 (Me or Ph), R3, or R4 (Me, n-Pr, butenyl),
in yields ranging between 38 and 65%. The isolated amount of
(PhSe)2 ranged between 15 and 26%. The substituted cyclopropanes
were isolated as cis and trans mixture at carbons 2 (R1) and 3 (R3)
from 40/60 to 60/40. When R2¼Me, trans isomer is formed
Me
Me
SePh
Me
SePh
O
Me
SePh
Ph3P=CHMe
THF
+
O
Me
Me
Me
Me
no diene observed
11b
15
Scheme 2. 1,4-Addition of phosphorus ylide to enone 11b.

S. Redon et al. / Tetrahedron 64 (2008) 9293–9304
9295
R1
R1
R4
R3
SePh
R1
SePh
O
R1
SePh
R4
R4
R3
SePh
O
Ph3P=CR3R4
THF
(PhSe)2
+
+
+
R2
O
R2
R2
R3
R2
R1=Me, procedure c: 50 °C, 10h
R1=Ar, procedure e: 67 °C, 2h30
Scheme 3. Cyclopropanation reactions from enones and phosphorus ylides.
Table 3
R1
R2
R1
SePh
R1
R3
SePh
R2
Entry
Enone
R1
R2
R3
R4
(PhSe)2
R4
R3
R4
R3
SePh
O
O
R2
Yielda (%)
cis/transb
d
77Se ppm
Yielda (%)
Yielda (%)
Yielda (%)
1
2
3
4
5
6
7
8
11b
11b
11b
9b
9b
9b
11c
11c
11c
14c
9c
Me
Me
Me
Me
Me
Me
Ph
Ph
Ph
Ph
Ph
Me
Me
Me
Ph
Ph
Ph
Me
Me
Me
t-Bu
Ph
Me
n-Pr
n-But-3-enyl
Me
n-Pr
n-But-3-enyl
Me
Me
n-Pr
Me
Me
n-Pr
n-But-3-enyl
Me
Me
Me
Me
Me
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
15c (65)
16c (41)
17c (38)
18c (61)
19c (45)
20c (45)
40/60
45/55
40/60
60/40
60/40
52/48
276.0/350.6
283.6/352.1
283.4/352.8
309.7/390.9
318.2/392.3
318.4/393.2
15
24
24
16
24
26
21d (24)
22e (10)
24f (27)
55/45
50/50
78/22
391.2/421.0
389.1/420.7
300.1/368.0
23 (11) 242.0
9
24
12
19
24
28
40
30
26
22
16
22
16
10
11
12
13
14
15
16
17
18
19
20
25e (41)
26 (16) 262.1
28 (47) 266.1
30 (7) 266.3
32 (5) 268.1
34 (33) 263.7
37 (9) 241.4
40 (35) 266.0
27e,g (22)
29e (53)
9c
9c
Ph
Ph
Ph
Ph
60/40
56/44
329.5/399.2
339.6/421.4
Ph
31e (32)
10c
11d
9d
11b
9b
Arh
Me
Ph
33e,g (25)
35e (13)
Arh
Arh
Me
Me
Ph
70/30
36 (10) 331.2
39 (10) 331.0
38e,g (13)
41c (46)
Me
Ph
Me
Ph
Me
Me
Me
Me
296.7
338.4
42c (44)
11c
9c
Me
Me
43e (traces)
44e (traces)
Ph
a
Isolated yields.
b
c
Determined by 77Se NMR spectrometry on crude mixture.
50 ꢀC, 10 h.
d
e
f
rt, 3 h.
67 ꢀC, 2h30.
50 ꢀC, 2 h.
g
h
Deselenenylated cyclopropane.
Ar¼p-methoxy-phenyl-.
predominantly whereas when R2¼Ph, the cis isomer is the major
one. The relationship between R1 and the selenium group is always
cis, as starting enones were of Z-configuration. These configura-
tions have been determined by NOE experiments on most of the
cyclopropanes. Furthermore, we can also notice that when protons
of the cyclopropane ring are cis to the acyl moiety, their chemical
shift is always higher than when trans. For example (Scheme 4), in
cyclopropanes 15 and 16, protons cis to the acetyl group have
a chemical shift of 2.0–2.2 ppm whereas when they are trans, their
chemical shift is lower (1.2–1.5 ppm). These results are consistent
with non-selenylated cyclopropanes values.20 Furthermore, 77Se
NMR analysis of cyclopropanes allowed us to correlate the chemical
shift to the cis or trans configuration. Thus, for cyclopropanes 15–17
less reactivity toward phosphorus ylides than 9b and 11b (R1¼Me)
and the formation of cyclopropane is more difficult, necessitating
the heating to the reflux of THF but for a shorter time to avoid
deselenenylation. Enone 11c is particularly less reactive and
gives rise to low yields in either cyclopropane (27% with butyli-
denetriphenylphosphorane, entry 9, trace amounts with
15 cis
Me
15 trans
O
O
Me
1.09
2.00 H
2.00
H
2.00
Me (R3)
H
Se
Ph
Se
Ph
(R1) Me
1.17
(R1) Me
1.24
Me (R3)
1.17
1.35
H
(R1¼R2¼Me), we observed 276.0<
d
77Se<283.6 for cis configuration
and 350.6<d
77Se<352.8 for trans configuration. In a similar man-
ner, for cyclopropanes 18–20 (R1¼Me, R2¼Ph), we observed
16 trans
16 cis
Me
309.7<d d
77Se<318.4 for cis configuration and 390.9< 77Se<393.2
O
Me
Pr (R3)
1.2-1.5
O
2.19
for trans configuration. These strong differences in chemical shifts
in 77Se NMR, in addition to 1H NMR, allowed us to unambiguously
attribute either cis or trans configuration to the cyclopropanes.
When we changed R1 to aryl (Table 3, entries 7–16 and 19–20),
the formation of cyclopropane was accompanied with diene and
dihydrofuran. Indeed, enones 9c and 11c (R1¼Ph) have shown
2.06
H
1.71
H
H
Se
Ph
Se
Ph
1) Me
(R
1.17
(R1) Me
1.25
Pr (R3)
H
Scheme 4. Chemical shifts
d
1H and NOE correlations of cyclopropanes 15 and 16.

9296
S. Redon et al. / Tetrahedron 64 (2008) 9293–9304
R4
R3
isopropylidenetriphenylphosphorane, entry 19) or dihydrofuran 23
(entry 8). On the contrary, arylenones 9c,10c and 9d (R1 and R2¼Ar)
are more reactive than 11c and afford mixtures of cyclopropanes
and dihydrofuran in better yields, the latter being sometimes the
main product (entries 11, 14, and 16); nevertheless, these enones do
not react with hindered ylides (entry 20).
For entries 7 and 8, a dramatic change in the course of the re-
action was observed if temperature was changed from rt to reflux:
at rt, only diene 21 was isolated in 24% whereas at reflux, only
cyclopropane 22 and dihydrofuran 23 were isolated in 10 and 11%
yield, respectively. This result emphasizes the versatility of this
reaction and shows that optimum temperature and reaction time
should be checked for each substrate.
R1
SePh
R1
1,4- addition
SePh
O
Ph3P
C
R4
R3
1,2- addition
R2
R2
1,2- addition
1,4- addition
R1
SePh
O
R1
SePh
R1
SePh
O
R3
R4
R3
R4
R3
R2
R4
R2
O
PPh3
PPh3
R2
PPh3
R1
R1
R4
R3
SePh
R2
?
R4
R3
SePh
O
In entries 11, 14, and 16 where R1 and R2 are phenyl or aryl and
R3 is methyl, the dihydrofuran was obtained as the major product
along with deselenylated cyclopropane and diene (entry 16). In
these cases, the formation of deselenylated cyclopropane, instead
of the generally observed selenylated one, is not yet understood.
Concerning the relative configuration of the dihydrofurans, NOE
experiments show a trans relationship between R1 and R3 on
dihydrofuran 28, the same stereochemistry was assigned to other
dihydrofurans by analogy. The dienes obtained were isolated as
mixtures of stereoisomers.
O
R2
Scheme 6. Mechanistic considerations.
mixture and recovery of triphenylphosphine after column chro-
matography. The formation of the diene is the result of the
normal Wittig reaction (1,2-addition) while diphenyldiselenide
arises from selenophilic reactions on starting enone or reaction
intermediates.
The cis/trans configuration of the selenylated cyclopropanes 24
and 25 has been determined by NOE experiments and by 1H and
77Se NMR analyses. By analogy, the configuration of cyclopropanes
22, 29, 31, and 35 has also been determined and shows that the cis
R1,R3 geometry is always the major one (Scheme 5).
Contrary to what was observed by Bernard et al. with a-phe-
nylsulfanylenones19, the formation of dihydrofuran or cyclopro-
pane is not R2 but R1 dependant, as dihydrofuran is only observed
when R1 is an aryl group, regardless of the nature of R2 (Table 1:
alkyl, entries 8 and 10 or aryl, entries 11–14 and 16). This difference
may be linked to either the nucleophile nature (sulfur ylide vs
phosphorus ylide) or the heteroatom on carbon
a to the carbonyl
24 trans
Me
24 cis
Me
(sulfur vs selenium). Bernard et al. observed also that the oxidation
level of the sulfur substituent plays an important role on the course
of the reaction as the more electronwithdrawing the substituent
was, the more dihydrofuran was isolated. This accounts for a better
stabilization of the enolate that drives the equilibrium to the for-
mation of the dihydrofuran. In order to determine whether the
difference in reactivity is due to the nucleophile (phosphorus or
sulfur ylide) or to the heteroatom (selenium or sulfur), we per-
formed the reaction with Corey’s ylide using Bernard’s procedure
(Scheme 7, Table 4).19
2.55
3.26
2.53
2.91
O
O
H
H
2.42
Pr (R3)
2.14
H
Se
Ph
Se
Ph
(R1) Ph
(R1) Ph
Pr (R3)
H
25 trans
25 cis
1.40
t-Bu
1.37
O
t-Bu
O
1.24
Me (R3)
2.58 H
(R1) Ph
H
2.71
2.32
H
Se
Ph
Se
Ph
(R1) Ph
Me (R3)
1.18
H
2.07
R1
R1
R3
XPh
R2
R1
XPh
XPh
O
Ylide
THF or DMSO
+
Scheme 5. Chemical shifts d
1H and NOE correlations of cyclopropanes 24 and 25.
R3
O
O
R2
R2
When
a more hindered phosphorus ylide such as iso-
R3=H or Me
propylidenetriphenylphosphorane is used (R3¼R4¼Me), the re-
action works well when R1¼Me (entries 17 and 18), but failed when
R1¼Ph (entries 19 and 20). When semi-stabilized phosphorus ylide
is used (R3¼Ph), no cyclopropanation occurred and only diene 45
resulting from Wittig reaction was observed, albeit in low yield
(27%, result not shown).
O
Ylide= Corey: (Me)2S=CH2
(Ph) P
Wittig:
or
3
Me
X= S, Se
Scheme 7. Influence of the ylide on the cyclopropane/dihydrofuran ratio.
From the results obtained in Table 4, it is clear that the cyclo-
propane/dihydrofuran ratio is more dependent on the nature of
the ylide (sulfur or phosphorus) than on the nature of the het-
eroatom (selenium or sulfur). Indeed, in entries 1 and 3, a dra-
matic reversal of the cyclopropane/dihydrofuran ratio is observed
when the ylide changed from phosphorus to sulfur, keeping the
heteroatom (X¼Se) unchanged. The result obtained in entry 1
(X¼Se, ylide¼Corey) is similar to the result obtained by Bernard19
(entry 2) as the cyclopropane is the major product. The same
observation can be made for entries 4–6 where the cyclopropane/
dihydrofuran ratios are similar when using Corey’s ylide (what-
ever the heteroatom is) and very different from the ratio obtained
when using phosphonium ylide; cyclopropane became almost the
unique product with Corey’s ylide. For entries 7 and 8, no
It should also be noted that when a stabilized phosphonate
(diethylphosphonoacetate)
triphenylphosphorane was used, no reaction occurred at all,
whatever the enone was (results not shown).
From a mechanistic point of view (Scheme 6), the formation of
cyclopropane and dihydrofuran can be explained by 1,4-addition
of the ylide onto the enone. The Michael adducts encompassing
an enolate and a phosphonium can then transform through two
different pathways. In the first one, the carbon of the enolate
displaces the phosphonium unit to generate the cyclopropane
while in the second one, the oxygen of the enolate substitutes the
phosphonium moiety to give the dihydrofuran. The leaving group
is triphenylphosphine as determined by 31P NMR of the crude
or
the
simple
methylidene-

S. Redon et al. / Tetrahedron 64 (2008) 9293–9304
9297
Table 4
Entry
R1
R2
R3
X
Ylide
Cyclopropane/dihydrofuran
Yield (%)
1
Ph
p-tol
Ph
Ph
Ph
Ph
Me
Me
Ph
Ph
Ph
Me
Me
Me
Ph
Ph
H
H
Me
H
H
Me
H
Me
Se
S
Se
Se
S
Se
Se
Se
Corey
Corey
Wittig
Corey
Corey
Wittig
Corey
Wittig
46 (70)/47 (30)
75/25
81
86
69
63
68
22
66
61
2 (Ref. 20)
3
4
27 (30)/28a (70)
48 (90)/49 (10)
100/0
5 (Ref. 20)
6
7
8
22 (50)/23 (50)
50 100/0
18 100/0
a
: Deselenenylated cyclopropane.
differences were observed and cyclopropane was always the only
isolated product.
O-
Ph
PhSe
+Ph3P
These results show that the formation of both dihydrofuran and
cyclopropane depends on the nature of the ylide and not on the
nature of the heteroatom. These two methods are complementary:
the use of Corey’s ylide leads mainly to the formation of the cy-
clopropane but is limited to the introduction of a methylene group.
