Studies on highly regio- and stereoselective selenohydroxylation reaction of 1,2-allenyl phosphine oxides with PhSeCl

Article abstract of DOI:10.1016/j.tet.2009.04.023

The selenohydroxylation of readily available 1,2-allenyl phosphine oxides with PhSeCl in MeCN/H₂O afforded 3-hydroxy-2-phenylselanyl-1(E)-alkenyl diphenyl phosphine oxides in good yields with very high regio- and stereoselectivities including t

Full text of DOI:10.1016/j.tet.2009.04.023

Tetrahedron 65 (2009) 4877–4889
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Studies on highly regio- and stereoselective selenohydroxylation reaction
of 1,2-allenyl phosphine oxides with PhSeCl
,
a,b,
*
Guangke He a, Hao Guo b, Rong Qian c, Yinlong Guo c, Chunling Fu a , Shengming Ma
*
a Laboratory of Molecular Recognition and Synthesis, Department of Chemistry, Zhejiang University, Hangzhou 310027, Zhejiang, PR China
b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai 200032, PR China
c Shanghai Mass Spectrometry Center, Shanghai Institute of Organic Chemistry Chinese Academy of Sciences, 354 Fenglin Road, Shanghai 200032, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
The selenohydroxylation of readily available 1,2-allenyl phosphine oxides with PhSeCl in MeCN/H2O
afforded 3-hydroxy-2-phenylselanyl-1(E)-alkenyl diphenyl phosphine oxides in good yields with very
high regio- and stereoselectivities including the high efficiency of the axial chirality transfer. The
E-stereoselectivity is believed to be determined by the neighboring group participation effect of the
diphenyl phosphine oxide functionality.
Received 6 December 2008
Received in revised form 4 April 2009
Accepted 7 April 2009
Available online 16 April 2009
Ó 2009 Elsevier Ltd. All rights reserved.
1. Introduction
of 1,2-allenylic phosphine oxides. Herein, we wish to report the
realization of selenohydroxylation of 1,2-allenyl diphenyl phos-
Phosphorous-containing compounds show important biological
activity.1 In addition to the biological potential, this type of com-
pounds also plays an important role in organic synthesis.2 On the
other hand, 1-alkenyl selenides are important organic inter-
mediates,3a,b particularly in synthesizing carbonyl compounds3c,d
and stereoselective preparation of functionalized alkenes.3e,f Thus,
development of new methods for the highly selective synthesis of
2-phosphoryl-1-alkenyl selenides is highly desired.
Recently, we have developed the halohydroxylation of 1,2-
allenyl sulfides,4,5 selenides,6 sulfoxides,7 sulfones,8 phosphine
oxides,9 and 3-aryl-1,2-allenes.10 In all the cases, the halogen atom
has been introduced to the center carbon atom of the allene moiety
while the hydroxyl group is connected to the 3-position of the
starting allenes referring to the carbon atom connected to
the heteroatom. The stereoselectivity depends on the nature of the
functional group: for sulfides and selenides the Z-products were
formed4–6 while for other cases E-products were produced.7–9 Re-
cently, we also studied the selenolactonization of 2,3-allenoic
acids11 and 2,3-allenoates.12,13 Similarly, the reaction of 1,2-allenylic
phosphonates, phosphinates, phosphoric acids with RSeCl and
RSeBr was also reported to afford 4-selenyl-2,5-dihydro-1,2-oxa-
phosphole 2-oxides.14–20 Furthermore, the selenohydroxylation of
1,2-allenylic sulfoxides with PhSeCl has been reported by this
group.21 Due to the similarity between the phosphine oxides and
sulfoxides or sulfones, we show interest in the selenohydroxylation
phine oxides affording (E)-3-hydroxy-2-phenylselanyl alkenyl
diphenyl phosphine oxides with high regio- and stereoselectivity.
2. Results and discussion
After some screening, it is observed that the reaction of 1a with
1.5 equiv of PhSeCl in CH2Cl2 at rt afforded the expected product E-
2a as the only stereoisomer in 41% yield (entry 1, Table 1). The re-
action in CH3NO2 afforded E-2a in 62% yield (entry 2, Table 1). The
solvent effect is obvious: the yields for the reaction in toluene, ethyl
acetate, and MeCN are much higher (entries 3–5, Table 1). Since the
formed hydroxyl group may have something to do with the water
present in the reaction media, H2O was added as the cosolvent to
MeCN and the yields were improved to 96% (entries 6–10, Table 1).
With 1.2 equiv of PhSeCl, the yield is lower (entry 10, Table 1). No
reaction was observed in aqueous acetone while the reaction in
aqueous THF, EtOH, or DMF afforded the product E-2a in 82–90%
yields (entries 12–14, Table 1).
With the optimized reaction conditions in hand (entry 7, Table
1), the scope of this selenohydroxylation reaction was demon-
strated (Table 2). The reaction is very general: for 3-mono-
substituted diphenyl phosphine oxide, the yield is good (entries 2
and 3, Table 2); the reaction of 3,3-disubstituted substituted (en-
tries 4–6, Table 2), 1-monosubstituted (entries 7 and 8, Table 2), 1,3-
disubstituted (entries 9 and 10, Table 2), and fully substituted
(entry 11, Table 2) 1,2-allenyl diphenyl phosphine oxides all worked
smoothly and cleanly to afford the corresponding E-selenohy-
droxylation products. The regio- and stereochemical outcome was
further established by the X-ray diffraction study of E-2b (Fig. 1).22
* Corresponding authors.
E-mail addresses: fud@zju.edu.cn (C. Fu), masm@mail.sioc.ac.cn (S. Ma).
0040-4020/$ – see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2009.04.023

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G. He et al. / Tetrahedron 65 (2009) 4877–4889
Table 1
Selenohydroxylation of 1-phenylocta-1,2-dienyl diphenyl phosphine oxide (1a) with
PhSeCla
O
P
O
P
HO
Ph
Ph
C5H11-n
Ph
Ph
C5H11-n
solvent
rt
+
PhSeCl
Ph
H
Ph
SePh
E-2a
1.5 equiv
1a
Entry
Solvent
T (h)
Yield of E-2ab
1
2
3
4
5
6
7
8
CH2Cl2
CH3NO2
Toluene
Ethyl acetate
MeCN
3.5
1.2
30.2
30.4
12
0.65
0.25
0.6
12
0.6
44.5
16
41
62
75
82
82
92
96
87
80
84
0d
MeCN/H2O¼40/1
MeCN/H2O¼20/1
MeCN/H2O¼10/1
MeCN/H2O¼5/1
MeCN/H2O¼20/1
Acetone/H2O¼20/1
THF/H2O¼20/1
9
10c
11
12
13
14
90
82
85
EtOH/H2O¼20/1
DMF/H2O¼20/1
28
17
a
The reaction was carried out using 0.2 mmol of 1a, 0.3 mmol of PhSeCl, and
Figure 1. ORTEP representation of E-2b.
4.0 mL of organic solvent.
b
NMR yield based on 1a using CH2Br2 as the internal standard.
PhSeCl (1.2 equiv) was used.
Compound 1a (91%) was recovered.
c
d
observe that the stereochemistry for the formation of the chlorides
3l–p is different from that for the selenohydroxylation product E-2.
In order to further confirm this difference, E-3o was prepared
from the sequential tosylation23 and chlorination24 of E-2o
(Scheme 1). It is still not clear why the formed allylic chloride is in
Z-configuration. After further screening, it was observed that when
reaction of 1l was conducted in MeCN/H2O (2:1) at 70 ꢀC, the yield
of E-2l and the ratio of E-2l/Z-3l is much higher (compare entries
1–6, Table 3).
However, in the case of R1¼R2¼H, R3¼alkyl group (except for
methyl group), the reaction is not clean, i.e., 3-chloro-2-phenyl-
selanyl-1(Z)-alkenyl diphenyl phosphine oxides were formed as the
by-product (entries 12–16, Table 2). In addition, it is interesting to
Table 2
Selenohydroxylation of differently substituted 1,2-propadienyl diphenyl phosphine
oxides 1 with PhSeCla
Some typical results of selenohydroxylation of 3-mono-
substituted or the simple allenyl phosphine oxides under this new
set of reaction conditions are summarized in Table 4.
O
P
O
P
HO
R2
R3
Ph
Ph
R2
R3
Ph
Ph
MeCN/H2O = 20/1
rt
+
PhSeCl
1.5 equiv
As optically active 1,2-allenyl phosphine oxides are easily
available from the corresponding optically active propargylic al-
cohols,25,26 we also investigated the possibility of synthesizing
optically active selenohydroxylation product by means of the
present method. The experimental results showed that the axial
chirality in allenyl phosphine oxides could be transferred to the
central chirality of the products with high efficiency (Scheme 2).
The absolute configuration of the products was determined by
X-ray diffraction analysis of S-(E)-2b by using the selenium atom in
the molecule as a reference (Fig. 2).27
R1
R1
SePh
1
E-2
Entry
R1
R2
R3
T (min)
Isolated yield
of E-2 (%)
1
Ph
H
n-C5H11 (1a)
Me (1b)
Ph (1c)
Me (1d)
n-Pr (1e)
14
12
28
19
18
10
16
14
10
5
91 (2a)
82 (2b)
85 (2c)
89 (2d)
80 (2e)
84 (2f)
67 (2g)
80 (2h)
90 (2i)
2
H
H
3
H
H
4
H
Me
5
H
n-Pr
6
H
(CH2)5 (1f)
In order to study the reaction mechanism, we carried out
this selenohydroxylation reaction of 1h using water and 18O-
labeled water. The normal product E-2h and the 18O-labeled
7
8
9
10
11
12
13
14
15
16
n-C4H9
Ph
Et
Ph
H
H
H
H
Me
H
H
H
H
H
H (1g)
H (1h)
Me (1i)
Et (1j)
product E-2h
*
were isolated and studied by ESI-MS technique
88 (2j)
n-C4H9
Me (1k)
i-Pr (1l)
H (1m)
Et (1n)
n-C6H13 (1o)
Bn (1p)
10
20
16
20
30
15
65 (2k)
76 (2l)b
13 (2m)c
82.5 (2n)d
64 (2o)e
64 (2p)f
H
H
H
H
H
O
P
O
P
HO
TsO
Ph
Ph
C6H13-n
Ph
C6H13-n
DMAP
CH2Cl2, 50 °C
86%
+
TsCl
Ph
SePh
SePh
a
The reaction was carried out using 0.3 mmol of 1a, 0.45 mmol of PhSeCl, 6.0 mL
E-2o
E-4o
of MeCN, and 0.3 mL of H2O.
b
The reaction also afforded 3-chloro-4-methyl-2-phenylselanyl-1(Z)-pentenyl
LiCl
DMF, 50 °C
60%
O
diphenyl phosphine oxide (Z-3l) in 7% isolated yield.
c
The reaction also afforded 3-chloro-2-phenylselanyl-1(Z)-propenyl diphenyl
Ph P
Ph
SePh
O
P
phosphine oxide (Z-3m) in 61.5% isolated yield.
Cl
C6H13-n
Cl
d
The reaction also afforded 3-chloro-4,-2-phenylselanyl-1(Z)-pentenyl diphenyl
H
Ph
Ph
C6H13-n
SePh
H
phosphine oxide (Z-3n) in 6% isolated yield.
e
The reaction also afforded 3-chloro-2-phenylselanyl-1(Z)-nonenyl diphenyl
NOE
phosphine oxide (Z-3o) in 6% isolated yield.
E-3o
Z-3o
f
The reaction also afforded 3-chloro-4-phenyl-2-phenylselanyl-1(Z)-butenyl
diphenyl phosphine oxide (Z-3p) in 14% isolated yield.
Scheme 1.