On the other hand, the use of a phosphonium ylide gives rise to the
formation of both cyclopropane and dihydrofuran, depending on
the substitution pattern, and can also generate molecular diversity
by changing the functional groups on the ylide.
SePh
Ph
O
0.030
0.025
0.020
0.015
9.90
0.010
0.005
0.000
-0.005
It is well known that acylcyclopropanes can rearrange to dihy-
drofuran under thermal,21 acidic,19 or Lewis-acidic conditions.22
Hence, we checked whether the formation of dihydrofuran could
arise from rearrangement of the cyclopropane during the reaction
and choose to study the rearrangement of cyclopropane 25 formed
in a reaction where dihydrofuran was also formed. Cyclopropane 25
was then heated in THF under reflux in the presence or absence of
1 equiv of LiBr (LiBr is present in cyclopropanation reaction as it is
formed by reaction of n-BuLi with alkylphosphonium bromide).
After 16 h of heating, and whatever the conditions were, the cy-
clopropane was recovered unchanged (Scheme 8). We can there-
fore postulate that the dihydrofuran does not arise from
a rearrangement of the cyclopropane but is formed via an SN2 re-
action of the enolate oxygen site on the phosphonium unit.
7.43
4.95
2.48
0.00
1700 1650 1600 1550 1500 1450
Wavenumber (cm-1)
Figure 1. Infrared spectra of cyclopropanation reaction with cyclopropane 18.
approximately after 10 h (Fig. 2). The red curve shows the in-
stantaneous formation and the progressive disappearance of in-
termediate enolate with a characteristic band at 1505 cmꢁ1. The
blue curve shows the progressive appearance of carbonyl group of
cyclopropane 18 with a characteristic band at 1667 cmꢁ1
.
Ph
Ph
Me
SePh
3. Conclusion
THF reflux, overnight
with or without LiBr
Me
SePh
O
O
26
In conclusion, we have shown that phosphorus ylides react with
25
a-phenylselanyl enones in a 1,4-addition, leading to cyclopropanes
and/or dihydrofurans, depending on the substitution pattern. This
unusual reactivity is due to the phenylselanyl moiety, hindering the
carbonyl of the enone and making it less prone to 1,2-additions or
promoting conjugate addition by electronic effects. The geometry
of the starting enones and cyclopropanes has been determined by
Scheme 8. Rearrangement of cyclopropane 25 under the reaction conditions.
The reaction between enone 9b and phosphorus ylide (R3¼Me)
was then monitored by infrared spectroscopy. The spectra were
recorded with ReactIRÔ 4000 fitted with an immersible DiComp
ATR probe (Fig. 1). The reaction was carried out by adding enone 9b
to the phosphorus ylide. Before adding n-BuLi, no spectra could be
recorded due to the insolubility of phosphonium salt. Then, addi-
tion of n-BuLi gave a quantitative conversion of phosphonium salt
to phosphorus ylide after 6 min of reaction (estimated by the sta-
bility of absorption spectra). After addition of enone 9b, no char-
acteristic absorption of carbonyl group of the enone was observed
showing a fast reaction between phosphorus ylide and enone. In-
deed, an intermediate species was directly observed with an ab-
sorption at 1505 cmꢁ1, characteristic wavenumber of a vibrational
C]C bond of an enolate.23 The appearance of carbonyl group ab-
sorption at 1667 cmꢁ1 allowed us to follow the kinetics of the
formation of the cyclopropane, the absorption band corresponding
to the C]C bond of the enolate simultaneously disappearing. The
complete reaction was determined from the stable absorption
intensity of the carbonyl group, and was estimated to occur
0.020
SePh
Ph
0.015
O
O-
Ph
PhSe
+Ph3P
0.010
0.005
0.000
0
2
4
6
8
Time (h)
Figure 2. Profile of cyclopropanation reaction with cyclopropane 18.

9298
S. Redon et al. / Tetrahedron 64 (2008) 9293–9304
the combined use of 1H NMR, NOESY, and 77Se NMR spectra, and
the course of the reaction has been followed by in situ IR
spectroscopy.
(EI): 304.00 (Mþ). Anal. Calcd for C16H16OSe (303.25): C, 63.37; H,
5.32. Found: C, 63.39; H, 5.38.
4.2.3. 1,3-Diphenyl-2-phenylselanylprop-2-en-1-ol 3c
4. Experimental
4.1. General
Yield 81%; yellow oil; Rf¼0.32 (EtOAc/pet. ether: 1/10); 77Se
NMR
d
(ppm) 323.4; 1H NMR
d
(ppm) 2.45 (d, 1H, J¼4.5 Hz),
5.32 (d, 1H, J¼4.5 Hz), 7.14–7.39 (m, 14H), 7.48–7.53 (m, 2H); 13C
NMR
d (ppm) 78.0, 127.2, 127.3, 128.1, 128.2, 128.6, 129.3, 129.6,
THF was distilled over sodium/benzophenone. Ether was dried
over sodium.
129.8, 132.5, 134.4, 135.8, 136.5, 141.8. IR (neat): 3394, 3058,
3027, 1576, 1492, 1476, 1438, 1265, 1062, 1022, 737, 694 cmꢁ1
.
NMR spectra were recorded on a Bruker DPX 300 spectrometer
operating at 300 MHz for proton and 75.4 MHz for carbon. This
probe is equipped with pulsed field (z) gradients. 77Se NMR spectra
were recorded at 21 ꢀC on a Bruker DPX 400 spectrometer oper-
Anal. Calcd for C21H18OSe (365.31): C, 69.04; H, 4.97. Found: C,
69.38; H, 4.92.
4.2.4. 3-(4-Methoxy-phenyl)-1-phenyl-2-phenylselanylprop-2-en-
1-ol 3d
ating at 76.29 MHz for 77Se, using a pulse length of 19
m
s (90ꢀ
s) and an optimized relaxation delay of 2 s. An average
of 1500 scans for 77Se NMR was necessary to have reliable in-
formation. Chemical shifts ( ) are expressed in parts per million
pulse¼19
m
Yield 85%; yellow oil; Rf¼0.27 (EtOAc/pet. ether: 15/85); 77Se
NMR
d
(ppm) 313.2; 1H NMR
d
(ppm) 2.54 (d, 1H, J¼4.8 Hz), 3.86 (s,
d
3H), 5.39 (d, 1H, J¼4.8 Hz), 6.89–6.92 (m, 2H), 7.20–7.43 (m, 11H),
relative to TMS for 1H and 13C nuclei and to Me2Se for 77Se nuclei;
coupling constants (J) are given in hertz; coupling multiplicities are
reported using conventional abbreviations. Elemental analyses
were obtained on a Carlo–Erba 1106 analyser and mass spectra on
an HP5890 (electronic impact 70 eV) using GC–MS coupling with
a Jeol AX 500.
7.59–7.62 (m, 2H); 13C NMR
d
(ppm) 55.4, 78.4 (C-1), 113.5, 127.0,
128.0, 128.5, 128.9, 129.3, 130.1, 131.1, 131.9, 133.2, 134.7, 141.9, 159.5.
IR (neat): 3417, 3059, 3030, 2933, 2836,1605,1575,1512,1476,1440,
1304, 1252, 1177, 1065, 1032, 909, 830, 736, 700 cmꢁ1. Anal. Calcd
for C22H20O2Se (395.34): C, 66.83; H, 5.10. Found: C, 66.53; H, 5.31.
4.2.5. 1-(4-Methoxy-phenyl)-3-phenyl-2-phenylselanylprop-2-en-
1-ol 4c
4.1.1. 3-(4-Methoxy-phenyl)-2-phenylselanylprop-2-enal 2d
Compound 2d was prepared using our reported procedure in
Ref. 2a. Yield 84%; yellow solid (mp¼72–74 ꢀC); Rf¼0.27 (EtOAc/pet.
Yield 73%; yellow oil; Rf¼0.41 (EtOAc/pet. ether: 1/5); 77Se NMR
d
(ppm) 327.5; 1H NMR
d
(ppm) 2.38 (d, 1H, J¼4.9 Hz, OH), 3.81 (s,
ether: 15/85); 77Se NMR
d
(ppm) 289.3; 1H NMR
d
(ppm) 3.86 (s,
3H), 5.26 (d, 1H, J¼4.6 Hz, H-1), 6.85–6.88 (m, 2H), 7.17–7.37 (m,
3H), 6.95 (d, 2H, J¼9.0 Hz), 7.17–7.20 (m, 3H), 7.35–7.39 (m, 2H),
10H), 7.42 (S, 1H, H-3), 7.51–7.55 (m, 2H); 13C NMR
d
(ppm) 55.4,
7.94–7.98 (m, 3H), 9.48 (s, 1H); 13C NMR
d
(ppm) 55.5, 114.1, 126.8,
78.2 (C-1), 113.9, 127.2, 127.9, 128.1, 128.4, 129.2, 129.5, 129.7, 132.5,
133.8 (C-3), 136.0, 136.5, 159.4. IR (neat): 3390, 3055, 2954, 2932,
2835,1610,1579,1513,1492,1476,1440,1303,1250,1173,1110,1065,
1034, 832, 737, 692, 591, 562 cmꢁ1. Anal. Calcd for C22H20O2Se
(395.34): C, 66.83; H, 5.10. Found: C, 66.59; H, 5.04.
127.0, 128.9, 129.3, 129.8, 131.2, 133.8, 154.0, 162.1, 191.7. IR (neat):
1682, 1603, 1584, 1563, 1508, 1257, 1177, 1123, 1105, 1022, 823,
738 cmꢁ1. Anal. Calcd for C16H14O2Se (317.23): C, 60.57; H, 4.45.
Found: C, 60.81; H, 4.38.
4.2. General procedure for the synthesis of 2-phenylselanyl-
2-en-1-ols 3–8
4.2.6. 3-Phenylselanylbut-3-en-2-ol 5a9,10
Yield 57%; yellow oil; Rf¼0.31 (EtOAc/pet. ether: 1/10); 77Se
NMR
d
(ppm) 381.0; 1H NMR
d
(ppm) 1.37 (d, 3H, J¼6.4 Hz), 1.97 (d,
For example, a solution of methyllithium (1.6 M in ether,
1.1 mmol, 0.69 ml) was added dropwise, under nitrogen, at ꢁ78 ꢀC,
to (Z)-2-(phenylselanyl)but-2-enal 2b (1 mmol, 225 mg) in anhy-
drous THF (12 ml). The mixture was stirred for 1 h and monitored
by TLC. The solution was then quenched with a saturated aqueous
NH4Cl solution (10 ml) and extracted with diethylether (3ꢂ12 ml).
The organic extracts were dried over magnesium sulfate and
concentrated under vacuum. The crude product was then
purified by chromatography on silica gel (eluent: EtOAc/pet. ether:
10/90).
1H, J¼6.0 Hz), 3.08 (br s, 1H), 4.37 (q, 1H, J¼6.0 Hz), 5.11 (s, 1H), 5.76
(s, 1H), 7.20–7.35 (m, 3H), 7.50–7.55 (m, 2H); 13C NMR
d
(ppm) 23.1,
71.6, 116.1, 127.2, 128.0, 129.3, 134.6, 148.1. IR (neat): 3388, 3071,
2975, 2926,1703,1608,1578,1476,1438,1368,1145,1067,1022, 739,
691 cmꢁ1. Anal. Calcd for C10H12OSe (227.16): C, 52.87; H, 5.32.
Found: C, 52.48; H, 5.16.
4.2.7. 3-Phenylselanylpent-3-en-2-ol 5b
Yield 88%; yellow oil; Rf¼0.30 (EtOAc/pet. ether: 1/10); 77Se
NMR
d
(ppm) 254.7; 1H NMR
d
(ppm) 1.34 (d, 3H, J¼6.4 Hz), 1.87 (d,
1H, J¼6.4 Hz), 1.97 (d, 1H, J¼6.0 Hz), 4.33 (m, 1H), 6.35 (q, 3H,
4.2.1. 1-Phenyl-2-phenylselanylprop-2-en-1-ol 3a9
J¼6.4 Hz), 7.15–7.30 (m, 3H), 7.35–7.40 (m, 2H); 13C NMR
d (ppm)
Yield 72%; yellow oil; Rf¼0.28 (EtOAc/pet. ether: 1/10); 77Se
17.6, 23.0, 72.9, 126.4, 129.4, 130.4, 131.0, 133.0, 138.2. IR (neat):
3382, 3070, 3050, 2972, 2928, 2870, 1577, 1476, 1437, 1372, 1296,
1109,1000, 984, 735, 691 cmꢁ1. MS (EI): 242.00 (Mþ), 205 (MþꢁPh),
197 (MþꢁC5H9O). Anal. Calcd for C11H14OSe (241.19): C, 54.78; H,
5.85. Found: C, 54.48; H, 5.86.
NMR
d
(ppm) 390.1; 1H NMR
d
(ppm) 2.34 (d, 1H, J¼4.6 Hz), 5.30 (s,
1H), 5.33 (s, 1H), 5.88 (s, 1H), 7.25–7.43 (m, 8H), 7.50–7.54 (m, 2H);
13C NMR
d
(ppm) 77.5, 118.2, 126.8, 128.1, 128.2, 128.5, 128.8, 129.5,
134.8, 141.1, 146.0. IR (neat): 3454, 3058, 2963, 1712, 1673, 1578,
1476, 1438, 1265, 1022, 738, 691 cmꢁ1. Anal. Calcd for C15H14OSe
(289.22): C, 62.29; H, 4.88. Found: C, 62.39; H, 5.03.
4.2.8. 4-Phenyl-3-phenylselanylbut-3-en-2-ol 5c11
Yield 88%; yellow oil; Rf¼0.26 (EtOAc/pet. ether: 1/10); 77Se
4.2.2. 1-Phenyl-2-phenylselanylbut-2-en-1-ol 3b
NMR
d
(ppm) 311.3; 1H NMR
d
(ppm) 1.44 (d, 3H, J¼6.4 Hz), 2.02 (d,
Yield 83%; red oil; Rf¼0.32 (EtOAc/pet. ether: 10/90); 77Se NMR
1H, J¼4. 9 Hz), 4.39 (m, 1H), 7.19–7.34 (m, 7H), 7.38–7.43 (m, 2H),
d
(ppm) 269.3; 1H NMR
d
(ppm) 1.88 (dd, 3H, J¼1.0, 6.7 Hz), 2.47 (d,
7.49–7.54 (m, 2H); 13C NMR
d
(ppm) 17.7, 78.3, 126.5, 126.7, 128.0,
1H, J¼5.9 Hz), 5.28 (d, 1H, J¼5.9 Hz), 6.38 (dq, 1H, J¼1.0, 6.7 Hz),
128.4, 129.3, 130.8, 134.3, 136.6, 141.8. IR (neat): 3325, 3056, 2976,
2928, 1577, 1490, 1476, 1443, 1367, 1265, 1129, 1070, 1045, 1022, 881,
738, 692 cmꢁ1. Anal. Calcd for C16H16OSe (303.25): 63.37; H, 5.32.
Found: C, 63.26; H, 5.43.
7.17–7.35 (m, 5H); 13C NMR
d
(ppm) 17.6, 78.2, 126.4, 126.7, 127.6,
128.3, 128.5, 129.2, 130.6, 134.1, 136.5, 141.7. IR (neat): 3390, 3058,
3030, 2909, 1577, 1476, 1438, 1373, 1067, 1022, 735, 691 cmꢁ1. MS

S. Redon et al. / Tetrahedron 64 (2008) 9293–9304
9299
4.2.9. 4-(4-Methoxy-phenyl)-3-phenylselanylbut-3-en-2-ol 5d
Yield 84%; yellow oil; Rf¼0.36 (EtOAc/pet. ether: 1/10); 77Se
1464, 1054, 690 cmꢁ1. Anal. Calcd for C14H20OSe (283.26): C, 59.36;
H, 7.12. Found: C, 59.61; H, 7.43.
NMR
d
(ppm) 301.4; 1H NMR
d
(ppm) 1.43 (d, 3H, J¼6.3 Hz), 2.09 (d,
1H, J¼4.9 Hz), 3.80 (s, 3H), 4.40 (m, 1H), 6.85 (dd, 2H, J¼1.9, 6.8 Hz),
4.2.16. 4,4-Dimethyl-1-phenyl-2-phenylselanylpent-1-en-3-ol 8c
Yield 31%; yellow oil; Rf¼0.44 (EtOAc/pet. ether: 1/10); 1H NMR
7.19–7.28 (m, 4H), 7.39–7.43 (m, 2H), 7.54 (d, 2H, J¼8.6 Hz); 13C
NMR
d
(ppm) 23.4, 55.3, 73.0, 113.5, 126.9, 128.9, 129.3, 130.4, 131.0,
d
(ppm) 1.02 (s, 9H), 2.37 (d, 1H, J¼7.2 Hz), 4.03 (d, 1H, J¼6.6 Hz),
131.5, 133.5, 135.1, 159.4. IR (neat): 3390, 3056, 2971, 2928, 2836,
1605, 1576, 1510, 1476, 1438, 1304, 1251, 1177, 1132, 886, 824, 736,
691 cmꢁ1. Anal. Calcd for C17H18O2Se (333.27): 61.26; H, 5.44.
Found: C, 61.42; H, 5.35.
7.08–7.47 (m, 11H); 13C NMR
130.0, 132.1, 135.4, 136.3. IR (neat): 3445, 2960, 2867, 1669, 1626,
d (ppm) 26.5, 36.2, 83.8, 126.2, 129.3,
1578, 1490, 1476, 1069, 1010, 757, 738, 691 cmꢁ1
.
4.3. General procedure for the synthesis of
enones 9–14
a
-phenylselanyl
4.2.10. 2-Phenylselanylhept-1-en-3-ol 6a
Yield 57%; yellow oil; Rf¼0.33 (EtOAc/pet. ether: 1/10); 77Se
NMR
d
(ppm) 379.6; 1H NMR
d
(ppm) 0.89 (t, 3H, J¼6.8 Hz), 1.20–
To a solution of diphenyldiselenide (280 mg, 0.9 mmol) in 10 ml
cyclohexane was added slowly a solution of tert-butyl hydroper-
oxide 70% in water (180 ml, 1.8 mmol). The mixture was refluxed for
1.32 (m, 4H), 1.63–1.73 (m, 2H), 1.88 (br s, 1H), 4.11 (q, 1H, J¼7.2 Hz),
5.12 (s, 1H), 5.75 (s, 1H), 7.25–7.33 (m, 3H), 7.55–7.60 (m, 2H); 13C
NMR
d
(ppm): 14.1, 22.6, 27.8, 36.1, 76.1, 116.5, 128.1, 128.5, 129.5,
30 min and then was introduced 1-phenyl-2-phenylselanylbut-2-
en-1-ol 3b (454 mg, 1.5 mmol) in cyclohexane (2 ml). The solution
was refluxed and monitored by TLC. After completion, the solution
was cooled to rt, dried over magnesium sulfate, filtrated, and
concentrated under vacuum. The crude product was then purified
by chromatography on silica gel (eluent: CH2Cl2/pet. ether: 1/5).
135.0, 147.4. IR (neat): 3386, 3072, 2955, 2931, 2859, 1807, 1578,
1476, 1438, 739 cmꢁ1. Anal. Calcd for C13H18OSe (269.23): C, 57.99;
H, 6.74. Found: C, 57.68; H, 7.02.
4.2.11. 3-Phenylselanyloct-2-en-4-ol 6b
Yield 75%; yellow oil; Rf¼0.36 (EtOAc/pet. ether: 1/10); 77Se
NMR
d
(ppm) 252.0; 1H NMR
d
(ppm) 0.86 (t, 3H, J¼6.8 Hz), 1.20–
4.3.1. 1-Phenyl-2-phenylselanylprop-2-en-1-one 9a12
1.32 (m, 4H), 1.55–1.63 (m, 2H), 1.87 (d, 3H, J¼6.4 Hz), 1.90 (s, 1H),
Yield 54%; yellow oil; Rf¼0.44 (EtOAc/cyclohexane: 1/9); 77Se
4.10 (m, 1H), 6.31 (q, 1H, J¼6.4 Hz), 7.18–7.27 (m, 3H), 7.38–7.42 (m,
NMR d d (ppm) 5.71 (s, 1H), 6.20 (s, 1H), 7.25–
(ppm) 390.8; 1H NMR
2H); 13C NMR
d
(ppm) 14.1, 17.2, 22.5, 28.0, 36.3, 77.2, 126.2, 129.3,
7.50 (m, 8H), 7.60–7.65 (m, 2H). IR (neat): 1694, 1673, 1597, 1579,
130.4, 131.1, 133.6, 137.3. IR (neat): 3388, 3070, 2956, 2931, 2858,
1578, 1476, 1438, 739 cmꢁ1. MS (EI): 284.00 (Mþ), 205 (MþꢁC4H9),
197 (MþꢁC5H9O). Anal. Calcd for C14H20OSe (283.26): C, 59.36; H,
7.12. Found: C, 59.32; H, 6.95.
1475, 1448, 1438, 1266, 1174, 1021, 737, 689 cmꢁ1
.
4.3.2. 1-Phenyl-2-phenylselanylbut-2-en-1-one 9b4
Yield 88%; red oil; Rf¼0.29 (CH2Cl2/pet. ether: 1/5); 77Se NMR
d
(ppm) 342.8; 1H NMR
d
(ppm) 2.08 (d, 3H, J¼6.9 Hz), 6.79 (q, 1H,
4.2.12. 1-Phenyl-2-phenylselanylhept-1-en-3-ol 6c
J¼6.9 Hz), 7.16–7.50 (m, 8H), 7.67–7.71 (m, 2H); 13C NMR
d (ppm)
Yield 66%; yellow oil; Rf¼0.28 (EtOAc/pet. ether: 1/10); 77Se
18.5, 127.2, 128.2, 129.2, 129.5, 130.1, 132.4, 132.5, 135.3, 137.2, 144.5,
194.6. IR (neat): 1655, 1596, 1578, 1477, 1447, 1438, 1263, 1063, 1022,
800, 736, 708 cmꢁ1. MS (EI): 302.00 (Mþ), 205 (MþꢁC7H5O), 197
(MþꢁC5H9O). Anal. Calcd for C16H14OSe (301.23): C, 63.79; H, 4.68.
Found: C, 63.69; H, 4.54.
NMR
d
(ppm) 310.9; 1H NMR
d
(ppm) 0.87 (t, 3H, J¼7.1 Hz), 1.22–
1.45 (m, 4H), 1.62–1.84 (m, 2H), 1.94 (d, 1H, J¼6.0 Hz), 4.19 (m, 1H),
7.18–7.55 (m, 11H); 13C NMR
d
(ppm) 14.2, 22.7, 28.0, 36.7, 76.8,
127.1, 127.9, 128.1, 129.3, 129.4, 130.1, 132.2, 133.8, 136.6, 137.0. IR
(neat): 3384, 3057, 2955, 2931, 2858, 1578, 1476, 1438, 1068, 1022,
739 cmꢁ1. Anal. Calcd for C19H22OSe (345.33): C, 66.08; H, 6.42.
Found: C, 66.36; H, 6.57.
4.3.3. 1,3-Diphenyl-2-phenylselanylprop-2-en-1-one 9c11,13
Yield 83%; yellow solid (mp¼51–53 ꢀC); Rf¼0.32 (CH2Cl2/pet.
ether: 1/5); 77Se NMR (ppm) 404.5; 1H NMR
d d (ppm) 7.08–7.17 (m,
4.2.13. 5-Methyl-3-phenylselanylhept-2-en-4-ol 7b
3H), 7.31–7.50 (m, 9H), 7.63–7.65 (m, 2H), 7.72–7.74 (m, 2H); 13C
NMR (ppm) 128.1, 128.2, 128.6, 129.2, 129.7, 129.9, 132.7, 134.5,
Yield 36%, two diastereomers 50/50; yellow oil; Rf¼0.40 (EtOAc/
d
pet. ether: 1/10); 77Se NMR
d
(ppm) 250.9; 1H NMR
d
(ppm) 0.78 (m,
135.6, 137.4, 139.0, 194.8. IR (KBr): 1656, 1596, 1579, 1476, 1446,
1244, 1022, 739, 690 cmꢁ1. Anal. Calcd for C21H16OSe (363.30): C,
69.42; H, 4.44. Found: C, 69.67; H, 4.27.
3H), 1.10–40 (m, 2H), 1.60–1.80 (m, 4H), 1.85 (d, 3H, J¼6.7 Hz), 6.25
(q, 1H, J¼6.7 Hz), 7.14–7.37 (m, 6H); 13C NMR
d (ppm): 11.3, 11.6,
13.7, 16.1, 17.6, 24.2 (C-7), 26.6 (C-7), 80.6 (C-3), 82.0 (C-3), 126.3,
126.5, 129.2, 130.5, 130.8, 130.9, 131.1, 134.9 (C-5), 133.8 (C-5), 136.2,
136.4. IR (neat): 3436, 2962, 2931, 2874, 1578, 1476, 1438, 1377,
1022, 735, 690 cmꢁ1. Anal. Calcd for C14H20OSe (283.26): C, 59.36;
H, 7.12. Found: C, 58.93; H, 6.96.
4.3.4. 3-(4-Methoxy-phenyl)-1-phenyl-2-phenylselanylprop-2-en-
1-one 9d
Yield 91%; yellow oil; Rf¼0.37 (EtOAc/pet. ether: 1/9); 77Se NMR
d
(ppm) 385.4; 1H NMR
d (ppm) 3.85 (s, 3H), 6.93–6.97 (m, 2H),
7.10–7.17 (m, 3H), 7.33–7.40 (m, 4H), 7.46–7.52 (m, 2H), 7.65–7.75
4.2.14. 4-Methyl-1-phenyl-2-phenylselanylhex-1-en-3-ol 7c
Yield 30%; yellow oil; Rf¼0.42 (EtOAc/pet. ether: 1/10); 77Se
(m, 4H); 13C NMR
d
(ppm) 55.5, 114.0, 127.7, 127.9, 128.2, 129.2,
129.6, 131.2, 132.1, 132.4, 133.6, 137.8, 141.2, 160.7, 195.1. IR (neat):
1657, 1604, 1579, 1509, 1476, 1446, 1439, 1307, 1293, 1253, 1175,
NMR d d (ppm) 0.76–0.80 (m, 3H), 0.85–0.93
(ppm) 306.9; 1H NMR
(m, 3H), 1.17–1.43 (m, 2H), 1.65–1.90 (m, 2H), 3.97–4.13 (m, 1H),
7.16–7.52 (m, 11H). IR (neat): 3437, 3057, 2961, 2928, 1682, 1577,
1066, 1024, 909, 828, 735, 706, 690 cmꢁ1
.
Anal. Calcd for
C22H18O2Se (393.33): C, 67.18; H, 4.61. Found: C, 67.03; H, 4.51.
1476, 1438, 1021, 736, 691 cmꢁ1
.