G. He et al. / Tetrahedron 65 (2009) 4877–4889
4879
Table 3
O
P
O
P
HO
Selenohydroxylation of 4-methylpenta-1,2-dienyl diphenyl phosphine oxide (1l)
with PhSeCl
Ph
Ph
H
Ph
Ph
CH3CN/H2O = 20/1
+
PhSeCl
rt, 12 min
86%
O
SePh
O
P
O
P
1.5 equiv
HO
Ph
Ph
P
Pr-i
S-(+)-1b, 99% ee
S-E-(+)-2b
99% ee
Ph
Ph
Pr-i Ph
SePh
Pr-i
solvent
+
PhSeCl
+
Ph
temp, time
H
1.5 equiv
SePh
O
P
O
P
HO
Cl
Z-3l
1l
Ph
Ph
H
E-2l
Ph
Ph
Et
CH3CN/H2O = 20/1
+ PhSeCl
1.5 equiv
rt, 8 min
94%
Ph
Et
Ph
S-E-(+)-2j
99% ee
SePh
Entry
Solvent
(MeCN/H2O)
Temp (ꢀC)
T (h)
Yield of
Ratio of
S-(+)-1j, 99% ee
E-2l (%)a
E-2l/Z-3lb
1
2
3
4
5
6
20/1
10/1
5/1
rt
rt
rt
rt
rt
70
0.50
0.37
0.60
13.4
65.7
0.57
64
76
84
89
77
82
90/10
91/9
94/6
97/3
98/2
97/3
O
P
O
P
HO
Ph
Ph
C6H13-n
Ph
C6H13-n
CH3CN/H2O = 2/1
Ph
+
PhSeCl
1.5 equiv
2/1
1/1
2/1
70 °C, 30 min
79%
H
H
SePh
R-E-(-)-2o
97% ee
R-(-)-1o, 97% ee
a
NMR yield based on 1l using CH2Br2 as the internal standard.
b
The ratio of E-2l/Z-3l was determined by 1H NMR analysis of the crude product.
Scheme 2.
(Figs. 3 and 4). The ESI-MS/MS spectra showed that the [MþH]þ
ion of E-2h at m/z¼491 fragmented to yield the daughter ion at
3. Conclusions
In conclusion, we have established an effective and practical
method to synthesize 3-hydroxy-2-phenylselanyl-1(E)-alkenyl
diphenyl phosphine oxides with high regio- and stereoselectivity
and observed the neighboring group participation effect of the
diphenylphosphinyl group by ESI-MS using H128O as the probe. Due
to the presence of carbon–carbon double bond, carbon–selenium
bond, and the hydroxyl group, this reaction will be useful in organic
synthesis. Further studies in this area including the factors de-
termining the stereoselectivity for the formation of Z-3o are cur-
rently being carried out in our laboratory.
m/z¼473 (Fig. 3c). While that of E-2h at m/z¼493 displayed
*
the same fragmentation chemistry to yield the corresponding
daughter ion at m/z¼475 (Fig. 4c). These results indicated that
18O atom was bound to phosphorous, and the oxygen atom of
the hydroxyl group comes from the phosphine oxide function-
ality in the starting allene. Similarly, the reactions of 1c and 1e
with PhSeCl in the presence of H128O were also conducted with
the results being summarized in Scheme 3 (for the MS spectra,
see Supplementary data).
Based on these results, a possible mechanism was proposed9
(Scheme 4). In the first step, the selenium intermediate 5 is afforded
by the reaction of the relatively electron-rich carbon–carbon dou-
ble bond with PhSeþ. Subsequently, a five-membered cyclic in-
termediate 6 is formed via neighboring group participation of the
oxygen atom of the diphenyl phosphine oxide functionality, which
is similar with what was observed in the iodohydroxylation of
allenylic sulfoxides7b and phosphine oxides9 or the bromohydroxy
lation of allenylic sulfones.8a Finally, the H128O molecule attacks at
the positively charged phosphorous atom to cleave the P–O bond,
4. Experimental
4.1. Starting materials
Known compounds 1b–d, 1f, 1h, 1i, and 1n were prepared
according to the known procedures.28 New compounds 1e, 1g, 1j,
1k, and 1p were also prepared according to this procedure.28 Due to
which forms the final product E-2
difficult to exclude other possibilities since the 18O incorporation is
still low (69.5%) for E-2e
*
(Scheme 4). Of course, it is
*
.
This reaction mechanism may also be used to explain the
chirality transfer observed in Scheme 2 (Scheme 5).
Table 4
Selenohydroxylation of differently 3-monosubstituted 1,2-allenyl diphenyl phos-
phine oxides with PhSeCl
O
P
O
P
O
P
HO
R3
Ph
Ph
SePh
R3
Ph
Ph
H
Ph
MeCN/H2O = 2/1
70 °C
PhSeCl
1.5 equiv
+
+
Ph
R3
H
SePh
H
Cl
E-2
1
Z-3
Entry
R3
Time (min)
Isolated yield
Ratio of E-2/Z-3a
of E-2 (%)
1
i-Pr
H
Et
n-C6H13
Bn
34
540
21
70
105
82 (2l)
97/3
2b
3
52.5 (2m)
78 (2n)
74 (2o)
77 (2p)
79/21
>99/1
98/2
4b
5
96.5/3.5
a
The ratio of E-2/Z-3 was determined by 1H NMR analysis of the crude product.
The ratio of MeCN/H2O in the solvent was 1/1.
b
Figure 2. ORTEP representation of S-E-2b.

4880
G. He et al. / Tetrahedron 65 (2009) 4877–4889
Figure 4. (a) ESI-MS spectrum for E-2h
*
, (b) ESI-SIM-MS spectrum for the precursor
ion of E-2h
m/z¼493.
*
at m/z¼493, and (c) ESI-MS/MS spectrum for the precursor ion of E-2h at
*
the coupling between 13C and 31P, the 13C NMR is very complicated
and the spectra are provided in Supplementary data.
4.1.1. 1-Phenylpenta-1,2-dienyl diphenyl phosphine oxide (1j)
General Procedure I. To a dried three-necked round-bottom flask
were added with 1-phenylpent-1-yn-3-ol (2.4336 g, 15 mmol),
Figure 3. (a)ESI-MS spectrum for E-2h, (b) ESI-SIM-MS spectrum for theprecursor ion of
E-2h at m/z¼491, and (c) ESI-MS/MS spectrum for the precursor ion of E-2h at m/z¼491.

G. He et al. / Tetrahedron 65 (2009) 4877–4889
4881
ꢁ64 ꢀC according to General Procedure I. After warming up to rt, the
reaction mixture was heated to reflux within 30 min and kept
under reflux for 30 h to afford 1e (1.3731 g, 28%) as a liquid. 1H NMR
18O
Ph
Ph
Ph
O
P
Ph
CH3CN/H218O = 20/1
rt, 45 min, 84%
P
OH
Ph
+
PhSeCl
1.5 equiv
Ph
SePh
(300 MHz, CDCl3)
(m, 1H), 1.84–1.64 (m, 4H), 1.30–1.12 (m, 4H), 0.77 (t, J¼5.6 Hz, 6H);
13C NMR (75 MHz, CDCl3)
d 7.78–7.65 (m, 4H), 7.50–7.37 (m, 6H), 5.81–5.70
1h
E-2h*
18O% incorporation: 94.5%
d
209.9, 132.8 (d, Jpc¼104.3 Hz), 131.4 (d,
18O
Jpc¼2.6 Hz), 131.2 (d, Jpc¼9.6 Hz), 128.0 (d, Jpc¼11.9 Hz), 106.2 (d,
Jpc¼13.7 Hz), 85.3 (d, Jpc¼107.6 Hz), 33.3 (d, Jpc¼5.9 Hz), 20.3
O
P
HO
CH3CN/H218O = 20/1
rt, 37 min, 85%
Ph
Ph
Ph
P
Ph
Ph
(d, Jpc¼1.4 Hz), 13.6; 31P NMR (121.5 MHz, CDCl3)
d
25.8; MS (EI,
+
PhSeCl
1.5 equiv
Ph
SePh
70 eV) m/z (%) 325 (Mþþ1, 1.45), 324 (Mþ, 3.08), 202 (100); IR
n
(neat, cmꢁ1) 1949, 1591, 1437, 1380, 1199, 1119. HRMS calcd for
C21H25OP: 324.1643. Found: 324.1645.
E-2c*
1c
18O% incorporation: 88.4%
18O
O
P
HO Pr-n
P Pr-n
CH3CN/H218O = 20/1
rt, 41 min
Ph
Pr-n
Pr-n
Ph
4.1.3. Hepta-1,2-dien-3-yl diphenyl phosphine oxide (1g)
Ph
+
PhSeCl
1.5 equiv
Ph
The reaction of hept-2-yn-1-ol (1.6865 g, 15 mmol), Et3N
(2.10 mL, d¼0.73 g/mL, 1.53 g, 15 mmol), and Ph2PCl (2.75 mL,
d¼1.20 g/mL, 3.30 g, 15 mmol) in 45 mL of CH2Cl2 for 7.5 h afforded
SePh
E-2e*
18O% incorporation: 69.5%
Scheme 3. Reactions conducted in the presence of H128O.
1e
1g (2.6667 g, 60%) as a liquid. 1H NMR (400 MHz, CDCl3)
d 7.77–7.63
(m, 4H), 7.52–7.46 (m, 2H), 7.45–7.38 (m, 4H), 4.67 (dt, J1¼11.2 Hz,
J2¼3.2 Hz, 2H), 2.28–2.15 (m, 2H), 1.53–1.40 (m, 2H), 1.35–1.24 (m,
2H), 0.82 (t, J¼7.4 Hz, 3H); 13C NMR (100 MHz, CDCl3)
d 211.0 (d,
Jpc¼7.1 Hz), 131.8 (d, Jpc¼103.9 Hz), 131.7 (d, Jpc¼5.0 Hz), 131.6 (d,
Jpc¼8.9 Hz), 128.2 (d, Jpc¼11.9 Hz), 97.6 (d, Jpc¼99.9 Hz), 77.4, 30.2
(d, Jpc¼5.5 Hz), 26.8 (d, Jpc¼6.1 Hz), 22.1, 13.7; 31P NMR (121.5 MHz,
Et3N (2.10 mL, d¼0.73 g/mL, 1.53 g, 15 mmol), and 40 mL of CH2Cl2.
A solution of chlorodiphenylphosphine (2.80 mL, d¼1.20 g/mL,
3.36 g, 15 mmol) in 5 mL of CH2Cl2 was then added dropwise at
ꢁ64 ꢀC within 30 min. After being warmed up naturally to room
temperature, the reaction was monitored by TLC (petroleum ether/
ethyl acetate¼1:1). Upon complete conversion of the alcohol, the
reaction was quenched with 20 mL of water. The organic layer was
separated and the aqueous layer was extracted with 20ꢂ3 mL of
CH2Cl2. The combined organic layer was washed with 20 mL of
brine and dried over anhydrous Na2SO4. After evaporation of the
solvent, chromatography on silica gel (eluent: CH2Cl2/ethyl
acetate¼10:1) of the crude product afforded 1j (2.1617 g, 41%) as
CDCl3)
d
29.5; MS (EI, 70 eV) m/z (%) 297 (Mþþ1, 3.53), 296 (Mþ,
12.30), 201 (100); IR
n
(neat, cmꢁ1) 1937, 1590, 1483, 1466, 1438,
1379, 1310, 1193, 1118, 1102. HRMS calcd for C19H21OP: 296.1330.
Found: 296.1331.
4.1.4. 2-Methylocta-2,3-dien-4-yl diphenyl phosphine oxide (1k)
The reaction of 2-methyloct-3-yn-2-ol (2.0734 g,15 mmol), Et3N
(2.10 mL, d¼0.73 g/mL, 1.53 g, 15 mmol), and Ph2PCl (2.80 mL,
d¼1.20 g/mL, 3.36 g, 15 mmol) in 45 mL of CH2Cl2 for 15 h afforded
1k (2.1277 g, 44%) as a liquid. 1H NMR (400 MHz, CDCl3)
d 7.72–7.60
a liquid. 1H NMR (400 MHz, CDCl3)
d 7.77–7.67 (m, 4H), 7.59 (d,
(m, 4H), 7.50–7.35 (m, 6H), 2.23–2.13 (m, 2H), 1.48–1.35 (m, 8H),
1.35–1.20 (m, 2H), 0.85–0.78 (m, 3H); 13C NMR (100 MHz, CDCl3)
J¼7.6 Hz, 2H), 7.45–7.30 (m, 6H), 7.18 (t, J¼7.4 Hz, 2H), 7.09 (t,
d
207.4 (d, Jpc¼6.4 Hz), 132.5 (d, Jpc¼102.6 Hz), 131.4, 131.3, 128.0 (d,
J¼7.2 Hz, 1H), 5.28 (dt, J1¼10.8 Hz, J2¼6.6 Hz, 1H), 1.85–1.71 (m, 2H),
0.74 (t, J¼7.6 Hz, 3H); 31P NMR (121.5 MHz, CDCl3)
d 30.2; MS (EI,
Jpc¼11.8 Hz), 98.4 (d, Jpc¼14.6 Hz), 96.4 (d, Jpc¼102.2 Hz), 30.4 (d,
Jpc¼6.2 Hz), 27.1 (d, Jpc¼8.4 Hz), 22.1, 19.1 (d, Jpc¼5.9 Hz), 13.8; 31P
70 eV) m/z (%) 345 (Mþþ1, 12.26), 344 (Mþ, 47.54), 201 (100); IR
n
31.9; MS (EI, 70 eV) m/z (%) 325 (Mþþ1,
(neat, cmꢁ1) 1939, 1593, 1493, 1437, 1304, 1190, 1117. Anal. Calcd for
C23H21OP: C, 80.21; H, 6.15. Found: C, 80.25; H, 6.19.