4.3.5. 1-(4-Methoxy-phenyl)-3-diphenyl-2-phenylselanylprop-2-
en-1-one 10c
4.2.15. 2,2-Dimethyl-4-phenylselanylhex-4-en-3-ol 8b
Yield 36%; yellow oil; Rf¼0.44 (EtOAc/pet. ether: 1/10); 1H NMR
Yield 80%; yellow solid (mp¼80–82 ꢀC); Rf¼0.30 (EtOAc/cyclo-
d
(ppm) 0.92 (s, 9H), 1.78 (d, 3H, J¼6.7 Hz), 2.41 (d, 1H, J¼8.8 Hz),
hexane: 1/5); 77Se NMR (ppm) 409.9; 1H NMR
d d (ppm) 3.86 (s,
3.90 (d, 1H, J¼8.8 Hz), 6.25 (q, 1H, J¼6.7 Hz), 7.14–7.26 (m, 3H),
7.36–7.39 (m, 2H); 13C NMR
(ppm) 18.2, 26.8, 33.2, 84.1, 126.5,
129.6, 130.2, 136.6. IR (neat): 3484, 2954, 2867, 1578, 1477, 1438,
3H), 6.83–6.86 (m, 2H), 7.07–7.17 (m, 3H), 7.33–7.46 (m, 6H), 7.61–
7.65 (m, 2H), 7.76–7.79 (m, 2H); 13C NMR
(ppm) 55.6, 92.1, 113.5,
128.2, 128.5, 129.0, 129.1, 129.7, 130.0, 132.1, 134.3, 134.7, 135.7, 137.1,
d
d

9300
S. Redon et al. / Tetrahedron 64 (2008) 9293–9304
163.4, 193.3. IR (KBr): 1652, 1599, 1574, 1508, 1445, 1313, 1253, 1167,
1023, 840, 770, 738, 690 cmꢁ1. Anal. Calcd for C22H18O2Se (393.33):
C, 67.18; H, 4.61. Found: C, 67.49; H, 4.48.
204.2. IR (neat): 2966, 2932, 1681, 1602, 1578, 1477, 1438, 1070,
1022, 736, 690 cmꢁ1. Anal. Calcd for C14H18OSe (281.24): C, 59.79;
H, 6.45. Found: C, 59.68; H, 6.34.
4.3.6. 3-Phenylselanylbut-3-en-2-one 11a6b,12,14
4.3.13. 4-Methyl-1-phenyl-3-phenylselanylhexen-3-one 13c
Yield 89%; yellow oil; Rf¼0.20 (CH2Cl2/pet. ether: 1/5); 77Se NMR
Yield 54%; yellow oil; 77Se NMR (ppm) 413.1; 1H NMR
d d (ppm)
2.44 (s, 3H), 5.49 (s, 1H), 6.46 (s, 1H), 7.37–7.39 (m, 3H), 7.58–7.61
d
(ppm) 349.7; 1H NMR
d
(ppm) 0.69 (t, 3H, J¼7.4 Hz), 0.89 (d, 3H,
(m, 2H); 13C NMR
196.6.
d
(ppm) 25.6, 124.4, 127.0, 129.1, 137.0, 146.6,
J¼6.9 Hz), 1.23–1.32 (m, 1H), 1.50–1.60 (m, 1H), 3.25–3.32 (m, 1H),
7.15–7.4 (m, 8H), 7.63–7.70 (m, 2H), 7.8 (s,1H). IR (neat): 2966, 2932,
2874, 1682, 1578, 1476, 1438, 1068, 738, 690 cmꢁ1
.
4.3.7. 3-Phenylselanylpent-3-en-2-one 11b
Yield 85%; yellow oil; Rf¼0.30 (CH2Cl2/pet. ether: 1/5); 77Se NMR
4.3.14. 2,2-Dimethyl-4-phenylselanylhex-4-en-3-one 14b
d
(ppm) 295.8; 1H NMR
d
(ppm) 2.10 (d, 3H, J¼6.8 Hz), 2.37 (s, 3H),
Yield 90%; yellow oil; Rf¼0.27 (CH2Cl2/pet. ether: 1/5); 77Se NMR
7.19–7.33 (m, 6H); 13C NMR
d
(ppm) 19.0, 27.5, 126.6, 129.3, 130.6,
d
(ppm) 338.0; 1H NMR
d
(ppm) 1.16 (s, 9H), 1.95 (d, 3H, J¼6.7 Hz),
130.7, 135.5, 147.4, 197.2. IR (neat): 1682, 1602, 1577, 1477, 1437,
6.39 (q, 1H, J¼6.7 Hz), 7.20–7.27 (m, 3H), 7.40–7.43 (m, 2H); 13C
1355, 1232, 1212, 1069, 1022, 737, 691 cmꢁ1. Anal. Calcd for
NMR
d (ppm) 18.0, 26.6, 36.3, 83.8, 126.2, 129.3, 130.0, 132.2, 135.4,
C
11H12OSe (239.17): C, 55.24; H, 5.06. Found: C, 54.98; H, 5.16.
136.2. IR (neat): 2965, 2931, 1677, 1578, 1477, 1438, 1364, 1137, 1098,
1022, 735, 690 cmꢁ1. MS (EI): 282 (Mþ), 205 (MþꢁC4H9). Anal.
Calcd for C14H18OSe (281.24): C, 59.79; H, 6.45. Found: C, 59, 97; H,
6.54.
4.3.8. 4-Phenyl-3-phenylselanylbut-3-en-2-one 11c15
Yield 89%; yellow solid (mp¼39–40 ꢀC); Rf¼0.30 (CH2Cl2/pet.
ether: 1/5); 77Se NMR
d d (ppm) 2.40 (s, 3H),
(ppm) 337.3; 1H NMR
7.19–7.42 (m, 8H), 7.66–7.70 (m, 2H), 7.97 (s, 1H); 13C NMR
d
(ppm)
4.3.15. 4,4-Dimethyl-1-phenyl-2-phenylselanylpent-1-en-
3-one 14c
28.3, 127.2, 128.3, 129.5, 129.8, 130.4, 130.7, 131.1, 132.8, 135.1, 143.9,
199.1. IR (neat): 1681, 1580, 1476, 1438, 1355, 1223, 1201, 1178, 1069,
1022, 736, 690 cmꢁ1. Anal. Calcd for C16H14OSe (301.24): C, 63.79;
H, 4.68. Found: C, 63.58; H, 4.74.
Yield 89%; orange solid (mp¼65–68 ꢀC); Rf¼0.25 (CH2Cl2/pet.
ether: 1/5); 77Se NMR
d d (ppm) 1.13 (s, 9H),
(ppm) 388.2; 1H NMR
7.01 (s, 1H), 7.20–7.55 (m, 10H); 13C NMR
128.4, 128.5, 128.6, 129.2, 129.4, 133.0, 133.1, 134.4, 135.6, 209.0. IR
(neat): 2964, 2862, 1682, 1474, 1436, 1116, 1075, 778, 746, 690 cmꢁ1
d (ppm) 27.9, 44.2, 128.2,
4.3.9. 4-(4-Methoxy-phenyl)-3-phenylselanylbut-3-en-2-one 11d
Yield 85%; yellow oil; Rf¼0.33 (EtOAc/cyclohexane: 15/85); 77Se
.
Anal. Calcd for C19H20OSe (343.31): C, 66.46; H, 5.87. Found: C,
66.05; H, 5.88.
NMR d d (ppm) 2.42 (s, 3H), 3.84 (s, 3H), 6.89–
(ppm) 325.2; 1H NMR
6.93 (m, 2H), 7.19–7.35 (m, 5H), 7.78–7.81 (m, 2H), 8.02 (s, 1H); 13
NMR (ppm) 28.1, 55.3, 113.8, 126.8, 127.3, 128.8, 129.4, 130.4, 131.1,
C
d
132.8, 145.0 (C-4), 161.1, 198.8. IR (neat): 1682, 1603, 1584, 1564,
1506, 1477, 1439, 1309, 1298, 1258, 1177, 1125, 1104, 1024, 829, 737,
690 cmꢁ1. MS (EI): 332 (Mþ, 24), 77 (Phþ, 18), 43 (MeCOþ, 100).
Anal. Calcd for C17H16O2Se (331.26): C, 61.63; H, 4.87. Found: C,
61.68; H, 4.65.
4.4. General procedure for the addition of phosphorus ylides
to
a-phenylselanyl enones
A solution of n-BuLi (1.6 M in hexanes, 0.75 ml, 1.2 mmol) was
added slowly, under argon, to ethyltriphenylphosphonium bro-
mide (448 mg, 1.2 mmol) in anhydrous THF (10 ml). After stirring
4.3.10. 3-Phenylselanyloct-2-en-4-one 12b
for 5 min at rt, the a-phenylselanyl enone (1 mmol) in THF (2 ml)
Yield 76%; yellow oil; Rf¼0.28 (CH2Cl2/pet. ether: 1/5); 77Se NMR
was added dropwise. The mixture was stirred at reflux or at
50 ꢀC and monitored by TLC. After completion, the solution was
cooled to rt, quenched with a saturated aqueous NH4Cl solution,
and extracted with diethylether. The organic extracts were dried
over magnesium sulfate and concentrated under vacuum. The
residue was purified by chromatography on silica gel (light
petroleum).
d
(ppm) 296.9; 1H NMR
d
(ppm) 0.83 (t, 3H, J¼7.4 Hz), 1.17–1.28 (m,
2H), 1.44–1.55 (m, 2H), 2.07 (d, 3H, J¼6.9 Hz), 2.70 (t, 2H, J¼7.4 Hz),
7.19–7.33 (m, 6H); 13C NMR
d
(ppm) 14.0, 19.0, 22.4, 26.8, 39.5,
126.8, 129.4, 130.8, 131.0, 135.5, 146.0, 200.3. IR (neat): 2957, 2931,
2871, 1682, 1596, 1578, 1477, 1438, 736, 690 cmꢁ1. MS (EI): 282.00
(Mþ), 205 (MþꢁPh), 197 (MþꢁC5H9O). Anal. Calcd for C14H18OSe
(281.24): C, 59.79; H, 6.45. Found: C, 59.88, H, 6.39.
4.4.1. 1-(2,3-Dimethyl-1-phenylselanyl-cyclopropyl)-ethanone 15
Yield 65%; yellow oil (cis/trans: 40/60). cis Isomer: Rf¼0.27
4.3.11. 1-Phenyl-2-phenylselanylhept-1-en-3-one 12c
Yield 88%; yellow oil; Rf¼0.30 (CH2Cl2/pet. ether: 1/5); major Z-
(cyclohexane/EtOAc: 97/3); 77Se NMR (ppm) 276.0; 1H NMR
d
isomer (65%); 77Se NMR
d
(ppm) 337.4; 1H NMR
d
(ppm) 0.81 (t, 3H,
d
(ppm) 1.17 (d, 6H, J¼6.4 Hz), 2.00 (m, 2H), 2.45 (s, 3H), 7.15–7.30
J¼7.4 Hz), 1.12–1.25 (m, 2H), 1.37–1.50 (m, 2H), 2.74 (t, J¼7.4 Hz,
2H), 7.15–7.65 (m, 10H), 7.88 (s, 1H); 13C NMR
(ppm) 14.0, 22.3,
26.8, 40.1, 127.3, 128.4, 128.5, 128.7, 130.4, 133.2, 134.5, 135.4, 142.6,
201.9. Minor E-isomer: (35%); 1H NMR
(m, 5H); 13C NMR
d
(ppm) 10.7 (2C), 28.6 (2C), 30.8, 43.8, 126.0,
d
128.5, 129.5, 131.2, 209.0. IR (neat): 2955, 2925, 2852, 1686, 1578,
1478, 1459, 1438, 1385, 1354, 1244, 1209, 1146, 1074, 1022, 997, 734,
690 cmꢁ1. trans Isomer: Rf¼0.33 (cyclohexane/EtOAc: 97/3), 77Se
d
(ppm) 0.95 (t, 3H, J¼7.4 Hz),
1.33–1.45 (m, 2H), 1.67–1.77 (m, 2H), 2.67 (t, J¼7.7 Hz, 2H), 7.15–
7.65 (m, 11H). IR (neat): 2957, 2931, 2871, 2202, 1676, 1579, 1476,
1444, 1134, 1070, 757; 737, 690 cmꢁ1. Anal. Calcd for C19H20OSe
(343.31): C, 66.47; H, 5.87. Found: C, 66.42; H, 6.18.
NMR
d
(ppm): 350.6; 1H NMR
d
(ppm) 1.09 (d, 3H, J¼6.1 Hz), 1.24
(d, 3H, J¼6.1 Hz), 1.35 (m, 1H), 2.00 (m, 1H), 2.46 (s, 3H), 7.15–7.35
(m, 5H); 13C NMR
d
(ppm) 12.9, 16.0, 26.0, 30.8, 32.2, 43.4, 126.3,
129.3, 129.5, 132.9, 206.5. IR (neat): 3058, 2956, 2927, 1688, 1579,
1478, 1450, 1438, 1381, 1354, 1256, 1191, 1137, 1083, 1071, 1023, 734,
691 cmꢁ1.GC–MS: tR¼9.9 min (cis), 10.3 min (trans). MS (EI, 70 eV)
m/z (relative intensity): 268 (Mþ, 26), 266 (14), 225 (MþꢁCH3CO,
6), 188 (35), 187 (34), 157 (PhSeþ, 20), 145 (23), 144 (17), 143 (16),
129 (17), 96 (35), 77 (Phþ, 28), 51 (30), 43 (CH3COþ, 100). Anal.
Calcd for C13H160Se (267.22): C, 58.43; H, 6.03. Found: C, 57.78; H,
5.89.