The following compounds were prepared according to General
Procedure I.
NMR (121.5 MHz, CDCl3)
d
5.97), 324 (Mþ, 3.35), 282 (100); IR (neat, cmꢁ1) 1955, 1590, 1483,
n
1437, 1376, 1193, 1118. HRMS calcd for C21H25OP: 324.1643. Found:
324.1645.
4.1.5. 4-Phenylbuta-1,2-dienyl diphenyl phosphine oxide (1p)
The reaction of 4-phenylbut-1-yn-3-ol (2.1919 g, 15 mmol), Et3N
(2.20 mL, d¼0.73 g/mL, 1.61 g, 15 mmol), and Ph2PCl (2.80 mL,
d¼1.20 g/mL, 3.36 g, 15 mmol) in 45 mL of CH2Cl2 for 12 h afforded
4.1.2. 3-Propylhexa-1,2-dienyl diphenyl phosphine oxide (1e)
The reaction of 3-propylhex-1-yn-3-ol (2.1020 g, 15 mmol), Et3N
(2.10 mL, d¼0.73 g/mL, 1.53 g, 15 mmol), and Ph2PCl (2.80 mL,
d¼1.20 g/mL, 3.36 g, 15 mmol) in 45 mL of CH2Cl2 was conducted at
O
P
18O
R2
HO
R2
+
R3
O
O
PhSeCl
R2
R3
R2
R3
H218O:
Ph
Ph
Ph
P
Ph
P
Ph
Ph
P
Ph
Ph
R3
+
R1
SePh
R1
Se
R1
R1
SePh
Cl-
Ph
1
E-2*
5
6
Scheme 4. The proposed mechanism.
R2
R3
O
P
O
P
HO
R2
R3
R2
R3
+
P
PhSeCl
O
O
H218O:
R2
R3
Ph
Ph
P
Ph
Ph
Ph
Ph
Ph
Ph
+
R1
SePh
R1
Se
R1
R1
SePh
Cl-
Ph
1
2
5
6
Scheme 5. Rationale for the axial chirality transfer observed in Scheme 2.

4882
G. He et al. / Tetrahedron 65 (2009) 4877–4889
1p (2.3521 g, 47%) as a liquid. 1H NMR (300 MHz, CDCl3)
d
7.68–7.57
1284, 1189, 1120. Anal. Calcd for C18H19OP: C, 76.58; H, 6.78.
Found: C, 76.56; H, 6.74.
(m, 4H), 7.55–7.46 (m, 2H), 7.46–7.37 (m, 4H), 7.25–7.18 (m, 3H),
6.97–6.90 (m, 2H), 5.87–5.79 (m, 1H), 5.44 (dq, J1¼10.8 Hz,
J2¼6.8 Hz, 1H), 3.30–3.20 (m, 2H); 31P NMR (121.5 MHz, CDCl3)
4.2.4. Nona-1,2-dienyl diphenyl phosphine oxide (1o)
d
24.5; MS (EI, 70 eV) m/z (%) 331 (Mþþ1, 8.27), 330 (Mþ, 33.90), 201
The reaction of non-1-yn-3-ol (2.1046 g, 15 mmol), Et3N
(3.20 mL, d¼0.73 g/mL, 2.34 g, 22.5 mmol), and Ph2PCl (4.20 mL,
d¼1.20 g/mL, 5.04 g, 22.5 mmol) in 45 mL of THF for 3.5 h afforded
(100); IR
n
(neat, cmꢁ1) 1954, 1494, 1452, 1437, 1383, 1174. HRMS
calcd for C22H19OP: 330.1174. Found: 330.1175.
1o (3.0060 g, 62%) as a liquid. 1H NMR (400 MHz, CDCl3)
d 7.81–7.66
4.2. Compounds 1a, 1l, 1o, S-(D)-1j, and R-(D)-1o
(m, 4H), 7.56–7.36 (m, 6H), 5.83–5.74 (m, 1H), 5.29–5.17 (m, 1H),
1.88–1.80 (m, 2H), 1.32–1.07 (m, 8H), 0.89–0.77 (m, 3H); 13C NMR
These compounds were prepared according to a known pro-
cedure described as General Procedure II.29 It should be noted that
conducting the preparation of R-(þ)-1o according to General Pro-
cedure I led to an ee value of R-(þ)-1o at the level of 60% from the
optically active propargylic alcohol (99% ee).
(75 MHz, CDCl3)
d
211.5, 132.6 (d, Jpc¼105.8 Hz), 132.5 (d,
Jpc¼105.5 Hz), 131.6 (d, Jpc¼2.6 Hz), 131.3 (d, Jpc¼9.7 Hz), 128.2 (d,
Jpc¼12.2 Hz), 92.8 (d, Jpc¼13.5 Hz), 85.1 (d, Jpc¼105.9 Hz), 31.4, 28.7
(d, Jpc¼3.2 Hz), 28.5, 27.1 (d, Jpc¼5.3 Hz), 22.3, 13.9; 31P NMR
(121.5 MHz, CDCl3)
d
24.2; MS (EI, 70 eV) m/z (%) 325 (Mþþ1, 2.06),
324 (Mþ, 3.15), 201 (100); IR (neat, cmꢁ1) 1949, 1590, 1483, 1465,
n
4.2.1. 1-Phenylocta-1,2-dienyl diphenyl phosphine oxide (1a)
1437, 1379, 1311, 1189, 1120, 1104. HRMS calcd for C21H25OP:
324.1643. Found: 324.1645.
General Procedure II. To a dried three-necked round-bottom
flask was charged with 1-phenyloct-1-yn-3-ol (3.0038 g, 15 mmol),
triethylamine (3.3 mL, d¼0.73 g/mL, 2.41 g, 22.5 mmol), and 50 mL
of THF. A solution of chlorodiphenylphosphine (4.30 mL, d¼1.20 g/
mL, 5.18 g, 22.5 mmol) in 10 mL of THF was then added dropwise at
ꢁ64 ꢀC within 22 min. After being warmed up naturally to room
temperature, the reaction was monitored by TLC (petroleum ether/
ethyl acetate¼1:1). Upon complete conversion of the alcohol, the
reaction was quenched with 20 mL of water. The organic layer was
separated and the aqueous layer was extracted with 30ꢂ3 mL of
Et2O. The combined organic layer was washed with 15 mL of brine
and dried over anhydrous Na2SO4. After evaporation of the solvent,
chromatography on silica gel (eluent: petroleum ether/ethyl
acetate¼5:1 to 2:1) of the crude product afforded 1a (4.1912 g, 73%)
4.2.5. R-Nona-1,2-dienyl diphenyl phosphine oxide (R-1o)
The reaction of R-(þ)-1-nonyn-3-ol (0.9757 g, 7.0 mmol, 99%
ee), Et3N (1.45 mL, d¼0.73 g/mL, 1.06 g, 10.5 mmol), and Ph2PCl
(1.95 mL, d¼1.20 g/mL, 2.34 g, 10.5 mmol) in 25 mL of THF for 3.0 h
afforded R-(þ)-1o (1.2900 g, 57%) as a liquid. 1H NMR (300 MHz,
CDCl3)
d 7.81–7.66 (m, 4H), 7.56–7.36 (m, 6H), 5.83–5.74 (m, 1H),
5.29–5.17 (m, 1H), 1.94–1.80 (m, 2H), 1.32–1.07 (m, 8H), 0.85 (t,
J¼6.3 Hz, 3H); HPLC conditions: Chiralcel OD-H, hexane/
i-PrOH¼90:10, 0.7 mL/min, n¼230 nm, tR 10.1 (major), 13.1 (minor);
20
[a
]
ꢁ123.8 (c 1.21, CHCl3).
D
4.3. Reaction of multi-substituted allenyl phosphine oxides
with PhSeCl
as a liquid. 1H NMR (300 MHz, CDCl3)
d 7.84–7.67 (m, 4H), 7.61 (d,
J¼7.8 Hz, 2H), 7.54–7.35 (m, 6H), 7.31–7.10 (m, 3H), 5.30 (dt,
J1¼10.5 Hz, J2¼7.1 Hz, 1H), 1.92–1.70 (m, 2H), 1.30–1.02 (m, 6H),
4.3.1. 3-Hydroxy-1-phenyl-2-phenylselanyl-1(E)-octenyl diphenyl
phosphine oxide (E-2a)
0.84 (t, J¼7.1 Hz, 3H); 31P NMR (121.5 MHz, CDCl3)
d 30.1; MS (EI,
70 eV) m/z (%) 387 (Mþþ1, 6.83), 386 (Mþ, 25.81), 201 (100); IR
n
General Procedure III. To a solution of PhSeCl (58.1 mg, 0.3 mmol)
in 3 mL of MeCN was added 0.2 mL of H2O. Then a solution of 1a
(77.7 mg, 0.2 mmol) in 1 mL of MeCN was added and the resulting
mixture was stirred at room temperature for 14 min. After com-
plete consumption of the starting material as monitored by TLC
(eluent: petroleum ether/ethyl acetate¼2:1), the mixture was
quenched with 5 mL of H2O, extracted with 20ꢂ3 mL of diethyl
ether, washed with 5 mL of brine, and dried over anhydrous
Na2SO4. Filtration, evaporation, and flash chromatography on silica
gel (petroleum ether/ethyl acetate¼3:1 to 2:1) afforded E-2a
(neat, cmꢁ1) 1940, 1595, 1492, 1438, 1387, 1319, 1190, 1182. Anal.
Calcd for C26H27OP: C, 80.80; H, 7.04. Found: C, 80.80; H, 7.09.
4.2.2. S-1-Phenylpenta-1,2-dienyl diphenyl phosphine
oxide (S-1j)25,26
The reaction of S-(ꢁ)-1-phenylpent-1-yn-3-ol (0.6390 g,
4.0 mmol, 99% ee), Et3N (0.83 mL, d¼0.73 g/mL, 0.61 g, 6.0 mmol),
and Ph2PCl (1.10 mL, d¼1.20 g/mL,1.32 g, 6.0 mmol) in 25 mL of THF
for 2.0 h afforded S-(þ)-1j (0.6290 g, 46%) as a liquid. 1H NMR
(300 MHz, CDCl3)
d
7.84–7.68 (m, 4H), 7.61 (d, J¼7.5 Hz, 2H), 7.55–
(102.3 mg, 91%) as a liquid. 1H NMR (400 MHz, CDCl3)
d 7.82–7.73
7.33 (m, 6H), 7.28–7.12 (m, 3H), 5.33 (dt, J1¼10.5 Hz, J2¼6.3 Hz, 1H),
(m, 2H), 7.61–7.50 (m, 3H), 7.49–7.40 (m, 3H), 7.40–7.24 (m, 7H),
7.16–7.08 (m, 2H), 7.00–6.92 (m, 1H), 6.92–6.83 (m, 1H), 6.78 (d,
J¼10.8 Hz, 1H), 6.52 (d, J¼7.6 Hz, 1H), 4.37 (t, J¼9.8 Hz, 1H), 2.22–
2.03 (m, 1H), 1.91–1.76 (m, 1H), 1.54–1.37 (m, 1H), 1.29–1.14 (m, 2H),
1.12–0.95 (m, 3H), 0.83 (t, J¼7.4 Hz, 3H); 31P NMR (121.5 MHz,
1.93–1.75 (m, 2H), 0.79 (t, J¼7.4 Hz, 3H); HPLC conditions: Chiralcel
OD-H, hexane/i-PrOH¼95:5, 0.7 mL/min, n¼230 nm, tR 14.8 (ma-
20
jor), 16.3 (minor); [
a
]
þ20.72 (c 0.74, CHCl3).