4.3.12. 5-Methyl-3-phenylselanylhept-2-en-4-one 13b
Yield 86%; yellow oil; Rf¼0.31 (CH2Cl2/pet. ether: 1/5); 77Se NMR
d
(ppm) 304.4; 1H NMR
d
(ppm) 0.72 (t, 3H, J¼7.4 Hz), 0.94 (d, 3H,
J¼6.9 Hz), 1.23–1.32 (m, 1H), 1.54–1.64 (m, 1H), 2.06 (d, 3H,
J¼6.9 Hz), 3.18–3.25 (m, 1H), 7.15–7.4 (m, 6H); 13C NMR
d (ppm)
11.7, 16.8, 19.0, 26.6, 43.0, 126.8, 129.4, 130.9, 131.1, 135.7, 145.3,

S. Redon et al. / Tetrahedron 64 (2008) 9293–9304
9301
4.4.2. 1-(2-Methyl-1-phenylselanyl-3-propyl-cyclopropyl)-
ethanone 16
(cis). MS (EI, 70 eV) m/z (relative intensity): 358 (8), 356 (6), 281 (8),
221 (14), 207 (32), 158 (44), 157 (20), 105 (PhCOþ, 100), 77 (69), 44
(42). trans Isomer: Rf¼0.38 (cyclohexane/EtOAc: 97/3); 77Se NMR
Yield 41%; yellow oil (cis/trans: 45/55). cis Isomer: Rf¼0.36 (cy-
clohexane/EtOAc: 97/3), 77Se
d
(ppm): 283.6; 1H NMR
d
(ppm) 0.93
d
(ppm) 392.3; 1H NMR
d
(ppm) 0.87 (t, 3H, J¼7.4 Hz), 1.38 (d, 3H,
(t, 3H, J¼7.3 Hz), 1.18 (d, 3H, J¼6.5 Hz), 1.41 (m, 2H), 1.54 (m, 2H),
J¼6.1 Hz), 1.30–1.50 (m, 5H), 1.73 (dq, 1H, J¼6.1, 6.4 Hz), 7.15–7.55
1.71 (m, 1H), 2.19 (dq, J¼6.5, 9.8 Hz, 1H), 2.46 (s, 3H), 7.15–7.30 (m,
(m, 8H), 7.85–7.90 (m, 2H); 13C NMR
d
(ppm) 13.9, 16.5, 22.5, 24.0
5H); 13C NMR
d
(ppm) 10.9, 14.1, 22.7, 27.4 (C-2), 28.2, 29.7, 35.1 (C-
(C-2), 32.6, 35.5 (C-3), 39.4 (C-1), 126.7, 128.1, 128.5, 129.1, 129.7,
131.0, 132.6, 136.7, 197.2. Anal. Calcd for C20H22OSe (357.34): C,
67.22; H, 6.20. Found: C, 67.15; H, 6.24.
3), 43.4 (C-1), 126.0, 128.5, 129.45, 134.0, 208.9. IR (neat): 2958,
2926, 1687, 1578, 1478, 1438, 1354, 1138, 1022, 734, 690 cmꢁ1. GC–
MS: tR¼10.9 min (trans), 11.2 min (cis). MS (EI, 70 eV) m/z (relative
intensity): 296 (Mþ, 26), 294 (14), 266 (14), 253 (MþꢁCH3CO, 16),
215 (43), 173 (16), 157 (PhSeþ, 25), 124 (19), 96 (88), 95 (75), 77
(Phþ, 32), 55 (42), 43 (CH3COþ, 100). trans Isomer: Rf¼0.45 (cyclo-
4.4.6. Phenyl-(2-but-3-enyl-3-methyl-1-phenylselanyl-
cyclopropyl)-methanone 20
Yield 45%, yellow oil (cis/trans: 52/48). cis Isomer: Rf¼0.32 (cy-
hexane/EtOAc: 97/3); 77Se NMR
d
(ppm) 352.1; 1H NMR
d
(ppm)
clohexane/EtOAc: 97/3); 77Se NMR (ppm) 318.4; 1H NMR
d d (ppm)
0.90 (t, 3H, J¼7.0 Hz), 1.25 (d, 3H, J¼6.1 Hz), 1.18–1.48 (m, 5H), 2.06
1.38 (d, 3H, J¼6.15 Hz), 1.70–1.80 (m, 2H), 1.85–1.96 (m, 2H), 2.14–
2.24 (m, 2H), 4.96–5.09 (m, 2H), 5.78–5.92 (m, 1H), 7.10–7.55 (m,
8H), 7.82–7.88 (m, 2H). IR (neat): 3059, 2976, 2926, 1666, 1579,
1479, 1448, 1438, 1267, 1233, 1177, 1069, 1023, 999, 736, 691,
657 cmꢁ1; GC–MS: tR¼18.4 min (trans). MS (EI, 70 eV) m/z (relative
intensity): 370 (Mþ, 4), 213 (21), 184 (22), 158 (34), 157 (23), 105
(PhCOþ, 100), 77 (56), 51 (14), 41 (16). trans Isomer: Rf¼0.38 (cy-
(dq, J¼6.1, 6.5 Hz, 1H), 2.46 (s, 3H), 7.15–7.30 (m, 5H); 13C NMR
d
(ppm) 13.9, 16.2, 22.7, 25.5 (C-2), 29.8, 30.8, 38.4 (C-3), 43.2 (C-1),
126.3, 129.2, 129.4, 131.9, 206.6. Anal. Calcd for C15H20OSe (295.28):
C, 61.01; H, 6.83. Found: C, 61.08; H, 6.92.
4.4.3. 1-(2-But-3-enyl-3-methyl-1-phenylselanyl-cyclopropyl)-
ethanone 17
clohexane/EtOAc: 97/3), 77Se NMR (ppm) 393.2; 1H NMR
d d (ppm)
Yield 38%; yellow oil (cis/trans: 40/60). cis Isomer: Rf¼0.36 (cy-
1.35 (d, 3H, J¼6.4 Hz), 1.70–1.80 (m, 2H), 1.85–1.96 (m, 2H), 2.14–
clohexane/EtOAc: 97/3); 77Se NMR
d
(ppm) 283.4; 1H NMR
d
(ppm)
2.24 (m, 2H), 4.96–5.09 (m, 2H), 5.78–5.92 (m, 1H), 7.10–7.55 (m,
1.24 (d, 3H, J¼6.5 Hz), 1.60–1.78 (m, 3H), 2.04–2.20 (m, 3H), 2.48 (s,
8H), 7.82–7.88 (m, 2H); 13C NMR
d (ppm) 10.6, 22.2 (C-3), 25.5, 27.9
(C-2), 33.5, 40.3 (C-1), 115.3, 126.75, 128.1, 129.1, 129.2, 129.7, 131.1,
132.4, 136.3, 138.1, 198.4. Anal. Calcd for C21H22OSe (369.35): C,
68.28; H, 6.00. Found: C, 67.96; H, 5.87.
3H), 4.96–5.06 (m, 2H), 5.73–5.86 (m, 1H), 7.15–7.35 (m, 5H); 13C
NMR
115.5, 126.1, 128.5, 129.2, 137.8, 206.5. trans Isomer: Rf¼0.45 (cy-
clohexane/EtOAc: 97/3), 77Se NMR (ppm) 352.8; 1H NMR
(ppm)
d (ppm) 16.1, 25.6, 27.1 (C-2), 29.7, 33.7, 33.7 (C-3), 38.1 (C-1),
d
d
1.18 (d, 3H, J¼6.5 Hz), 1.60–1.76 (m, 3H), 2.04–2.20 (m, 3H), 2.46 (s,
4.4.7. 1-Phenyl-3-methyl-2-phenylselanylpent-1,3-diene 21
3H), 4.96–5.06 (m, 2H), 5.73–5.86 (m, 1H), 7.15–7.35 (m, 5H); 13C
Yield 24%; yellow oil; Rf¼0.68 (cyclohexane/EtOAc: 90/10). Mi-
NMR
d
(ppm) 10.9, 25.7, 27.3 (C-2), 29.7, 33.6, 34.5 (C-3), 43.3 (C-1),
nor isomer: 1H NMR
d
(ppm) 1.58 (d, 3H, J¼6.9 Hz), 1.71 (s, 3H), 5.95
115.5, 126.1, 128.5, 129.5, 137.9, 208.7. IR (neat): 3074, 2954, 2925,
2360, 1683, 1640, 1579, 1470, 1438, 1354, 1253, 1207, 1147, 1071,
1023, 997, 912, 735, 691, 668 cmꢁ1. MS (EI, 76 eV) m/z (relative in-
tensity): 308 (Mþ, 2), 265 (MþꢁCH3CO, 2), 157 (PhSeþ, 8), 77 (Phþ,
10), 43 (CH3COþ, 100). Anal. Calcd for C16H200Se (307.28): C, 62.53;
H, 6.56. Found C, 62.35; H, 6.71.
(q, 1H, J¼6.7 Hz, H-4), 7.04 (s, 1H, H-1), 7.15–7.36 (m, 8H), 7.49–7.54
(m, 2H); major isomer: 77Se NMR (ppm) 300.3; 1H NMR
d
d
(ppm)
1.64 (dd, 3H, J¼1.3, 6.8 Hz), 1.71 (s, 3H), 5.20 (q, 1H, J¼6.8 Hz, H-4),
6.70 (s, 1H, H-1), 7.15–7.36 (m, 8H), 7.49–7.54 (m, 2H); 13C NMR
d
(ppm) 15.3, 24.5, 123.8, 127.3, 127.8, 128.2, 128.3, 128.6, 129.1,
129.3, 129.4, 131.6, 135.4, 137.6. IR (neat): 3057, 2924, 2854, 1577,
1475, 1373, 1022, 736, 691 cmꢁ1
.
4.4.4. (2,3-Dimethyl-1-phenylselanyl-cyclopropyl)-phenyl-
methanone 18
4.4.8. 1-(2-Methyl-3-phenyl-1-phenylselanyl-cyclopropyl)-
ethanone 22
Yield 61%, yellow oil (cis/trans: 60/40); Rf¼0.30 (cyclohexane/
EtOAc: 97/3). cis Isomer: 77Se NMR
d
(ppm) 309.7; 1H NMR
d
(ppm)
Yield 10%, Rf¼0.34 (cyclohexane/EtOAc: 97/3), yellow oil (cis/
1.33 (d, 3H, J¼4.3 Hz), 1.34 (d, 3H, J¼4.3 Hz), 1.86 (m, 2H), 7.15–7.90
trans: 55/45). cis Isomer: 77Se (ppm) 391.2; 1H NMR
d d (ppm) 1.31 (d,
(m, 10H); 13C NMR
d
(ppm) 10.3, 10.4, 22.3, 40.6, 126.6, 128.7, 129.2,
3H, J¼6.3 Hz), 2.59 (s, 3H), 2.71 (m, 1H, H-2), 2.83 (d, 1H, J¼9.8 Hz),
130.7, 132.0, 132.4, 133.3, 198.3. IR (neat): 3057, 2959, 2927, 2871,
1662, 1596, 1578, 1479, 1438, 1265, 1199, 1071, 1023, 736, 693,
541 cmꢁ1. GC–MS: tR¼13.9 min (cis), 14.6 min (trans). MS (EI,
70 eV) m/z (relative intensity): 330 (Mþ, 13), 328 (7), 249 (12), 173
(6), 158 (61), 157 (PhSeþ, 25), 129 (16), 105 (PhCOþ, 100), 77 (Phþ,
7.15–7.35 (m,10H); 13C NMR
d
(ppm) 12.9, 26.5 (C-2), 29.6, 38.3 (C-3),
43.5 (C-1),126.1,127.4,128.6,128.7,129.5,129.9,131.6,135.2, 208.1. IR
(neat): 3059, 2958, 2927, 1682, 1578, 1496, 1478, 1446, 1355, 1265,
1215, 1170, 1072, 1055, 1022, 998, 746, 704 cmꢁ1. trans Isomer: 77Se
NMR
d
(ppm) 421.0; 1H NMR
d
(ppm) 1.26 (d, 3H, J¼5.6 Hz), 2.20 (m,
78), 51 (28). trans Isomer: 77Se NMR
1.11 (d, 3H, J¼6.3 Hz), 1.36 (d, 3H, J¼6.3 Hz), 1.51 (m, 1H), 1.73 (m,
1H), 7.15–7.95 (m, 10H); 13C NMR
(ppm) 15.4, 16.1, 24.4, 30.0, 39.4,
d
(ppm) 390.9; 1H NMR
d
(ppm)
1H, H-2), 2.54 (s, 3H), 3.21 (d, 1H, J¼7.7 Hz), 7.15–7.35 (m, 10H); 13
C
NMR d (ppm) 13.4, 22.8 (C-2), 29.8, 36.5 (C-3), 46.0 (C-1),126.8,127.8,
d
129.0, 129.1, 129.6, 130.3, 130.8, 137.2, 205.2. GC–MS: tR¼15.0 min.
MS (EI, 70 eV) m/z (relative intensity): 330 (Mþ, 6), 328 (4), 221 (12),
207 (12),158 (12),157 (7),129 (20),115 (15), 91 (10), 77 (12), 51 (14),
44 (21), 43 (100). Anal. Calcd for C18H18OSe (329.29): C, 65.65; H,
5.51. Found: C, 65.32; H, 5.67.
126.6, 128.1, 128.5, 129.1, 129.6, 130.7, 132.1, 132.6, 197.2. Anal. Calcd
for C18H18OSe (329,29): C, 65.65; H, 5.51. Found: C, 65.41; H, 5.45.