D
4.2.3. 4-Methylpenta-1,2-dienyl diphenyl phosphine oxide (1l)
The reaction of 4-methylpent-1-yn-3-ol (2.0619 g (contami-
nated with THF, purity: 95%), 20 mmol), Et3N (4.20 mL, d¼0.73 g/
mL, 3.07 g, 30 mmol), and Ph2PCl (5.50 mL, d¼1.20 g/mL, 6.60 g,
30 mmol) in 55.5 mL of THF for 12 h afforded 1l (2.4698 g, 44%) as
CDCl3)
d
32.4; MS (ESI) m/z (%) 561 (Mþ(80Se)þ1, 3.49), 546
(Mþ(82Se)þ1ꢁOH, 6.10), 544 (Mþ(80Se)þ1ꢁOH, 45.35), 542
(Mþ(78Se)þ1ꢁOH, 16.86), 545 (Mþ(82Se)ꢁOH, 27.33), 543
(Mþ(80Se)ꢁOH, 100), 541 (Mþ(78Se)ꢁOH or Mþ(77Se)þ1ꢁOH,
56.40), 540 (Mþ(77Se)ꢁOH or Mþ(76Se)þ1ꢁOH, 24.42), 539
a solid. Mp 63–64 ꢀC (Et2O). 1H NMR (400 MHz, CDCl3)
d
7.79–7.70
(Mþ(76Se)ꢁOH, 30.23); IR
n
(neat, cmꢁ1) 3280, 1560, 1473, 1437,
(m, 4H), 7.55–7.41 (m, 6H), 5.91–5.84 (m, 1H), 5.24 (dt, J1¼10.8 Hz,
1168. Anal. Calcd for C32H33O2PSe: C, 68.69; H, 5.94. Found: C,
J2¼6.4 Hz, 1H), 2.27–2.15 (m, 1H), 0.81 (d, J¼6.8 Hz, 3H), 0.80 (d,
68.67; H, 5.91.
J2¼6.8 Hz, 3H); 13C NMR (100 MHz, CDCl3)
d
210.3, 132.6 (d,
The following compounds were prepared according to General
Procedure III.
Jpc¼105.9 Hz), 132.3 (d, Jpc¼105.9 Hz), 131.6 (d, Jpc¼2.7 Hz), 131.4
(d, Jpc¼8.8 Hz), 131.3 (d, Jpc¼9.7 Hz), 128.2 (d, Jpc¼1.5 Hz), 128.1 (d,
Jpc¼1.8 Hz), 99.8 (d, Jpc¼13.5 Hz), 86.4 (d, Jpc¼105.9 Hz), 27.2 (d,
Jpc¼5.2 Hz), 22.1 (d, Jpc¼3.6 Hz), 21.8 (d, Jpc¼2.6 Hz); 31P NMR
4.3.2. 3-Hydroxy-2-phenylselanyl-1(E)-butenyl diphenyl phosphine
oxide (E-2b)
The reaction of 1b (77.0 mg, 0.30 mmol) and PhSeCl (87.1 mg,
0.45 mmol) in 0.3 mL of H2O and 6 mL of CH3CN for 12 min afforded
(121.5 MHz, CDCl3)
d
24.9; MS (EI, 70 eV) m/z (%) 283 (Mþþ1, 6.22),
282 (Mþ, 25.02), 201 (100); IR (KBr, cmꢁ1) 1945, 1592, 1464, 1440,
n

G. He et al. / Tetrahedron 65 (2009) 4877–4889
4883
E-2b (106.3 mg, 82%) as a solid. Mp 145–146 ꢀC (hexane/ethyl ac-
etate). 1H NMR (400 MHz, CDCl3)
7.62–7.27 (m, 15H), 5.98 (d,
J¼7.2 Hz, 1H), 5.59 (d, J¼20.4 Hz, 1H), 5.05–4.92 (m, 1H), 1.55
80.7 (d, Jpc¼5.4 Hz), 44.4, 16.6, 14.4; 31P NMR (121.5 MHz, CDCl3)
d
d
24.9; MS (ESI) m/z (%) 484 (Mþ(82Se)þ1ꢁOH, 14.91), 482
(Mþ(80Se)þ1ꢁOH, 58.19), 480 (Mþ(78Se)ꢁOHþ1, 28.65), 478
(Mþ(76Se)þ1ꢁOH or Mþ(77Se)ꢁOH, 46.78), 476 (Mþ(74Se)þ1ꢁOH,
1.75), 483 (Mþ(82Se)ꢁOH, 47.37), 481 (Mþ(80Se)ꢁOH, 100), 479
(Mþ(78Se)ꢁOH or Mþ(77Se)þ1ꢁOH, 83.63), 477 (Mþ(76Se)ꢁOH or
(d, J¼5.6 Hz, 3H); 13C NMR (100 MHz, CDCl3)
d 170.4, 136.7, 133.4
(d, Jpc¼105.4 Hz), 133.1 (d, Jpc¼105.1 Hz), 131.62 (d, Jpc¼4.3 Hz),
131.59 (d, Jpc¼4.5 Hz), 130.7 (d, Jpc¼10.0 Hz), 130.6 (d, Jpc¼9.8 Hz),
129.7, 129.2, 128.4 (d, Jpc¼12.0 Hz), 127.5, 112.8 (d, Jpc¼96.1 Hz),
Mþ(77Se)ꢁH2O, 39.18), 475 (Mþ(74Se)ꢁOH, 4.68); IR
n )
(neat, cmꢁ1
69.9 (d, Jpc¼6.7 Hz), 23.5; 31P NMR (121.5 MHz, CDCl3)
d
23.7;
3212, 1571, 1473, 1435, 1313, 1168, 1121, 1099. Anal. Calcd for
C27H31O2PSe: C, 65.19; H, 6.28. Found: C, 65.28; H, 6.21.
MS (EI, 70 eV) m/z (%) 386 (Mþ(82Se)þ1ꢁCH3CHOH, 1.68), 384
(Mþ(80Se)þ1ꢁCH3CHOH, 2.32), 382 (Mþ(78Se)þ1ꢁCH3CHOH, 1.92),
380 (Mþ(76Se)þ1ꢁCH3CHOH or Mþ(77Se)ꢁCH3CHOH, 0.75), 385
(Mþ(82Se)ꢁCH3CHOH, 4.83), 383 (Mþ(80Se)ꢁCH3CHOH, 5.09), 381
(Mþ(78Se)ꢁCH3CHOH, or Mþ(77Se)þ1ꢁCH3CHOH, 2.16), 379
4.3.6. 3-Hydroxy-3,3-pentamethylene-2-phenylselanyl-1(E)-
propenyl diphenyl phosphine oxide (E-2f)
The reaction of 1f (93.3 mg, 0.30 mmol) and PhSeCl (87.5 mg,
0.45 mmol) in 0.3 mL of H2O and 6 mL of CH3CN for 10 min afforded
E-2f (122.9 mg, 84%) as a solid. Mp 134–135 ꢀC (hexane/ethyl ace-
(Mþ(76Se)ꢁCH3CHOH, 0.58), 271 (100); IR
n
(KBr, cmꢁ1) 3300, 1591,
1566, 1477, 1436, 1360, 1273, 1172, 1119, 1104. Anal. Calcd for
C22H21O2PSe: C, 61.83; H, 4.95. Found: C, 61.85; H, 4.96.
tate). 1H NMR (300 MHz, CDCl3)
d
7.51 (d, J¼7.8 Hz, 2H), 7.48–7.24 (m,
13H), 6.68 (s,1H), 5.45 (d, J¼18.3 Hz,1H), 2.04–1.76 (m, 6H),1.76–1.54
(m, 3H), 1.32–1.12 (m, 1H); 13C NMR (100 MHz, CDCl3)
174.6 (d,
4.3.3. 3-Hydroxy-3-phenyl-2-phenylselanyl-1(E)-propenyl
diphenyl phosphine oxide (E-2c)
The reaction of 1c (94.9 mg, 0.30 mmol) and PhSeCl (87.1 mg,
0.45 mmol) in 0.3 mL of H2O and 6 mL of CH3CN for 28 min afforded
E-2c (125.5 mg, 85%) as a solid. Mp 163–164 ꢀC (ethyl acetate). 1H
d
Jpc¼2.1 Hz), 136.9, 133.3 (d, Jpc¼107.5 Hz), 131.4 (d, Jpc¼2.3 Hz), 130.7
(d, Jpc¼9.8 Hz), 129.8, 129.2, 129.1, 128.3 (d, Jpc¼12.1 Hz), 113.0 (d,
Jpc¼97.2 Hz), 76.2 (d, Jpc¼5.4 Hz), 36.6, 25.3, 21.5; 31P NMR
(121.5 MHz, CDCl3)
d
26.1; MS (EI, 70 eV) m/z (%) 402 (Mþ(77Se)ꢁC6H5
NMR (300 MHz, CDCl3)
d
7.60–7.23 (m, 20H), 6.33 (d, J¼6.6 Hz, 1H),
or Mþ(78Se)ꢁC6H5ꢁ1, 2.82), 401 (Mþ(76Se)ꢁC6H5, 9.01), 386
(Mþ(82Se)þ1ꢁC6H10OH, 0.77), 384 (Mþ(80Se)þ1ꢁC6H10OH, 4.41),
382 (Mþ(78Se)þ1ꢁC6H10OH, 1.30), 381 (Mþ(77Se)þ1ꢁC6H10OH
or Mþ(78Se)ꢁC6H10OH, 1.57), 380 (Mþ(76Se)þ1ꢁC6H10OH or
Mþ(77Se)ꢁC6H10OH, 0.87), 385 (Mþ(82Se)ꢁC6H10OH, 1.90), 383
6.00 (d, J¼5.4 Hz, 1H), 5.80 (d, J¼19.5 Hz, 1H); 13C NMR (75 MHz,
CDCl3)
d
168.0, 140.7, 136.7, 133.1 (d, Jpc¼106.0 Hz), 133.0 (d,
Jpc¼107.0 Hz), 131.76 (d, Jpc¼12.4 Hz), 131.72 (d, Jpc¼12.0 Hz), 130.9
(d, Jpc¼14.9 Hz), 130.7 (d, Jpc¼16.1 Hz), 129.8, 129.3, 128.6 (d,
Jpc¼12.0 Hz), 128.5 (d, Jpc¼12.2 Hz), 128.2, 128.1, 127.8, 127.0, 115.6
(d, Jpc¼96.2 Hz), 74.9 (d, Jpc¼7.1 Hz); 31P NMR (121.5 MHz, CDCl3)
(Mþ(80Se)ꢁC6H10OH, 8.00), 201 (100); IR
n
(KBr, cmꢁ1) 3182, 1561,
1543, 1443, 1435, 1168, 1155, 1117, 1097. Anal. Calcd for C26H27O2PSe:
C, 64.87; H, 5.65. Found: C, 64.87; H, 5.66.
d
23.8; MS (ESI) m/z (%) 492 (Mþ(82Se), 9.30), 491 (Mþ(80Se)þ1,
43.72), 489 (Mþ(78Se)þ1, 20.35), 476 (Mþ(82Se)þ1ꢁOH, 6.98), 474
(Mþ(80Se)þ1ꢁOH, 29.94), 472 (Mþ(78Se)þ1ꢁOH, 12.79), 470
(Mþ(77Se)ꢁOH or Mþ(76Se)þ1ꢁOH, 19.19), 475 (Mþ(82Se)ꢁOH,
26.74), 473 (Mþ(80Se)ꢁOH, 100), 471 (Mþ(78Se)ꢁOH or
4.3.7. 1-Hydroxy-2-phenylselanyl-2(E)-hepten-3-yl diphenyl
phosphine oxide (E-2g)
The reaction of 1g (88.9 mg, 0.30 mmol) and PhSeCl (86.6 mg,
0.45 mmol) in 0.3 mL of H2O and 6 mL of CH3CN for 16 min afforded
E-2g (94.6 mg, 67%) as a solid. Mp 113–114 ꢀC (hexane/ethyl ace-
Mþ(77Se)þ1ꢁOH, 51.16), 469 (Mþ(76Se)ꢁOH,14.83); IR
n )
(KBr, cmꢁ1
3275, 1592, 1571, 1493, 1474, 1439, 1274, 1186, 1173, 1118. Anal. Calcd
for C27H23O2PSe: C, 66.26; H, 4.74. Found: C, 66.25; H, 4.77.
tate). 1H NMR (300 MHz, CDCl3)
d 7.78–7.43 (m, 12H), 7.41–7.28 (m,
3H), 5.61 (t, J¼7.5 Hz, 1H), 4.22 (d, J¼7.5 Hz, 2H), 2.37–2.15 (m, 2H),
4.3.4. 3-Hydroxy-3-methyl-2-phenylselanyl-1(E)-butenyl diphenyl
phosphine oxide (E-2d)
The reaction of 1d (81.0 mg, 0.30 mmol) and PhSeCl (86.4 mg,
0.45 mmol) in 0.3 mL of H2O and 6 mL of CH3CN for 19 min afforded
E-2d (118.6 mg, 89%) as a solid. Mp 103–104 ꢀC (hexane/ethyl ace-
1.10–0.90 (m, 4H), 0.60 (t, J¼6.5 Hz, 3H); 31P NMR (121.5 MHz,
CDCl3)
d
32.9; MS (ESI) m/z (%) 473 (Mþ(82Se)þ1, 19.25), 471
(Mþ(80Se)þ1 or Mþ(82Se)ꢁ1, 100), 469 (Mþ(78Se)þ1 or Mþ(80Se)ꢁ1,
49.37), 468 (Mþ(77Se)þ1 or Mþ(78Se), 20.08), 467 (Mþ(76Se)þ1 or
Mþ(77Se) or Mþ(78Se)ꢁ1, 21.76), 472 (Mþ(82Se), 25.94), 470
tate). 1H NMR (400 MHz, CDCl3)
d
7.51 (d, J¼7.2 Hz, 2H), 7.47–7.24
(Mþ(80Se), 30.13), 466 (Mþ(76Se) or Mþ(77Se)ꢁ1, 19.25); IR
n (KBr,
(m, 13H), 7.02 (s, 1H), 5.47 (d, J¼18.0 Hz, 1H), 1.65 (s, 6H); 13C NMR
cmꢁ1) 3307, 1577, 1548, 1466, 1440, 1167, 1145. Anal. Calcd for
C25H27O2PSe: C, 63.97; H, 5.80. Found: C, 63.98; H, 5.82.
(100 MHz, CDCl3)
d
173.4, 136.9, 133.1 (d, Jpc¼106.5 Hz), 131.5 (d,
Jpc¼2.5 Hz), 130.8 (d, Jpc¼9.0 Hz), 129.9, 129.3, 128.9, 128.4 (d,
Jpc¼12.3 Hz), 113.0 (d, Jpc¼96.6 Hz), 75.0 (d, Jpc¼5.7 Hz), 29.8; 31P
4.3.8. 3-Hydroxy-1-phenyl-2-phenylselanyl-1(E)-propenyl
diphenyl phosphine oxide (E-2h)
NMR (121.5 MHz, CDCl3)
d
25.9; MS (ESI) m/z (%) 445 (Mþ(82Se)þ1,
21.43), 443 (Mþ(80Se)þ1 or Mþ(82Se)ꢁ1, 100), 441 (Mþ(78Se)þ1 or
Mþ(80Se)ꢁ1, 48.41), 440 (Mþ(77Se)þ1 or Mþ(78Se), 18.25), 439
(Mþ(76Se)þ1 or Mþ(77Se) or Mþ(78Se)ꢁ1, 15.87), 444 (Mþ(82Se),
The reaction of 1h (95.3 mg, 0.30 mmol) and PhSeCl (88.6 mg,
0.45 mmol) in 0.3 mL of H2O and 6 mL of CH3CN for 14 min afforded
E-2h (117.9 mg, 80%) as a solid. Mp 138–139 ꢀC (hexane/ethyl ace-
24.60), 442 (Mþ(80Se), 14.29); IR
n
(KBr, cmꢁ1) 3242, 1583, 1568,
tate). 1H NMR (400 MHz, CDCl3)
d
7.68–7.52 (m, 6H), 7.51–7.42 (m,
1438, 1358, 1190, 1160, 1117, 1097. Anal. Calcd for C23H23O2PSe: C,
62.59; H, 5.25. Found: C, 62.54; H, 5.31.
2H), 7.41–7.29 (m, 7H), 7.18–7.06 (m, 3H), 6.84 (d, J¼8.0 Hz, 2H),
5.94 (br s, 1H), 4.40 (s, 2H); 31P NMR (121.5 MHz, CDCl3)
d 30.5; MS
(ESI) m/z (%) 493 (Mþ(82Se)þ1, 16.23), 491 (Mþ(80Se)þ1 or
Mþ(82Se)ꢁ1, 100), 489 (Mþ(78Se)þ1 or Mþ(80Se)ꢁ1, 52.27), 488
(Mþ(77Se)þ1 or Mþ(78Se), 21.75), 487 (Mþ(76Se)þ1 or Mþ(77Se) or
Mþ(78Se)ꢁ1, 16.23), 492 (Mþ(82Se), 33.44), 490 (Mþ(80Se), 17.86); IR
4.3.5. 3-Hydroxy-2-phenylselanyl-3-propyl-1(E)-hexenyl diphenyl
phosphine oxide (E-2e)
The reaction of 1e (97.3 mg, 0.30 mmol) and PhSeCl (85.5 mg,
0.45 mmol) in 0.3 mL of H2O and 6 mL of CH3CN for 18 min affor-
ded E-2e (119.7 mg, 80%) as a liquid. 1H NMR (400 MHz, CDCl3)
n
(KBr, cmꢁ1) 3325, 1576, 1558, 1474, 1440, 1160. Anal. Calcd for
C27H23O2PSe: C, 66.26; H, 4.74. Found: C, 66.24; H, 4.79.
d
7.55 (d, J¼6.8 Hz, 2H), 7.47–7.36 (m, 7H), 7.35–7.28 (m, 6H), 6.53
(s, 1H), 5.71 (d, J¼18.4 Hz, 1H), 1.90–1.70 (m, 4H), 1.53–1.32 (m, 4H),
4.3.9. 5-Hydroxy-4-phenylselanyl-3(E)-hexen-3-yl diphenyl
phosphine oxide (E-2i)
The reaction of 1i (90.3 mg, 0.30 mmol) and PhSeCl (87.1 mg,
0.45 mmol) in 0.3 mL of H2O and 6 mL of CH3CN for 10 min afforded
0.91 (t, J¼7.4 Hz, 6H); 13C NMR (100 MHz, CDCl3)
d 172.1, 137.2,
134.0 (d, Jpc¼107.2 Hz), 131.2 (d, Jpc¼2.4 Hz), 130.7 (d, Jpc¼9.3 Hz),
129.9, 129.3, 128.6, 128.2 (d, Jpc¼11.8 Hz), 115.8 (d, Jpc¼97.4 Hz),

4884
G. He et al. / Tetrahedron 65 (2009) 4877–4889
E-2i (130.6 mg, 90%) as a liquid. 1H NMR (300 MHz, CDCl3)
7.62 (m, 4H), 7.62–7.41 (m, 8H), 7.36–7.27 (m, 3H), 6.62 (br s, 1H),
d
7.80–
129.7, 129.2, 128.32 (d, Jpc¼12.7 Hz), 128.30 (d, Jpc¼11.6 Hz), 127.7,
113.9 (d, Jpc¼96.8 Hz), 78.5 (d, Jpc¼5.3 Hz), 34.6, 19.7, 18.5; 31P NMR
4.64–4.52 (m, 1H), 2.55–2.21 (m, 2H), 1.49 (d, J¼6.6 Hz, 3H), 0.44 (t,
(121.5 MHz, CDCl3)
d
22.6; MS (ESI) m/z (%) 482 (Mþ(82Se)þNaþ1,
J¼7.2 Hz, 3H); 31P NMR (121.5 MHz, CDCl3)
d
33.7; MS (ESI) m/z (%)
5.88), 480 (Mþ(80Se)þNaþ1, 25.21), 478 (Mþ(78Se)þNaþ1, 12.61),
481 (Mþ(82Se)þNa, 21.85), 479 (Mþ(80Se)þNa, 100), 477
(Mþ(78Se)þNa or Mþ(77Se)þNaþ1, 51.68), 476 (Mþ(77Se)þNa or
Mþ(76Se)þNaþ1, 15.97), 475 (Mþ(76Se)þNa, 9.24), 459
(Mþ(82Se)þ1, 8.40), 457 (Mþ(80Se)þ1, 36.13), 455 (Mþ(78Se)þ1,
17.23), 458 (Mþ(82Se), 11.76), 456 (Mþ(80Se), 3.36), 454 (Mþ(78Se) or
459 (Mþ(82Se)þ1, 21.01), 457 (Mþ(80Se)þ1 or Mþ(82Se)ꢁ1,100), 455
(Mþ(78Se)þ1 or Mþ(80Se)ꢁ1, 54.62), 454 (Mþ(77Se)þ1 or Mþ(78Se),
17.65), 453 (Mþ(76Se)þ1 or Mþ(77Se) or Mþ(78Se)ꢁ1, 18.49), 458
(Mþ(82Se), 26.89), 456 (Mþ(80Se), 14.29), 452 (Mþ(76Se) or
Mþ(77Se)ꢁ1, 21.01), 439 (Mþ(80Se)ꢁOH, 13.87); IR
n )
(neat, cmꢁ1
3240, 1576, 1557, 1476, 1437, 1363, 1167, 1117. Anal. Calcd for
C24H25O2PSe: C, 63.30; H, 5.53. Found: C, 63.33; H, 5.57.
Mþ(77Se)þ1, 9.66), 453 (Mþ(77Se) or Mþ(76Se)þ1, 8.40); IR
n (KBr,
cmꢁ1) 3299, 1592, 1578, 1570, 1437, 1288, 1172. Anal. Calcd for
C24H25O2PSe: C, 63.30, H, 5.53. Found: C, 63.34; H, 5.54. Compound
4.3.10. 3-Hydroxy-1-phenyl-2-phenylselanyl-1(E)-pentenyl
diphenyl phosphine oxide (E-2j)
The reaction of 1j (103.7 mg, 0.30 mmol) and PhSeCl
(87.8 mg, 0.45 mmol) in 0.3 mL of H2O and 6 mL of CH3CN for
Z-3l: liquid. 1H NMR (300 MHz, CDCl3)
d 7.93–7.83 (m, 2H), 7.83–
7.73 (m, 2H), 7.60–7.43 (m, 6H), 7.43–7.23 (m, 5H), 7.10 (dd,
J1¼21.3 Hz, J2¼0.9 Hz, 1H), 4.28 (dd, J1¼3.2 Hz, J2¼0.9 Hz, 1H), 2.49–
2.31 (m, 1H), 0.87 (d, J¼6.6 Hz, 3H), 0.82 (d, J¼6.6 Hz, 3H); 13C NMR
5 min afforded E-2j (137.8 mg, 88%) as
(300 MHz, CDCl3)
a
liquid. 1H NMR
(75 MHz, CDCl3)
d
157.0 (d, Jpc¼1.4 Hz), 136.0, 134.1 (d,
d
7.74 (dd, J1¼12.5 Hz, J2¼7.4 Hz, 2H), 7.61–
Jpc¼106.2 Hz), 133.1 (d, Jpc¼105.8 Hz), 131.7 (d, Jpc¼2.8 Hz), 131.6 (d,
Jpc¼2.7 Hz), 131.3 (d, Jpc¼10.1 Hz), 130.8 (d, Jpc¼9.5 Hz), 129.4, 129.1,
128.6 (d, Jpc¼12.5 Hz), 128.4 (d, Jpc¼12.2 Hz), 126.9, 123.5 (d,
Jpc¼105.9 Hz), 70.3 (d, Jpc¼14.3 Hz), 32.7, 20.7, 15.3; 31P NMR
7.22 (m, 13H), 7.16–7.07 (m, 2H), 7.01–6.90 (m, 1H), 6.90–6.79
(m, 1H), 6.74 (d, J¼11.4 Hz, 1H), 6.51 (d, J¼7.2 Hz, 1H), 4.22 (t,
J¼9.5 Hz, 1H), 2.22–2.01 (m, 1H), 1.98–1.82 (m, 1H), 0.80 (t,
J¼7.4 Hz, 3H); 31P NMR (121.5 MHz, CDCl3)
d
32.3; MS (ESI) m/z
(121.5 MHz, CDCl3)
d
21.5; MS (ESI) m/z (%) 479 (Mþ(82Se37Cl)þ1,
(%) 504 (Mþ(82Se)þ1ꢁOH, 8.77), 502 (Mþ(80Se)þ1ꢁOH or
Mþ(82Se)ꢁH2O, 56.14), 500 (Mþ(78Se)þ1ꢁOH or Mþ(80Se)ꢁH2O,
42.69), 503 (Mþ(82Se)ꢁOH, 38.60), 501 (Mþ(80Se)ꢁOH, 100), 499
(Mþ(78Se)ꢁOH or Mþ(77Se)þ1ꢁOH, 72.81), 498 (Mþ(77Se)ꢁOH
4.20), 477 (Mþ(82Se35Cl)þ1 or Mþ(80Se37Cl)þ1, 39.50), 475
(Mþ(80Se35Cl)þ1 or Mþ(78Se37Cl)þ1, 100), 471 (Mþ(77Se35Cl) or
Mþ(76Se35Cl)þ1 or Mþ(74Se37Cl)þ1, 13.45), 478 (Mþ(82Se37Cl),
10.08), 476 (Mþ(82Se35Cl) or Mþ(80Se37Cl), 25.21), 474 (Mþ(80Se35Cl)
or Mþ(78Se37Cl), 15.13), 473 (Mþ(77Se37Cl) or Mþ(78Se35Cl)þ1 or
Mþ(76Se37Cl)þ1, 43.70), 472 (Mþ(76Se37Cl) or Mþ(78Se35Cl), 12.61);
or
Mþ(76Se)þ1ꢁOH
or
Mþ(78Se)ꢁH2O,
43.27),
497
(Mþ(76Se)ꢁOH or Mþ(77Se)ꢁH2O, 35.07), 495 (Mþ(74Se)ꢁOH,
2.92); IR
n
(neat, cmꢁ1) 3422, 1560, 1550, 1473, 1437, 1380, 1160,
IR n
(neat, cmꢁ1) 3056, 2967, 2929, 2871, 1560, 1476, 1437, 1195.