4.4.5. Phenyl-(2-methyl-1-phenylselanyl-3-propyl-cyclopropyl)-
methanone 19
Yield 45%, yellow oil (cis/trans: 60/40). cis Isomer: Rf¼0.32 (cy-
4.4.9. trans-2,5-Dimethyl-3-phenyl-4-phenylselanyl-2,3-
dihydrofuran 23
clohexane/EtOAc: 97/3); 77Se NMR (ppm) 318.2; 1H NMR
d d (ppm)
0.98 (t, 3H, J¼7.3 Hz), 1.33 (d, 3H, J¼6.4 Hz), 1.53 (m, 2H), 1.60–1.82
Yield 11%; yellow oil; Rf¼0.47 (cyclohexane/EtOAc: 97/3), 77Se
(m, 3H), 1.965 (dq, 1H, J¼6.4, 9.4 Hz), 7.15–7.55 (m, 8H), 7.85–7.90
NMR
d
(ppm) 242.0; 1H NMR
d
(ppm) 1.46 (d, 3H, J¼6.3 Hz), 2.14 (d,
(m, 2H); 13C NMR
d
(ppm) 10.7, 14.3, 22.1 (C-2), 22.7, 28.1, 28.5 (C-3),
3H, J¼1.7 Hz), 3.63 (dd, 1H, J¼1.7, 6.3 Hz, H-3), 4.60 (m, 1H, H-2),
40.35 (C-1), 126.6,128.1, 129.1, 129.2, 129.6, 131.0, 132.4, 136.4, 198.7.
IR (neat): 3058, 2958, 2927, 2871,1666,1597,1579,1479,1448,1264,
1231, 1177, 1070, 1023, 735, 691, 657 cmꢁ1. GC–MS: tR¼16.8 min
7.10–7.35 (m, 10H); 13C NMR (
d
ppm) 13.7, 21.6, 60.9 (C-3), 85.8 (C-
2), 98.2, 126.0, 127.0, 128.0, 128.6, 129.1, 129.6, 132.1, 143.2 (C-4),
162.0 (C-5). IR (neat): 3359, 2970, 2924, 2853, 1578, 1475, 1454,

9302
S. Redon et al. / Tetrahedron 64 (2008) 9293–9304
1438, 1376, 1108, 1073, 1021, 736, 699 cmꢁ1. MS (EI) m/z (relative
intensity): 330 (Mþ, 8), 157 (PhSeþ, 8), 77 (Phþ, 10), 43 (CH3COþ,
100). Anal. Calcd for C18H18OSe (329,29): C, 65.65; H, 5.51. Found: C,
65.57; H, 5.61.
1H, J¼5.8 Hz, H-3) 4.66 (m, 1H, H-2), 7.05–7.35 (m, 15H); 13C NMR
d
(ppm) 21.6, 62.2 (C-3), 84.7 (C-2), 99.3, 126.4, 127.2, 128.1, 128.2,
128.3, 128.7, 129.2, 129.6, 130.3, 130.8, 131.4, 143.1 (C-4), 158.4 (C-5).
IR (neat): 3059, 3028, 2971, 2925, 2360,1664,1597,1577,1492,1476,
1446, 1438, 1266, 1221, 1069, 1022, 909, 736, 692, 668 cmꢁ1. MS (EI)
m/z (relative intensity): 392 (Mþ, 14), 105 (PhCOþ, 100), 77 (Phþ,
34). Anal. Calcd for C23H20OSe (391.35): C, 70.58; H, 5.15. Found: C,
70.48; H, 5.20.
4.4.10. 1-(2-Phenyl-1-phenylselanyl-3-propyl-cyclopropyl)-
ethanone 24
Yield 27%; yellow oil, Rf¼0.34 (cyclohexane/EtOAc: 97/3) (cis/
trans: 50/50). cis Isomer: 77Se (ppm) 390.1; 1H NMR
d d (ppm) 0.88 (t,
3H, J¼7.2 Hz),1.45–1.54 (m, 3H),1.62–1.74 (m,1H), 2.42 (m,1H, H-3),
4.4.15. Phenyl-(2-phenyl-1-phenylselanyl-3-propyl-cyclopropyl)-
methanone 29
2.53 (s, 3H), 2.91 (d, 1H, J¼10.0 Hz), 7.10–7.35 (m, 10H); 13C NMR
d
(ppm) 14.3, 23.0, 29.2, 29.6, 32.4 (C-3), 37.4 (C-2), 43.3 (C-1),126.2,
Yield 53%, yellow oil (cis/trans: 60/40), Rf¼0.37 (cyclohexane/
127.3, 128.5, 128.9, 129.4, 129.9, 131.4, 135.5, 207.8. IR (neat): 3059,
2958, 2925, 2854, 2360,1684,1578,1478,1438,1354,1265,1211,1170,
EtOAc: 97/3). cis Isomer: 77Se NMR (ppm) 329.5; 1H NMR
d d (ppm)
0.83 (t, 3H, J¼7.3 Hz), 1.43 (m, 2H), 1.72 (m, 2H), 2.25 (dt, 1H, J¼6.8,
1072,1022, 736, 699 cmꢁ1. trans Isomer: 77Se NMR (ppm) 420.7; 1H
d
10.3 Hz, H-3), 2.81 (d, 1H, J¼10.3 Hz, H-2), 7.00–7.45 (m, 13H), 7.83–
NMR
1H), 2.10–2.18 (m, 1H, H-3), 2.55 (s, 3H), 3.26 (d, 1H, J¼7.8 Hz), 7.05–
7.35 (m,10H); 13C NMR
(ppm) 14.0, 22.7, 30.2, 30.7, 35.6 (C-3), 35.9
d
(ppm) 0.93 (t, 3H, J¼7.0 Hz), 1.33–1.52 (m, 3H), 1.59–1.69 (m,
7.85 (m, 2H); 13C NMR
d (ppm) 14.4, 22.7, 29.3 (C-3), 29.4, 33.4 (C-2),
41.5 (C-1), 127.1, 127.2, 128.1, 128.4, 129.0, 129.3, 130.15, 132.2, 133.3,
135.8, 136.4, 198.1. IR (neat): 3059, 2958, 2929, 2871, 2360, 1667,
1598, 1579, 1496, 1479, 1447, 1438, 1258, 1177, 1023, 909, 736, 694,
668 cmꢁ1. MS (EI) m/z (relative intensity): 420 (Mþ, 8), 157 (PhSeþ,
d
(C-2), 45.9 (C-1), 126.8, 126.9, 127.8, 129.0, 129.1, 130.3, 131.0, 137.3,
205.3. MS (EI) m/z (relative intensity): 358 (Mþ, 4), 315 (MþꢁCH3CO),
157 (PhSeþ, 30), 77 (Phþ, 6), 43 (CH3COþ, 100). Anal. Calcd for
12), 105 (PhCOþ, 100), 77 (Phþ, 46). trans Isomer: 77Se NMR
d
(ppm)
(ppm) 0.78 (t, 3H, J¼7.3 Hz), 1.43 (m, 2H), 1.72 (m,
2H), 2.20 (m, 1H, H-3), 2.79 (d, 1H, J¼7.0 Hz, H-2), 7.00–7.45 (m,
13H), 7.89–7.92 (m, 2H); 13C NMR
(ppm): 13.9, 22.5, 32.8 (C-3),
C20H22OSe (357.34): C, 67.22; H, 6.20. Found: C, 67.28; H, 5.94.
399.2; 1H NMR
d
4.4.11. 2,2-Dimethyl-1-(2-methyl-3-phenyl-1-phenylselanyl-
cyclopropyl)-propan-1-one 25
d
33.0, 34.5 (C-2), 42.6 (C-1), 126.7, 127.3, 127.5, 127.7, 128.3, 128.7,
129.2, 129.9, 132.4, 135.8, 136.3, 196.0. Anal. Calcd for C25H24OSe
(419.42): C, 71.59; H, 5.77. Found: C, 71.28; H, 5.94.
Yield 41%; yellow oil (cis/trans: 78/22); Rf¼0.30 (cyclohexane/
EtOAc: 98/2). cis Isomer: 77Se NMR
d d (ppm)
(ppm) 300.1; 1H NMR
1.18 (d, 3H, J¼6.4 Hz), 1.40 (s, 9H), 2.32 (m, 1H, H-2), 2.58 (d, 1H,
J¼10.1 Hz, H-3), 7.08–7.38 (m,10H); 13C NMR
d
(ppm) 12.4, 22.1 (C-2),
4.4.16. trans-3,5-Diphenyl-4-phenylselanyl-2-propyl-2,3-
dihydrofuran 30
29.1, 32.1(C-3), 39.8, 45.0,126.1,126.9,128.3,129.0,129.4,130.2,131.0,
135.2, 211.3. IR (neat): 3059, 2966, 2958, 2969,1677,1610,1579,1497,
Yield 7%; yellow oil; Rf¼0.51 (cyclohexane/EtOAc: 97/3), 77Se
1470, 1433, 1393, 1363, 1265, 1118, 1102, 1074, 1023, 735, 699 cmꢁ1
.
NMR
d
(ppm) 266.3; 1H NMR
d
(ppm) 0.96 (t, 3H, J¼7.1 Hz), 1.55 (m,
trans Isomer: 77Se NMR
J¼6.4 Hz), 1.37 (s, 9H), 2.07 (m, 1H, H-2), 2.71 (d, 1H, J¼7.1 Hz, H-3),
7.08–7.38 (m,10H); 13C NMR
(ppm) 16.5, 26.3 (C-2), 27.9, 28.7, 35.0
d
(ppm) 368.0; 1H NMR
d
(ppm) 1.24 (d, 3H,
1H), 1.68 (m, 2H), 1.87 (m, 1H), 3.75 (d, 1H, J¼5.7 Hz, H-3), 4.62 (dt,
1H, J¼5.3, 5.7 Hz, H-2), 7.12–7.40 (m, 13H), 7.94–7.99 (m, 2H); 13C
d
NMR d (ppm) 14.2, 18.7, 38.2, 60.7 (C-3), 88.2 (C-2), 99.4, 126.4,
(C-3), 42.4, 44.4, 126.4, 126.5, 128.2, 128.4, 128.7, 129.0, 136.6, 210.5.
MS (EI) m/z (relative intensity): 372 (Mþ, 36), 157 (PhSeþ, 58), 129
(MþꢁPhSe–(CH3)3CCO, 100), 77 (Phþ, 24). Anal. Calcd for C21H24OSe
(372.37): C, 67.92; H, 6.51. Found: C, 68.31; H, 6.40.
127.1, 128.1, 128.2, 128.7, 129.2, 129.6, 130.4, 130.8, 131.3, 143.5 (C-4),
158.4 (C-5). IR (neat): 3360, 3058, 2958, 2930, 2871, 2359, 1668,
1598, 1576, 1491, 1475, 1455, 1437, 1265, 1183, 1120, 1070, 1022, 736,
694, 539 cmꢁ1. MS (EI) m/z (relative intensity): 420 (Mþ, 8), 157
(PhSeþ, 14), 105 (PhCOþ, 100), 77 (Phþ, 34). Anal. Calcd for
4.4.12. trans-5-tert-Butyl-2-methyl-3-phenyl-4-phenylselanyl-2,3-
dihydrofuran 26
C25H24OSe (419.42): C, 71.59; H, 5.77. Found: C, 71.49; H, 5.91.
Yield 16%; yellow oil; Rf¼0.43 (cyclohexane/EtOAc: 98/2); 77Se
4.4.17. Phenyl-(2-but-3-enyl-3-phenyl-1-phenylselanyl-
cyclopropyl)-methanone 31
NMR
d
(ppm) 262.1; 1H NMR
d
(ppm) 1.35 (d, 3H, J¼6.9 Hz), 137 (s,
9H), 3.40 (d, 1H, J¼4.5 Hz, H-3), 4.48 (m, 1H, H-2), 7.05–7.30 (m,
Yield 32%, yellow oil (cis/trans: 56/44). cis Isomer: Rf¼0.32 (cy-
10H); 13C NMR
d
(ppm) 21.6, 29.5, 34.5, 61.9 (C-3), 83.7 (C-2), 94.6,
clohexane/EtOAc: 97/3), 77Se NMR (ppm) 339.6; 1H NMR
d d (ppm)
125.9, 127.0, 127.8, 128.6, 129.1, 129.5, 132.7, 144.1 (C-4), 168.9 (C-5).
IR (neat): 3062, 3028, 2967, 2924, 2852, 1603, 1578, 1476, 1455,
1438, 1373, 1360, 1312, 1226, 1133, 1102, 1036, 1022, 969, 734,
699 cmꢁ1. MS (EI) m/z (relative intensity): 372 (Mþ, 34), 157 (PhSeþ,
44), 129 (MþꢁPhSe–(CH3)3CCO, 54), 77 (Phþ, 22). Anal. Calcd for
1.91 (m, 2H), 2.18 (m, 2H), 2.34 (m, 1H), 2.87 (m, 1H), 4.94 (m, 2H),
5.76 (m, 1H), 7.15–7.60 (m, 13H), 7.82–7.95 (m, 2H); 13C NMR
d
(ppm) 26.7, 28.7, 33.4 (2C), 41.5, 115.2, 127.7, 128.1, 128.6, 128.7,
129.1, 129.4, 129.6, 130.1, 132.3, 133.6, 134.8, 137.0, 138.1, 197.8. IR
(neat): 3060, 2925, 2360, 1661, 1598, 1579, 1496, 1478, 1448, 1224,
1176, 1069, 1022, 911, 737, 691, 668 cmꢁ1. MS (EI) m/z (relative in-
tensity): 432 (Mþ, 2), 157 (PhSeþ, 26), 105 (PhCOþ, 100), 77 (Phþ,
80). trans Isomer: Rf¼0.38 (cyclohexane/EtOAc: 97/3); 77Se NMR
C
21H24OSe (372.37): C, 67.92; H, 6.51. Found: C, 68.20; H, 6.38.