1116, 1098. Anal. Calcd for C29H27O2PSe: C, 67.31; H, 5.26. Found:
C, 67.27; H, 5.28.
Anal. Calcd for C24H24ClOPSe: C, 60.84; H, 5.11; Cl, 7.48. Found: C,
60.86; H, 5.13; Cl, 7.31.
4.3.11. 2-Hydroxy-2-methyl-3-phenylselanyl-3(E)-octen-4-yl
diphenyl phosphine oxide (E-2k)
4.3.13. 3-Hydroxy-2-phenylselanyl-1(E)-propenyl diphenyl
phosphine oxide (E-2m) and 3-chloro-2-phenylselanyl-1(Z)-
propenyl diphenyl phosphine oxide (Z-3m)
The reaction of 1k (95.5 mg, 0.30 mmol) and PhSeCl (86.2 mg,
0.45 mmol) in 0.3 mL of H2O and 6 mL of CH3CN for 10 min afforded
The reaction of 1m (71.8 mg, 0.3 mmol) and PhSeCl (86.6 mg,
0.45 mmol) in 0.3 mL of H2O and 6.0 mL of MeCN afforded E-2m
(15.7 mg, 13%) and Z-3m (less polar, 79.4 mg, 61.5%). E-2m/Z-
3m¼17.5:82.5. Compound E-2m: solid. Mp 136.7–137.6 ꢀC (petro-
E-2k (94.7 mg, 65%) as a liquid. 1H NMR (400 MHz, CDCl3)
d 7.71–
7.61 (m, 4H), 7.56–7.49 (m, 2H), 7.48–7.40 (m, 6H), 7.34 (s,1H), 7.30–
7.20 (m, 3H), 2.25–2.12 (m, 2H), 1.65 (s, 6H), 1.05–0.95 (m, 2H),
0.85–0.73 (m, 2H), 0.51 (t, J¼7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3)
leum/ethyl acetate). 1H NMR (300 MHz, CDCl3)
d 7.64–7.31 (m,15H),
d
163.1 (d, Jpc¼4.6 Hz), 136.1 (d, Jpc¼78.8 Hz), 133.4 (d, Jpc¼1.9 Hz),
6.11 (t, J¼7.2 Hz, 1H), 5.79 (d, J¼21.0 Hz, 1H), 4.52 (d, J¼5.1 Hz, 2H);
132.8 (d, Jpc¼104.2 Hz), 132.1 (d, Jpc¼10.1 Hz), 131.8 (d, Jpc¼2.6 Hz),
129.9, 129.3, 128.3 (d, Jpc¼12.0 Hz), 126.6, 77.2 (d, Jpc¼4.9 Hz), 38.1
(d, Jpc¼14.9 Hz), 31.3, 30.4, 22.5, 13.3; 31P NMR (121.5 MHz, CDCl3)
13C NMR (100 MHz, CDCl3)
d
164.3, 136.4, 132.9 (d, Jpc¼106.1 Hz),
131.8 (d, Jpc¼3.1 Hz), 130.7 (d, Jpc¼10.4 Hz), 129.8, 129.4, 128.5 (d,
Jpc¼12.1 Hz), 127.3, 114.6 (d, Jpc¼95.8 Hz), 64.3 (d, Jpc¼6.8 Hz); 31P
d
37.3; MS (ESI) m/z (%) 484 (Mþ(82Se)þ1ꢁOH, 17.58), 482
NMR (121.5 MHz, CDCl3)
d
25.1; MS (ESI) m/z (%) 417 (Mþ(82Se)þ1,
(Mþ(80Se)þ1ꢁOH or Mþ(82Se)ꢁH2O, 72.73), 483 (Mþ(82Se)ꢁOH,
61.82), 481 (Mþ(80Se)ꢁOH, 100), 479 (Mþ(78Se)ꢁOH or
Mþ(77Se)þ1ꢁOH, 91.82), 477 (Mþ(76Se)ꢁOH or Mþ(77Se)ꢁH2O,
19.83), 415 (Mþ(80Se)þ1 or Mþ(82Se)ꢁ1, 100), 413 (Mþ(78Se)þ1 or
Mþ(80Se)ꢁ1, 6.47), 416 (Mþ(82Se), 18.53), 414 (Mþ(80Se), 14.22), 412
(Mþ(78Se) or Mþ(77Se)þ1, 17.24), 411 (Mþ(77Se) or Mþ(78Se)ꢁ1 or
57.58), 475 (Mþ(74Se)ꢁOH, 5.45); IR
n
(neat, cmꢁ1) 3209, 1576, 1534,
Mþ(76Se)þ1, 15.52), 410 (Mþ(76Se) or Mþ(77Se)ꢁ1, 14.66); IR
n (KBr,
1476,1437,1354,1186,1164,1116,1095. Anal. Calcd for C27H31O2PSe:
C, 65.19; H, 6.28. Found: C, 65.21; H, 6.30.
cmꢁ1) 3231, 1567, 1439, 1279, 1169, 1121, 1105, 1076. Anal. Calcd for
C21H19O2PSe: C, 61.03; H, 4.63. Found: C, 61.11; H, 4.55. Compound
Z-3m: liquid. 1H NMR (300 MHz, CDCl3)
d 7.89–7.74 (m, 4H), 7.60–
4.3.12. 3-Hydroxy-4-methyl-2-phenylselanyl-1(E)-pentenyl
diphenyl phosphine oxide (E-2l) and 3-chloro-4-methyl-2-
7.42 (m, 8H), 7.40–7.24 (m, 3H), 7.02 (dt, J1¼21.0 Hz, J2¼1.7 Hz, 1H),
4.06 (t, J¼1.5 Hz, 2H); 13C NMR (75 MHz, CDCl3)
d 152.6 (d,
phenylselanyl-1(Z)-pentenyl diphenyl phosphine oxide (Z-3l)
The reaction of 1l (422.6 mg, 1.5 mmol) and PhSeCl (431.8 mg,
2.25 mmol) in 1.0 mL of H2O and 20 mL of MeCN afforded a crude
mixture, which was purified by flash chromatography on silica gel
(eluent: CH2Cl2/ethyl acetate¼40:1 to 3:1) to yield E-2l (525.5 mg,
76%) and Z-3l (less polar, 52.1 mg, 7%). E-2l/Z-3l¼92:8. Compound
E-2l: solid. Mp 149–150 ꢀC (n-hexane/ethyl acetate). 1H NMR
Jpc¼2.0 Hz),136.7,133.2 (d, Jpc¼106.0 Hz),131.8 (d, Jpc¼2.9 Hz),131.1
(d, Jpc¼9.3 Hz), 129.4, 129.3, 128.6 (d, Jpc¼12.0 Hz), 125.8, 121.2 (d,
Jpc¼105.1 Hz), 48.7 (d, Jpc¼16.4 Hz); 31P NMR (121.5 MHz, CDCl3)
d
22.1; MS (ESI) m/z (%) 437 (Mþ(82Se37Cl)þ1, 5.88), 436
(Mþ(82Se37Cl), 7.56), 435 (Mþ(82Se35Cl)þ1 or Mþ(80Se37Cl)þ1,
42.86), 434 (Mþ(82Se35Cl) or Mþ(80Se37Cl), 18.49), 433
(Mþ(80Se35Cl)þ1 or Mþ(78Se37Cl)þ1, 100), 431 (Mþ(77Se37Cl) or
Mþ(78Se35Cl)þ1 or Mþ(76Se37Cl)þ1, 45.38), 430 (Mþ(76Se37Cl)
or Mþ(78Se35Cl), 18.49), 429 (Mþ(77Se35Cl) or Mþ(76Se35Cl)þ1 or
(400 MHz, CDCl3)
d 7.59–7.52 (m, 2H), 7.52–7.27 (m, 13H), 5.71 (d,
J¼7.6 Hz, 1H), 5.65 (d, J¼20.4 Hz, 1H), 4.60 (t, J¼7.2 Hz, 1H), 2.22–
2.10 (m, 1H), 1.07 (d, J¼6.4 Hz, 3H), 0.92 (d, J¼7.2 Hz, 3H); 13C NMR
Mþ(74Se37Cl)þ1, 16.81); IR
n
(neat, cmꢁ1) 3054, 1589, 1560, 1475,
(100 MHz, CDCl3)
Jpc¼105.8 Hz), 131.4, 130.6 (d, Jpc¼6.5 Hz), 130.5 (d, Jpc¼6.5 Hz),
d
168.9, 136.8, 133.7 (d, Jpc¼105.9 Hz), 133.5 (d,
1437, 1261, 1183, 1118. Anal. Calcd for C21H18ClOPSe: C, 58.42; H,
4.20; Cl, 8.21. Found: C, 58.31; H, 4.25; Cl, 8.08.

G. He et al. / Tetrahedron 65 (2009) 4877–4889
4885
4.3.14. 3-Hydroxy-2-phenylselanyl-1(E)-pentenyl diphenyl
phosphine oxide (E-2n) and 3-chloro-2-phenylselanyl-1(Z)-
pentenyl diphenyl phosphine oxide (Z-3n)
Mþ(77Se)ꢁH2O, 23.10); IR
n
(KBr, cmꢁ1) 3330, 1590, 1560, 1437, 1187,
1118. Anal. Calcd for C27H31O2PSe: C, 65.19; H, 6.28. Found: C, 65.21;
H, 6.19. Compound Z-3o: liquid. 1H NMR (300 MHz, CDCl3)
d 7.93–
The reaction of 1n (321.0 mg, 1.2 mmol) and PhSeCl (345.3 mg,
1.8 mmol) in 0.9 mL of H2O and 18.0 mL of MeCN afforded E-2n
(436.1 mg, 82.5%) and Z-3n (less polar, 33.9 mg, 6%). E-2n/Z-
3n¼93:7. Compound E-2n: solid. Mp 146.5–147.5 ꢀC (hexane/ethyl
7.73 (m, 4H), 7.58–7.23 (m, 11H), 7.11 (d, J¼21.0 Hz, 1H), 4.29 (dd,
J1¼9.0 Hz, J2¼3.3 Hz, 1H), 2.08–1.96 (m, 1H), 1.82–1.66 (m, 1H),
1.47–1.32 (m, 1H), 1.31–1.02 (m, 7H), 0.85 (t, J¼6.9 Hz, 3H); 13C NMR
(75 MHz, CDCl3)
d
158.5 (d, Jpc¼1.3 Hz), 136.0, 133.9 (d,
acetate). 1H NMR (300 MHz, CDCl3)
d
7.64–7.31 (m, 15H), 5.71 (d,
Jpc¼106.1 Hz), 133.1 (d, Jpc¼105.8 Hz), 131.7 (d, Jpc¼2.6 Hz), 131.6 (d,
Jpc¼2.9 Hz), 131.3 (d, Jpc¼9.9 Hz), 130.9 (d, Jpc¼9.7 Hz), 129.4, 129.1,
128.6 (d, Jpc¼9.7 Hz), 128.5 (d, Jpc¼10.4 Hz), 127.0, 122.5 (d,
Jpc¼105.5 Hz), 63.9 (d, Jpc¼14.9 Hz), 38.6 (d, Jpc¼1.6 Hz), 31.4, 28.2,
J¼9.0 Hz, 1H), 5.64 (d, J¼20.1 Hz, 1H), 4.67–4.51 (m, 1H), 2.00–1.80
(m, 2H), 1.01 (t, J¼7.4 Hz, 3H); 13C NMR (75 MHz, CDCl3)
d 169.3,
136.7, 133.5 (d, Jpc¼106.4 Hz), 133.2 (d, Jpc¼105.8 Hz), 131.6, 130.7
(d, Jpc¼8.6 Hz), 130.6 (d, Jpc¼9.8 Hz), 129.7, 129.3, 128.4 (d,
Jpc¼11.9 Hz), 127.6, 113.3 (d, Jpc¼96.9 Hz), 75.4 (d, Jpc¼5.3 Hz), 30.6,
26.1, 22.4, 14.0; 31P NMR (121.5 MHz, CDCl3)
d 21.7; MS (ESI) m/z (%)
556 (Mþ(80Se35Cl)þKþ or Mþ(78Se37Cl)þKþ, 3.35), 535 (Mþ(80Se35
Cl)þNHþ4 or Mþ(78Se37Cl)þNH4þ, 8.37), 533 (Mþ(77Se37Cl) or
Mþ(78Se35Cl)þNH4þ or Mþ(76Se37Cl)þNHþ4 , 16.74), 521 (Mþ(82Se37
Cl)þ1, 4.60), 519 (Mþ(82Se35Cl)þ1 or Mþ(80Se37Cl)þ1, 53.56), 517
(Mþ(80Se35Cl)þ1 or Mþ(78Se37Cl)þ1, 100), 515 (Mþ(77Se37Cl) or
Mþ(78Se35Cl)þ1 or Mþ(76Se37Cl)þ1, 50.21), 513 (Mþ(77Se35Cl) or
Mþ(76Se35Cl)þ1 or Mþ(74Se37Cl)þ1, 14.23), 520 (Mþ(82Se37Cl),
13.81), 518 (Mþ(82Se35Cl) or Mþ(80Se37Cl), 15.06), 516 (Mþ(80Se35Cl)
or Mþ(78Se37Cl), 18.41), 514 (Mþ(76Se37Cl) or Mþ(78Se35Cl), 16.32);
10.7; 31P NMR (121.5 MHz, CDCl3)
d 23.6; MS (ESI) m/z (%) 468
(Mþ(82Se)þNaþ1, 4.17), 466 (Mþ(80Se)þNaþ1, 20.00), 464
(Mþ(78Se)þNaþ1, 7.08), 467 (Mþ(82Se)þNa, 20.00), 465
(Mþ(80Se)þNa, 100), 463 (Mþ(78Se)þNa or Mþ(77Se)þNaþ1, 50.83),
462 (Mþ(77Se)þNa or Mþ(76Se)þNaþ1, 18.75), 461 (Mþ(76Se)þNa,
18.33), 445 (Mþ(82Se)þ1, 10.00), 443 (Mþ(80Se)þ1, 41.67), 441
(Mþ(78Se)þ1, 25.42), 439 (Mþ(77Se) or Mþ(76Se)þ1, 6.67), 444
(Mþ(82Se), 14.58), 442 (Mþ(80Se), 4.58), 440 (Mþ(78Se) or
Mþ(77Se)þ1, 6.25); IR
n
(KBr, cmꢁ1) 3342, 3072, 3049, 1605, 1584,
IR n
(neat, cmꢁ1) 3055, 1567, 1476, 1437, 1196, 1118, 1104. Anal. Calcd
for C27H30ClOPSe: C, 62.86; H, 5.86. Found: C, 62.88; H, 5.77.
1568, 1435, 1302, 1274, 1173, 1117, 1098. Anal. Calcd for
C23H23O2PSe: C, 62.59; H, 5.25. Found: C, 62.61; H, 5.26. Compound
Z-3n: liquid. 1H NMR (300 MHz, CDCl3)
d
7.94–7.83 (m, 2H), 7.83–
4.3.16. 3-Hydroxy-4-phenyl-2-phenylselanyl-1(E)-butenyl diphenyl
phosphine oxide (E-2p) and 3-chloro-4-phenyl-2-phenylselanyl-
1(Z)-butenyl diphenyl phosphine oxide (Z-3p)
7.72 (m, 2H), 7.58–7.44 (m, 6H), 7.44–7.24 (m, 5H), 7.12 (d,
J¼21.0 Hz, 1H), 4.25 (dd, J1¼8.0 Hz, J2¼3.5 Hz, 1H), 2.14–2.01 (m,
1H), 1.90–1.73 (m, 1H), 0.87 (t, J¼7.4 Hz, 3H); 13C NMR (75 MHz,
The reaction of 1p (200.2 mg, 0.60 mmol) and PhSeCl (172.2 mg,
0.90 mmol) in 0.6 mL of H2O and 12 mL of CH3CN for 15 min
afforded E-2p (196.4 mg, 64%) and Z-3p (less polar, 43.5 mg,14%). E-
2p/Z-3p¼82:18. Compound E-2p: solid. Mp 177–178 ꢀC (ethyl ac-
CDCl3)
d
157.9, 135.9, 134.0 (d, Jpc¼105.9 Hz), 133.2 (d,
Jpc¼106.0 Hz), 131.7 (d, Jpc¼2.8 Hz), 131.6 (d, Jpc¼2.7 Hz), 131.4 (d,
Jpc¼9.5 Hz), 130.9 (d, Jpc¼9.5 Hz), 129.5, 129.1, 128.6 (d, Jpc¼11.6 Hz),
128.5 (d, Jpc¼12.2 Hz), 127.1, 123.1 (d, Jpc¼105.2 Hz), 65.4 (d,
etate). 1H NMR (300 MHz, CDCl3)
d 7.65–7.36 (m,15H), 7.35–7.17 (m,
Jpc¼14.0 Hz), 31.7, 10.5; 31P NMR (121.5 MHz, CDCl3)
d
21.6; MS (ESI)
5H), 5.71 (d, J¼19.8 Hz, 1H), 5.52 (d, J¼8.1 Hz, 1H), 5.15–5.04 (m,
m/z (%) 465 (Mþ(82Se37Cl)þ1, 6.03), 464 (Mþ(82Se37Cl), 11.21), 463
(Mþ(82Se35Cl)þ1 or Mþ(80Se37Cl)þ1, 44.83), 462 (Mþ(82Se35Cl) or
Mþ(80Se37Cl), 25.86), 461 (Mþ(80Se35Cl)þ1 or Mþ(78Se37Cl)þ1, 100),
459 (Mþ(77Se37Cl) or Mþ(78Se35Cl)þ1 or Mþ(76Se37Cl)þ1, 50.86),
458 (Mþ(76Se37Cl) or Mþ(78Se35Cl) or Mþ(77Se35Cl)þ1, 16.81), 457
1H), 3.31–3.14 (m, 2H); 31P NMR (121.5 MHz, CDCl3)
d 23.3; MS (ESI)
m/z (%) 507 (Mþ(82Se)þ1, 23.03), 505 (Mþ(80Se)þ1 or Mþ(82Se)ꢁ1,
100), 503 (Mþ(78Se)þ1 or Mþ(80Se)ꢁ1, 50.91), 506 (Mþ(82Se),
28.48), 504 (Mþ(80Se), 15.15), 502 (Mþ(78Se) or Mþ(77Se)þ1, 20.00),
501 (Mþ(77Se) or Mþ(76Se)þ1 or Mþ(78Se)ꢁ1, 16.36); IR
n (KBr,
(Mþ(77Se35Cl) or Mþ(76Se35Cl)þ1 or Mþ(74Se37Cl)þ1, 15.95); IR
n
(neat,
cmꢁ1) 3209, 1564, 1496, 1437, 1306, 1177, 1119. Anal. Calcd for
C28H25O2PSe: C, 66.80; H, 5.01. Found: C, 66.86; H, 5.01. Compound
cmꢁ1) 3055, 1567, 1476, 1458, 1437, 1381, 1306, 1194, 1118. HRMS calcd
for C23H22ClNaOPSeþ (MþNa)þ: 483.0162. Found: 483.0139.
Z-3p: liquid. 1H NMR (300 MHz, CDCl3)
d 7.89–7.79 (m, 2H), 7.75–
7.64 (m, 2H), 7.58–7.41 (m, 8H), 7.41–7.35 (m, 1H), 7.35–7.27 (m,
2H), 7.22–7.15 (m, 3H), 7.07 (d, J¼20.7 Hz, 1H), 6.90–6.82 (m, 2H),
4.56 (dd, J1¼8.7 Hz, J2¼3.9 Hz, 1H), 3.41 (dd, J1¼14.7 Hz, J2¼3.9 Hz,
1H), 2.92 (dd, J1¼14.4 Hz, J2¼8.7 Hz, 1H); 13C NMR (75 MHz, CDCl3)
4.3.15. 3-Hydroxy-2-phenylselanyl-1(E)-nonenyl diphenyl
phosphine oxide (E-2o) and 3-chloro-2-phenylselanyl-1(Z)-nonenyl
diphenyl phosphine oxide (Z-3o)
The reaction of 1o (649.3 mg, 2.0 mmol) and PhSeCl (575.4 mg,
3.0 mmol) in 1.5 mL of H2O and 30 mL of CH3CN for 30 min afforded
E-2o (642.2 mg, 64%) and Z-3o (less polar, 61.2 mg, 6%). E-2o/Z-
3o¼91:9. Compound E-2o: solid. Mp 104–105 ꢀC (hexane/ethyl
d
156.9 (d, Jpc¼1.3 Hz), 136.4, 136.2, 133.7 (d, Jpc¼106.1 Hz), 133.0 (d,
Jpc¼105.2 Hz), 131.8 (d, Jpc¼2.7 Hz), 131.7 (d, Jpc¼2.8 Hz), 131.3,
131.2, 130.9 (d, Jpc¼9.6 Hz), 129.7, 129.3, 129.2, 128.6 (d,
Jpc¼11.8 Hz), 128.5 (d, Jpc¼12.4 Hz), 128.2, 126.9 (d, Jpc¼2.3 Hz),
123.4 (d, Jpc¼104.9 Hz), 64.0 (d, Jpc¼14.0 Hz), 44.2 (d, Jpc¼1.3 Hz);
acetate). 1H NMR (400 MHz, CDCl3)
d 7.62–7.43 (m, 8H), 7.42–7.31
(m, 7H), 5.75 (br s, 1H), 5.64 (d, J¼20.0 Hz, 1H), 4.70–4.58 (m, 1H),
31P NMR (121.5 MHz, CDCl3)
d 21.9; MS (ESI) m/z (%) 539
1.95–1.75 (m, 2H), 1.60–1.48 (m, 1H), 1.41–1.17 (m, 7H), 0.85 (t,
(Mþ(77Se37Cl)þNH4þ or Mþ(78Se35Cl)þNH4þ or Mþ(76Se37Cl)þNH4þ,10.88),
527 (Mþ(82Se37Cl)þ1, 8.37), 525 (Mþ(82Se35Cl)þ1 or Mþ(80Se37Cl)þ1,
34.31), 523 (Mþ(80Se35Cl)þ1 or Mþ(78Se37Cl)þ1, 100), 521 (Mþ(77Se37Cl)
or Mþ(78Se35Cl)þ1 or Mþ(76Se37Cl)þ1, 31.80), 519 (Mþ(77Se35Cl) or
Mþ(76Se35Cl)þ1 or Mþ(74Se37Cl)þ1, 11.30), 526 (Mþ(82Se37Cl), 6.69),
524 (Mþ(82Se35Cl) or Mþ(80Se37Cl), 22.18), 522 (Mþ(80Se35Cl) or
J¼7.0 Hz, 3H); 13C NMR (100 MHz, CDCl3)
d 169.3, 136.7, 133.6 (d,
Jpc¼105.1 Hz), 133.3 (d, Jpc¼107.6 Hz), 131.6, 130.8 (d, Jpc¼10.0 Hz),
130.7 (d, Jpc¼9.1 Hz), 129.8, 129.3, 128.5 (d, Jpc¼12.3 Hz), 127.7, 113.4
(d, Jpc¼97.0 Hz), 74.3 (d, Jpc¼6.2 Hz), 37.4, 31.7, 28.9, 26.1, 22.5, 14.0;
31P NMR (121.5 MHz, CDCl3)
d 23.3; MS (ESI) m/z (%) 501
(Mþ(82Se)þ1, 13.45), 499 (Mþ(80Se)þ1 or Mþ(82Se)-1, 68.13), 497
(Mþ(78Se)þ1 or Mþ(80Se)-1, 31.87), 500 (Mþ(82Se), 26.32), 498
(Mþ(80Se), 10.23), 496 (Mþ(78Se) or Mþ(77Se)þ1, 10.06), 495
(Mþ(77Se) or Mþ(76Se)þ1 or Mþ(78Se)-1, 8.48), 484
(Mþ(82Se)þ1ꢁOH, 15.20), 482 (Mþ(80Se)þ1ꢁOH or Mþ(82Se)ꢁH2O,
65.79), 480 (Mþ(78Se)þ1ꢁOH or Mþ(80Se)ꢁH2O, 32.16), 483
Mþ(78Se37Cl), 16.74), 520 (Mþ(76Se37Cl) or Mþ(78Se35Cl), 8.37); IR
n
(neat, cmꢁ1) 3056, 1565, 1495, 1476, 1437, 1307, 1195, 1118. HRMS
calcd for C28H25ClOPSeþ (MþþH): 523.0480. Found: 523.0491.