4.4.13. Phenyl-(2-methyl-3-phenyl-cyclopropyl)-methanone
2720a,24
d d (ppm) 2.05 (m, 2H), 2.20 (m, 2H), 2.34 (m,
(ppm) 421.4; 1H NMR
Yield 22%, white solid, mp 42 ꢀC, 1H NMR
d
(ppm) 1.01 (d, 3H,
1H), 2.98 (m, 1H), 4.95 (m, 2H), 5.76 (m, 1H), 7.05–7.60 (m, 13H),
J¼6.2 Hz), 2.04 (dqd, 1H, J¼4.6, 6.2, 9.6 Hz, H-2), 2.84 (dd, 1H, J¼4.6,
7.92–7.97 (m, 2H); 13C NMR
d
(ppm) 30.5, 32.3 (C-3), 33.4, 34.6 (C-
4.7 Hz), 3.00 (dd,1H, J¼4.7, 9.6 Hz), 7.15–7.55 (m, 8H), 8.02–8.06 (m,
2), 42.7 (C-1), 115.2, 126.7, 127.7, 128.1, 128.3, 128.5, 128.7, 129.2,
129.9, 132.3, 132.9, 133.4, 137.0, 137.7, 195.8.
2H); 13C NMR
d (ppm) 13.1, 27.1, 32.0, 35.5, 126.7, 127.7, 128.2, 128.4,
128.7, 129.1, 133.0, 137.0, 199.5. IR (neat): 1665, 1598, 1578, 1448,
1264, 1222, 1023, 737, 696 cmꢁ1
.
4.4.18. 2-But-3-enyl-3,5-diphenyl-4-phenylselanyl-2,3-
dihydrofuran 32
4.4.14. trans-2-Methyl-3,5-diphenyl-4-phenylselanyl-2,3-
dihydrofuran 28
Yield 5%; yellow oil; Rf¼0.53 (cyclohexane/EtOAc: 97/3), 77Se
NMR
d d (ppm) 1.80 (m, 1H), 2.00 (m, 1H),
(ppm) 268.1; 1H NMR
Yield 47%; yellow oil; Rf¼0.64 (cyclohexane/EtOAc: 97/3), 77Se
2.27 (m, 2H), 3.75 (d, 1H, J¼5.6 Hz, H-3), 4.62 (dt, 1H, J¼5.3, 5.6 Hz,
NMR
d
(ppm) 266.1; 1H NMR
d
(ppm) 1.43 (d, 3H, J¼6.3 Hz), 3.62 (d,
H-2), 4.94–5.06 (m, 2H), 5.77–5.89 (m, 1H), 7.14–7.40 (m, 13H),

S. Redon et al. / Tetrahedron 64 (2008) 9293–9304
9303
7.94–7.99 (m, 2H); 13C NMR
d
(ppm) 29.6, 35.3, 60.7 (C-3), 87.7 (C-
d (ppm) 13.8, 21.5, 55.3, 60.1 (C-3), 86.0 (C-2), 98.6, 114.0, 126.0,
2), 99.6, 115.3, 126.5, 127.2, 128.1, 128.2, 128.7, 129.2, 129.6, 130.5,
130.74, 131.2, 132.2, 132.3, 137.8, 143.3 (C-4), 158.3 (C-5). IR (neat):
2925, 2853, 1732, 1641, 1598, 1576, 1490, 1475, 1446, 1070, 1028,
999, 911, 736, 693, 668, 658, 538 cmꢁ1. MS (EI) m/z (relative in-
tensity): 432 (Mþ, 20), 157 (PhSeþ, 12), 105 (PhCOþ, 100), 77 (Phþ,
40).
129.0, 129.1, 129.6, 132.2, 135.3, 158.7 (C-4), 161.8 (C-5). IR (neat):
2923, 2854, 1644, 1613, 1578, 1513, 1475, 1454, 1439, 1375, 1302,
1247, 1216, 1175, 1111, 1037, 955, 852, 823, 735, 690 cmꢁ1. MS (EI)
m/z (relative intensity): 360 (Mþ, 14), 157 (PhSeþ, 26), 77 (Phþ, 12),
43 (CH3COþ, 100). Anal. Calcd for C19H20O2Se (359.31): C, 63.51; H,
5.61. Found: C, 63.76; H, 5.49.
4.4.19. (4-Methoxy-phenyl)-(2-methyl-3-phenyl-cyclopropyl)-
methanone 33
4.4.24. Phenyl-(2-methyl-3-(p-methoxy-phenyl)-cyclopropyl)-
methanone 38
Yield 25%, yellow oil, Rf¼0.18 (cyclohexane/EtOAc: 95/5); 1H
Yield 13%, yellow oil, Rf¼0.13 (cyclohexane/EtOAc: 95/5); 1H
NMR
d
(ppm) 0.94 (d, 3H, J¼6.4 Hz), 1.94 (dqd, 1H, J¼4.6, 6.4, 9.4 Hz,
NMR
d
(ppm) 1.05 (d, 3H, J¼6.0 Hz), 2.00 (dqd,1H, J¼4.8, 6.0, 9.3 Hz,
H-2), 2.73 (dd, 1H, J¼4.6, 4.8 Hz), 2.90 (dd, 1H, J¼4.8, 9.4 Hz), 6.86–
H-2), 2.79 (dd,1H, J¼4.6, 4.8 Hz), 2.97 (dd,1H, J¼4.6, 9.3 Hz), 3.81 (s,
6.90 (m, 2H), 7.15–7.25 (m, 5H), 7.94–7.98 (m, 2H); 13C NMR
d
(ppm)
3H), 6.85 (m, 2H), 7.18 (m, 2H), 7.45–7.58 (m, 3H), 8.02–8.06 (m,
13.1, 26.5, 31.5, 35.0, 55.6, 113.9, 126.6, 128.4, 129.2, 130.4, 131.1,
132.1, 137.2, 197.9. IR (neat): 2960, 2991, 1698, 1600, 1575, 1510,
2H); 13C NMR
d (ppm) 13.1, 27.1 (C-2), 32.3 (C-1), 34.9 (C-3), 55.4,
113.8, 128.1, 128.7, 130.2, 131.3, 132.9, 136.8, 138.2, 199.6. IR (neat):
2958, 2991, 1661, 1613, 1580, 1514, 1418, 1327, 1286, 1247, 1221, 1179,
1424, 1311, 1260, 1229, 1168, 1028, 737, 700 cmꢁ1
.
1040, 801, 737, 692 cmꢁ1
.
4.4.20. trans-2-Methyl-3-phenyl-5-(p-methoxy-phenyl)-4-
phenylselanyl-2,3-dihydrofuran 34
4.4.25. 1-(4-Methoxy-phenyl)-3-phenyl-2-phenylselanyl-penta-
1,3-diene 39
Yield 33%; white solid (mp¼75–78 ꢀC); Rf¼0.4 (cyclohexane/
EtOAc: 95/5); 77Se NMR
d
(ppm) 263.7; 1H NMR
d
(ppm) 1.42 (d, 3H,
Yield 10%, Rf¼0.31 (cyclohexane/EtOAc: 97/3). Major isomer: 1H
J¼6.3 Hz), 3.62 (d, 1H, J¼5.8 Hz, H-3), 3.75 (s, 3H), 4.63 (dq, 1H,
NMR
d
(ppm) 2.14 (d, 3H, J¼7.0 Hz, H-5), 3.83 (s, 3H, OMe), 6.49 (q,
J¼6.1, 6.3 Hz, H-2), 6.81–6.85 (m, 2H), 7.05–7.30 (m, 10H), 7.85–7.90
1H, J¼7.0 Hz, H-4), 6.89 (s, 1H, H-1), 7.00–7.40 (m, 10H), 6.45–7.50
(m, 2H); 13C NMR
d
(ppm) 21.6, 55.4 (C-3), 62.3, 84.5 (C-2), 97.2,
(m, 2H), 7.60–7.70 (m, 2H). IR (neat): 2927, 2854, 2836, 1604, 1508,
113.5, 123.3, 126.2, 127.1, 128.1, 128.6, 129.2, 129.7, 129.9, 131.7, 143.2
(C-4), 158.5 (C-5). IR (neat): 3060, 3028, 2969, 2925, 1608, 1577,
1506, 1476, 1455, 1439, 1254, 1177, 1081, 1030, 832, 737 cmꢁ1. MS
(EI) m/z (relative intensity): 422 (Mþ, 8), 135 (MeOꢁC6H4–COþ,
100), 77 (Phþ, 18). Anal. Calcd for C24H22O2Se (421.38): C, 68.40; H,
5.26. Found: C, 68.38, H, 5.22.
1464, 1456, 1440, 1290, 1247, 1172, 1107, 1035, 831, 759, 697 cmꢁ1
.
MS (EI) m/z (relative intensity): 406 (Mþ, 26), 157 (PhSeþ, 36), 77
(Phþ, 44).
4.4.26. trans-2-Methyl-3-(p-methoxy-phenyl)-5-phenyl-4-
phenylselanyl-2,3-dihydrofuran 40
Yield 35%; yellow oil; Rf¼0.26 (cyclohexane/EtOAc: 97/3); 77Se
4.4.21. 1-[2-(4-Methoxy-phenyl)-3-methyl-1-phenylselanyl-
cyclopropyl]-ethanone 35
NMR
d
(ppm) 266.0; 1H NMR
d
(ppm) 1.50 (d, 3H, J¼6.2 Hz), 3.66 (d,
1H, J¼5.7 Hz, H-3), 3.80 (s, 3H), 4.70 (m, 1H, H-2), 6.82 (d, 2H,
J¼8.6 Hz), 7.06 (d, 2H, J¼8.6 Hz), 7.18–7.40 (m, 8H), 7.95–8.00 (m,
Yield 13%, yellow oil (cis/trans: 70/30). cis Isomer: Rf¼0.32 (cy-
clohexane/EtOAc: 97/3), 1H NMR
d
(ppm) 1.31 (d, 3H, J¼6.2 Hz), 2.57
2H); 13C NMR
d (ppm) 21.4, 55.2, 61.4 (C-3), 84.7 (C-2), 99.6, 114.0,
(s, 3H), 2.69 (m, 1H, H-2), 2.76 (d, 1H, J¼9.9 Hz), 3.82 (s, 3H), 6.85–
126.3, 128.1, 128.2, 129.0, 129.1, 129.5, 130.2,130.8,131.3, 135.1, 158.1,
158.7. IR (neat): 3058, 2968, 2925, 2834, 1614, 1674, 1544, 1493,
1476, 1446, 1374, 1337, 1303, 1246, 1175, 1111, 1069, 1033, 954, 865,
826, 769, 735, 691, 650, 560 cmꢁ1. MS (EI) m/z (relative intensity):
422 (Mþ, 8), 135 (MeOPhCOþ, 100), 77 (Phþ, 18). Anal. Calcd for
6.90 (m, 2H), 7.15–7.35 (m, 7H); 13C NMR
d
(ppm) 12.8, 26.7 (C-2),
29.6, 37.8 (C-3), 43.9 (C-1), 55.35, 114.0, 126.1, 127.2, 128.7, 129.5,
120.2, 131.0, 131.6, 208.1. IR (neat): 2957, 2928, 1682, 1611, 1578,
1514, 1478, 1463, 1455, 1439, 1354, 1291, 1248, 1218, 1175, 1072,
1035, 838, 735, 691 cmꢁ1. trans Isomer: Rf¼0.34 (cyclohexane/
C24H22O2Se (421.38): C, 68.40; H, 5.26. Found: C, 68.52, H, 5.10.
EtOAc: 97/3), 1H NMR
d
(ppm) 1.28 (d, 3H, J¼6.2 Hz), 2.14 (m, 1H, H-
2), 2.52 (s, 3H), 3.16 (d, 1H, J¼8.0 Hz), 3.76 (s, 3H), 6.85–6.90 (m,
4.4.27. 1-(2,2,3-Trimethyl-1-phenylselanyl-cyclopropyl)-
ethanone 41
2H), 7.15–7.35 (m, 7H); 13C NMR
d
(ppm) 13.3, 30.2 (C-2), 30.8, 36.2
(C-3), 46.0 (C-1), 55.35, 113.2, 126.7, 127.2, 129.1, 129.1, 130.0, 130.6,
131.6, 205.5. MS (EI) m/z (relative intensity): 360 (Mþ, 8), 157
(PhSeþ, 8), 77 (Phþ,10), 43 (MeCOþ,100). Anal. Calcd for C19H20O2Se
(359.31): C, 63.51; H, 5.61. Found: C, 63.62; H, 5.69.
Yield 46%; yellow oil; Rf¼0.35 (cyclohexane/EtOAc: 97/3); 77Se
NMR
d d (ppm) 1.10 (s, 3H), 1.17 (d, 3H,
(ppm) 296.7; 1H NMR
J¼6.4 Hz), 1.29 (s, 3H), 1.95 (q, 1H, J¼6.4 Hz), 2.40 (s, 3H), 7.15–
7.35 (m, 5H); 13C NMR
d
(ppm) 11.64, 18.44, 22.8, 27.0 (C-3), 29.7
(C-2), 30.4, 49.9 (C-1), 126.4, 129.3, 129.8, 132.9, 206.3. IR (neat):
3053, 2956, 2926, 1665, 1575, 1478, 1447, 1248, 1022, 742,
693 cmꢁ1. MS (EI) m/z (relative intensity): 282 (Mþ, 10), 157
(PhSeþ, 8), 125 (MþꢁPhSe, 8), 77 (Phþ, 12), 43 (CH3COþ, 100).
Anal. Calcd for C14H18OSe (281.24): C, 59.78; H, 6.45. Found: C,
59.71; H, 6.47.
4.4.22. 1-(4-Methoxy-phenyl)-3-methyl-2-phenylselanyl-penta-
1,3-diene 36
Yield 10%, yellow oil; Rf¼0.49 (cyclohexane/EtOAc: 95/5). Major
isomer: 1H NMR
d
(ppm) 1.64 (s, 3H, Me-3), 1.82 (d, 3H, J¼6.6 Hz, H-
5), 3.76 (s, 3H, OMe), 5.68 (q, 1H, J¼6.6 Hz, H-4), 6.70 (s, 1H, H-1),
7.05–7.65 (m, 9H). IR (neat): 2928, 2361, 1605, 1576, 1558, 1507,
1475, 1456, 1438, 1249, 1175, 1119, 1034, 827, 738, 721, 692 cmꢁ1. MS
(EI) m/z (relative intensity): 344 (Mþ, 36), 157 (PhSeþ, 44), 77 (Phþ,
56).
4.4.28. 1-Phenyl-(2,2,3-trimethyl-1-phenylselanyl-cyclopropyl)-
methanone 42
Yield 44%; white solid (mp¼136 ꢀC); Rf¼0.37 (cyclohexane/
EtOAc: 97/3); 77Se NMR (ppm) 338.4; 1H NMR
d d (ppm) 1.09 (s, 3H),
4.4.23. trans-2,5-Dimethyl-3-(4-methoxy-phenyl)-4-
phenylselanyl-2,3-dihydrofuran 37
1.26 (d, 3H, J¼6.4 Hz), 1.48 (s, 3H), 1.88 (q, 1H, J¼6.4 Hz), 7.15–7.57
(m, 8H), 7.83–7.86 (m, 2H); 13C NMR
d
(ppm) 11.9, 18.2, 24.6 (C-2),
Yield 9%; yellow oil; Rf¼0.36 (cyclohexane/EtOAc: 95/5), 77Se
26.6, 28.6 (C-3), 45.6 (C-1), 126.6, 128.1, 129.1, 129.5, 129.6 (Cq.),
131.0, 132.4, 137.0 (Cq.), 197.5 (C]O). IR (neat): 2925, 1664, 1479,
1378, 1244, 1215, 1023, 739, 704 cmꢁ1. MS (EI) m/z (relative in-
tensity): 344 (Mþ, 12), 157 (PhSeþ, 14), 105 (PhCOþ, 100), 77 (Phþ,
NMR
d
(ppm) 241.4; 1H NMR
d
(ppm) 1.43 (d, 3H, J¼6.2 Hz), 2.11 (d,
3H, J¼1.5 Hz), 3.63 (dd, 1H, J¼1.5, 6.4 Hz, H-3) 4.52 (m, 1H, H-2),
6.78–6.81 (m, 2H), 7.00–7.03 (m, 2H), 7.15–7.26 (m, 10H); 13C NMR

9304
S. Redon et al. / Tetrahedron 64 (2008) 9293–9304
78). Anal. Calcd for C19H20OSe (343.31): C, 66.46; H, 5.87. Found: C,
66.66; H, 5.92.
1272, 1437, 1477, 1578, 1668, 2925, 3056 cmꢁ1. MS (EI) m/z (relative
intensity): 315 (Mþ, 60), 317 ((Mþ2)þ, 100).
4.4.29. 1,4-Diphenyl-3-methyl-2-phenylselanylbuta-1,3-diene 45
References and notes
Yield 27%; yellow oil; 1H NMR
d
(ppm) 2.17 (s, 3H), 2.35 (s, 3H),
7.1–8.2 (m, 16H); 13C NMR
137.1, 139.2.
d (ppm) 17.0, 77.2, 125.7, 127.3, 132.4,
1. (a) Wirth, T. Organoselenium Chemistry: Modern developments in Organic Syn-
thesis. Topics in Current Chemistry; Springer: Berlin, Heidelberg, 2000; Vol. 208;
(b) Back, T. G. Organoselenium Chemistry: A Practical Approach; Oxford University
Press: New York, NY, 1999; (c) Krief, A.; Hevesi, L. Organoselenium Chemistry I;
Springer: Berlin, 1988; (d) Liotta, D. C. Organoselenium Chemistry; Wiley: New
York, NY, 1987; (e) Patai, S. The Chemistry of Organic Selenium and Tellurium
Compounds; Wiley: New York, NY, 1987; Vols. 1 and 2; (f) Paulmier, C. Selenium
Reagents and Intermediates in Organic Synthesis; Pergamon: Oxford, 1986.
2. (a) Redon, S.; Berthe-Berkaoui, A.-L.; Pannecoucke, X.; Outurquin, F. Tetrahedron
2007, 63, 3707–3717; (b) Huot, J.-F. Ph.D. Thesis, Univ. Rouen: Rouen, 1991.
3. (a) Zima, G.; Liotta, D. Synth. Commun. 1979, 697–703; (b) Liotta, D.; Saindane,
M.; Barnum, C.; Zima, G. Tetrahedron 1985, 41, 4881–4889.
4.4.30. Phenyl(2-phenyl-1-(phenylselanyl)cyclopropyl)-
methanone 46
Yield 57%; yellow oil; Rf¼0.45 (cyclohexane/EtOAc: 95/5); 1H
NMR
d
(ppm) 1.73 (dd, 1H, J¼6.0, 7.5 Hz), 2.43 (dd, 1H, J¼6.0,
9.4 Hz), 2.81 (dd, 1H, J¼7.5, 9.4 Hz), 7.15–7.60 (m, 13H), 7.9 (d, 2H,
J¼6.0 Hz). 13C NMR
d (ppm) 18.9, 32.1, 38.0, 127.4, 128.2, 128.3,
128.6, 129.0, 129.1, 129.4, 132.5, 132.8, 135.5, 136.1, 197.1. IR: 693,
737, 993, 1023, 1071, 1266, 1447, 1580, 1598, 1652, 2923,
3061 cmꢁ1. MS (EI) m/z (relative intensity): 377 (Mþ, 48), 379
((Mþ2)þ, 100).
4. Reich, H. J.; Renga, J. M. J. Org. Chem. 1975, 40, 3313–3314.
5. Buckley, D. J.; Mc Kervey, M. A. J. Chem. Soc., Perkin Trans. 1 1985, 2193–2200.
6. (a) Reich, H. J.; Shah, S. K. J. Am. Chem. Soc. 1977, 99, 263–265; (b) Reich, H. J.;
Shah, S. K.; Gold, P. M.; Olson, R. E. J. Am. Chem. Soc. 1981, 103, 3112–3120.
7. Hase, T. A.; Kukkola, P. Synth. Commun. 1980, 10, 451–455.
8. Kuwajima, I.; Shimizu, M.; Urabe, H. J. Org. Chem. 1982, 47, 837–842.
9. Barros, O. S.; Land, E. S.; Fernandes de Oliveira, C. A.; Peppe, C.; Zeni, G. Tet-
rahedron Lett. 2002, 43, 7921–7923.
4.4.31. 2,3-Dihydro-3,5-diphenyl-4-(phenylselanyl)furan 47
Yield 24%; yellow oil; Rf¼0.72 (cyclohexane/EtOAc: 95/5); 1H
10. Renard, M.; Hevesi, L. Tetrahedron 1985, 41, 5939–5954.
NMR
d
(ppm) 4.15 (dd, 1H, J¼5.3, 10.2 Hz), 4.52 (dd, 1H, J¼5.3,
11. Braga, A. L.; Zeni, G.; De Andrade, L. H.; Silveira, C. C. Synlett 1997, 595–596.
12. (a) Piettre, S.; Janousek, Z.; Merenyi, R.; Viehe, H. G. Tetrahedron 1985, 41, 2527–
2543; (b) Janousek, Z.; Piettre, S.; Gorissen-Hervens, F.; Viehe, H. G. J. Orga-
nomet. Chem. 1983, 250, 197–202.
13. Ponthieux, S.; Outurquin, F.; Paulmier, C. Tetrahedron Lett. 1998, 39, 4017–4020.
14. (a) Berlin, S.; Engman, L. Tetrahedron Lett. 2000, 41, 3701–3704; (b) De Cock, C.;
Piettre, S.; Lahousse, F.; Janousek, Z.; Merenyi, R.; Viehe, H. G. Tetrahedron 1985,
41, 4183–4193.
15. Huang, Z.-Z.; Huang, X.; Huang, Y.-Z. J. Chem. Soc., Perkin Trans. 1 1995, 95–96.
16. (a) Freeman, J. P. Chem. Ind. (London) 1959, 1254–1255; (b) Bohlmann, F. Chem.
Ber. 1956, 89, 2191–2197; (c) Franzen; Driessen, H. E. Chem. Ber. 1963, 96, 1881–
1888; (d) Grieco, P. A.; Finkelhor, R. S. Tetrahedron Lett. 1972, 13, 3781–3783; (e)
Lowe, P. A. Chem. Ind. (London) 1970, 1070–1079; (f) Heldeweg, R. F.; Hogeveen,
H.; Schudde, E. P. J. Org. Chem. 1978, 43, 1912–1916; (g) Krief, A.; Lecomte, P.
Tetrahedron Lett. 1993, 34, 2695–2698; (h) De Vos, M. J.; Krief, A. Tetrahedron
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hedron 1989, 45, 3039–3052.
9.1 Hz), 4.83 (dd, 1H, J¼9.1, 10.2 Hz), 7.15–7.40 (m, 13H), 7.94–7.97
(m, 2H). 13C NMR
d
(ppm) 54.7, 100.8, 126.6, 127.2, 127.9, 128.2,
128.7, 129.2, 129.6, 130.5, 130.5, 131.2, 143.2, 158.9. MS (EI) m/z
(relative intensity): 393 ((MþO)þ, 62), 317 ((MþOþ2)þ, 92).
4.4.32. 1-(2-Phenyl-1-(phenylselanyl)cyclopropyl)ethanone 48
Yield 57%; yellow oil; Rf¼0.25 (cyclohexane/EtOAc: 95/5); 1H
NMR
d
(ppm) 1.84 (dd,1H, J¼4.7, 7.7 Hz), 2.50 (dd,1H, J¼4.7, 9.2 Hz),
2.56 (s, 3H), 2.99 (dd,1H, J¼7.7, 9.2 Hz), 7.15–7.40 (m,10H); 13C NMR
d
(ppm) 24.0, 29.5, 35.9, 39.1, 126.7, 127.5, 128.1, 129.2, 129.4, 130.1,
131.0, 136.5, 207.3. MS (EI) m/z (relative intensity): 315 (Mþ, 88), 317
((Mþ2)þ, 100).
17. For related 1,4-addition with phosphorus ylides on 1,2-dioxines, see: (a) Avery,
T. D.; Taylor, D. K.; Tiekink, E. R. T. J. Org. Chem. 2000, 65, 5531–5546; (b) Avery,
T. D.; Fallon, G.; Greatrex, B. W.; Pyke, S. M.; Taylor, D. K.; Tiekink, E. R. T. J. Org.
Chem. 2001, 66, 7955–7966; (c) Kimber, M. C.; Taylor, D. K. J. Org. Chem. 2002,
67, 3142–3144; (d) Greatrex, B. G.; Taylor, D. K. J. Org. Chem. 2005, 70, 470–476.
18. (a) Lebel, H.; Marcoux, J.-F.; Molinaro, C.; Charette, A. B. Chem. Rev. 2003, 103,
977–1050; (b) For enantioselective reaction with ammonium ylides see:
Papageorgiou, C. D.; Cubillo de Dios, M. A.; Ley, S. V.; Gaunt, M. J. Angew. Chem.,
Int. Ed. 2004, 43, 4641–4644.
4.4.33. 2,3-Dihydro-5-methyl-3-phenyl-4-(phenylselanyl)furan 49
Yield 6%; yellow oil; Rf¼0.56 (cyclohexane/EtOAc: 95/5); 1H
NMR
d
(ppm) 2.12 (d, 3H, J¼1.5 Hz), 4.06 (dd, 1H, J¼5.8, 10.2 Hz),
4.38 (dd, 1H, J¼5.8, 9.1 Hz), 4.74 (dd, 1H, J¼9.1, 10.2 Hz), 7.10–7.40
(m, 8H), 7.5–7.6 (m, 2H). IR: 689, 733, 1022, 1378, 1455, 1579, 1645,
2853, 2922 cmꢁ1
.
19. Bernard, A. M.; Frongia, A.; Piras, P. P.; Secci, F.; Spiga, M. Org. Lett. 2005, 7,
4565–4568.
20. (a) Aggarwal, V. K.; Smith, H. W.; Hynd, G.; Jones, R. V. H.; Fieldhouse, R.; Spey,
S. E. J. Chem. Soc., Perkin Trans. 1 2000, 3267–3276; (b) McGreer, D. E.; McKinley,
J. W. Can. J. Chem. 1971, 49, 105–117.
21. McGreer, D. E.; McKinley, J. W. Can. J. Chem. 1973, 51, 1487–1493.
22. Yadav, V. K.; Balamurugan, R. Org. Lett. 2001, 3, 2717–2719.
23. Corset, J.; Castella`-Ventura, M.; Froment, F.; Strzalko, T.; Wartski, L. J. Raman
4.4.34. (2-Methyl-1-(phenylselanyl)cyclopropyl)(phenyl)-
methanone 50
Yield 66%; yellow oil; Rf¼0.25 (cyclohexane/EtOAc: 95/5); 1H
NMR
d
(ppm) 1.24 (dd, 1H, J¼5.3, 6.0 Hz), 1.53 (d, 3H, J¼6.2 Hz),
1.60–1.70 (m, 1H), 1.96 (dd, 1H, J¼5.3, 8.8 Hz), 7.15–7.60 (m, 8H),
7.90 (d, 2H, J¼6.0 Hz). 13C NMR
d (ppm) 16.2, 21.3, 21.6, 35.2, 127.1,
Spectrosc. 2002, 33, 652–668.
24. Johnson, C. R.; Janiga, E. R. J. Am. Chem. Soc. 1973, 95, 7692–7700.
128.4, 129.2, 130.7, 131.8, 132.7, 135.9, 197.7. IR: 689, 736, 1022, 1066,