4.3.17. Synthesis of 3-chloro-2-phenylselanyl-1(E)-nonenyl
diphenyl phosphine oxide (E-3o)
(Mþ(82Se)ꢁOH,
53.22),
481
(Mþ(80Se)ꢁOH, 100),
479
(Mþ(78Se)ꢁOH or Mþ(77Se)þ1ꢁOH, 70.76), 478 (Mþ(77Se)ꢁOH or
4.3.17.1. 3-Tosyloxy-2-phenylselanyl-1(E)-nonenyl diphenyl phos-
Mþ(76Se)þ1ꢁOH or Mþ(78Se)ꢁH2O, 27.19), 477 (Mþ(76Se)ꢁOH or
phine oxide (E-4o).23 To a solution of E-2o (152.7 mg, 0.31 mmol),

4886
G. He et al. / Tetrahedron 65 (2009) 4877–4889
p-TsCl (235.0 mg, 1.24 mmol) in 1.0 mL of anhydrous CH2Cl2 was
added dropwise 4-dimethylaminopyridine (225.5 mg, 1.86 mmol)
in 1.0 mL of anhydrous CH2Cl2 under the atmosphere of N2. Then
the resulting mixture was refluxed at 50 ꢀC for 2.5 h. After evapo-
ration, purification by flash chromatography on silica gel (petro-
leum ether/ethyl acetate¼3:1 to 2:1) afforded E-4o (172.2 mg, 86%)
as a solid. Mp 130–131 ꢀC (n-hexane/ethyl acetate). 1H NMR
6.45), 519 (Mþ(82Se35Cl)þ1 or Mþ(80Se37Cl)þ1, 41.58), 517
(Mþ(80Se35Cl)þ1 or Mþ(78Se37Cl)þ1, 78.85), 515 (Mþ(77Se37Cl) or
Mþ(78Se35Cl)þ1 or Mþ(76Se37Cl)þ1, 32.26), 513 (Mþ(77Se35Cl) or
Mþ(76Se35Cl)þ1 or Mþ(74Se37Cl)þ1,11.47), 520 (Mþ(82Se37Cl),10.75),
518 (Mþ(82Se35Cl) or Mþ(80Se37Cl), 22.94), 516 (Mþ(80Se35Cl)
or Mþ(78Se37Cl), 13.62), 514 (Mþ(76Se37Cl) or Mþ(78Se35Cl),
14.70), 506 (Mþ(82Se)þNaꢁCl, 2.15), 504 (Mþ(80Se)þNaꢁCl, 10.39),
(300 MHz, CDCl3)
d
7.82 (d, J¼8.4 Hz, 2H), 7.58–7.29 (m, 15H), 7.17
502
(Mþ(78Se)þNaꢁCl,
6.45),
505
(Mþ(82Se)þNaꢁHCl,
(d, J¼8.1 Hz, 2H), 6.66 (dd, J1¼8.4 Hz, J2¼4.2 Hz, 1H), 5.47 (d,
J¼19.8 Hz, 1H), 2.37 (s, 3H), 2.01–1.86 (m, 1H), 1.80–1.66 (m, 1H),
1.31–0.93 (m, 8H), 0.81 (t, J¼6.9 Hz, 3H); 13C NMR (75 MHz, CDCl3)
7.89), 503 (Mþ(80Se)þNaꢁHCl, 42.29), 501 (Mþ(78Se)þNaꢁHCl or
Mþ(77Se)þNaꢁCl,
20.07),
500
(Mþ(77Se)þNaꢁHCl
or Mþ(76Se)þNaꢁCl, 6.45), 499 (Mþ(76Se)þNaꢁHCl, 8.24), 484
(Mþ(82Se)þ1ꢁCl, 3.58), 482 (Mþ(80Se)þ1ꢁCl, 21.51), 480
d
162.7, 144.4, 137.1, 133.7 (d, Jpc¼104.1 Hz), 133.6 (d, Jpc¼105.4 Hz),
133.1, 131.6 (d, Jpc¼2.7 Hz), 131.5 (d, Jpc¼2.8 Hz), 130.9 (d,
Jpc¼9.5 Hz), 130.5 (d, Jpc¼9.6 Hz), 129.8, 129.45, 129.41, 128.49,
128.47 (d, Jpc¼14.9 Hz), 128.43 (d, Jpc¼14.3 Hz), 126.9, 115.8 (d,
Jpc¼93.9 Hz), 80.6 (d, Jpc¼6.3 Hz), 36.3, 31.5, 28.5, 24.8, 22.3, 21.6,
(Mþ(78Se)þ1ꢁCl,
14.70),
483
(Mþ(82Se)ꢁCl,
19.00),
481 (Mþ(80Se)ꢁCl, 100), 479 (Mþ(78Se)ꢁCl or Mþ(77Se)þ1ꢁCl,
50.18), 478 (Mþ(77Se)ꢁCl or Mþ(76Se)þ1ꢁCl, 19.00), 477
(Mþ(76Se)ꢁCl, 14.70); IR
n
(neat, cmꢁ1) 3057, 1585, 1574, 1466, 1437,
14.0; 31P NMR (121.5 MHz, CDCl3)
d
20.8; MS (ESI) m/z (%) 694
1274, 1195, 1117. Anal. Calcd for C27H30ClOPSe: C, 62.86; H, 5.86.
Found: C, 62.85; H, 5.89.
(Mþ(82Se)þKþ1, 7.55), 692 (Mþ(80Se)þKþ1, 16.55), 690
(Mþ(78Se)þKþ1, 9.71), 693 (Mþ(82Se)þK, 22.66), 691 (Mþ(80Se)þK,
51.08), 689 (Mþ(78Se)þK or Mþ(77Se)þKþ1, 32.37), 688
(Mþ(77Se)þK or Mþ(76Se)þKþ1, 9.35), 687 (Mþ(76Se)þK, 8.63), 678
(Mþ(82Se)þNaþ1, 10.07), 676 (Mþ(80Se)þNaþ1, 34.17), 674
(Mþ(78Se)þNaþ1, 19.78), 677 (Mþ(82Se)þNa, 28.78), 675
(Mþ(80Se)þNa, 100), 673 (Mþ(78Se)þNa or Mþ(77Se)þNaþ1, 50.36),
672 (Mþ(77Se)þNa or Mþ(76Se)þNaþ1, 24.10), 671 (Mþ(76Se)þNa,
17.63), 655 (Mþ(82Se)þ1, 25.90), 653 (Mþ(80Se)þ1, 87.77), 651
(Mþ(78Se)þ1, 41.01), 650 (Mþ(78Se) or Mþ(77Se)þ1, 20.86), 649
(Mþ(77Se) or Mþ(76Se)þ1, 8.63), 654 (Mþ(82Se), 26.62), 652
4.3.18. Synthesis of 18O-labeled 3-hydroxy-1-phenyl-2-
phenylselanyl-1(E)-propenyl diphenyl phosphine oxide (E-2h )
*
The starting material 1h was dried in vacuo over P2O5 for one
day. MeCN was firstly heated with CaH2 under reflux in an argon
atmosphere for 24 h. Then the distilled MeCN was treated with
P2O5 under reflux in an argon atmosphere for another 24 h. After
distillation, the generated anhydrous MeCN was stored in a bottle
with molecular sieves and placed in the glove box under nitrogen
atmosphere. H128O (96%) was bought from J&K Chemical LTD. All the
operation was carried out in the glove box under nitrogen
atmosphere.
A solution of PhSeCl (87.1 mg, 0.45 mmol) in anhydrous CH3CN
(2.0 mL) and H128O (0.1 mL) was stirred at rt for 262 min. Then
a solution of 1h (95.1 mg, 0.30 mmol) in anhydrous CH3CN (2.0 mL)
and H128O (0.2 mL), which had been stirred at rt for 259 min, was
added subsequently. Anhydrous CH3CN (1.0 mLꢂ2) was used to
wash the container for 1h and transferred into the reaction mix-
ture. After being stirred at rt for 10 min, the reaction mixture was
directly purified with flash chromatography on silica gel (eluent:
(Mþ(80Se),15.11); IR (KBr, cmꢁ1) 3060, 1595, 1572,1440, 1361, 1311,
n
1283, 1190, 1175, 1118. Anal. Calcd for C34H37O4PSSe: C, 62.67; H,
5.72. Found: C, 62.74; H, 5.75.
4.3.17.2. 3-Chloro-2-phenylselanyl-1(E)-nonenyl diphenyl phosphine
oxide (E-3o).24 To a solution of tosylate E-4o (80.4 mg, 0.15 mmol) in
1.5 mL of anhydrous DMF was added anhydrous LiCl (53.7 mg,
1.20 mmol) at the atmosphere of N2. Then the resulting mixture was
stirredat50 ꢀCfor29 handquenchedwith5 mLofwater. Theaqueous
layerwasextractedwith20ꢂ3 mLof Et2O. The combined organic layer
was washed with 5 mL of H2O, 5 mL of 5% diluted aqueous HCl and
5 mL of saturated brine, and dried over anhydrous Na2SO4. After fil-
tration and evaporation of the solvent, chromatography on silica gel
(eluent: petroleum ether/ethyl acetate¼3:1) of the crude product
afforded E-3o (38.1 mg, 60%) as a liquid. 1H NMR (300 MHz, CDCl3)
petroleum ether/ethyl acetate¼2:1) to afford 124.8 mg (84%) of E-
18
2h
*
(94.5% of O incorporation) as a solid. Mp 142.5–143.3 ꢀC (n-
hexane/ethyl acetate). 1H NMR (300 MHz, CDCl3)
d 7.68–7.52 (m,
6H), 7.51–7.42 (m, 2H), 7.41–7.29 (m, 7H), 7.18–7.06 (m, 3H), 6.87–
6.81 (m, 2H), 5.97 (t, J¼7.6 Hz, 1H), 4.39 (dd, J1¼7.6 Hz, J2¼0.9 Hz,
d
7.65–7.56 (m, 2H), 7.56–7.31 (m, 13H), 6.24–6.15 (m, 1H), 5.70 (d,
2H); 31P NMR (121.5 MHz, CDCl3)
d 30.6; MS (ESI) m/z (%) 518
J¼19.8 Hz,1H), 2.10–1.94 (m, 2H),1.57–1.41 (m,1H),1.37–1.12 (m, 7H),
(Mþ(82Se)þNaþ1, 5.02), 516 (Mþ(80Se)þNaþ1, 10.60), 514
(Mþ(78Se)þNaþ1, 7.10), 512 (Mþ(77Se)þNa or Mþ(76Se)þNaþ1,
8.27), 517 (Mþ(82Se)þNa, 9.52), 515 (Mþ(80Se)þNa, 36.16), 513
(Mþ(78Se)þNa or Mþ(77Se)þNaþ1, 20.01), 511 (Mþ(76Se)þNa,
8.07), 495 (Mþ(82Se)þ1, 22.58), 493 (Mþ(80Se)þ1, 100), 491
(Mþ(78Se)þ1, 56.66), 489 (Mþ(77Se) or Mþ(76Se)þ1, 20.64), 494
(Mþ(82Se), 28.07), 492 (Mþ(80Se), 18.08), 490 (Mþ(78Se) or
0.86 (t, J¼6.9 Hz, 3H); 13C NMR(75 MHz, CDCl3)
d 164.5, 137.0, 133.6 (d,
Jpc¼105.2 Hz), 133.5 (d, Jpc¼105.5 Hz), 131.7 (d, Jpc¼2.7 Hz), 131.6 (d,
Jpc¼2.8 Hz), 130.7 (d, Jpc¼12.4 Hz), 130.6 (d, Jpc¼11.6 Hz), 129.9, 129.4,
128.55 (d, Jpc¼12.4 Hz), 128.46 (d, Jpc¼12.0 Hz), 127.5, 118.5 (d,
Jpc¼93.2 Hz), 60.5 (d, Jpc¼6.9 Hz), 39.0, 31.5, 28.6, 26.5, 22.4, 14.1; 31
P
NMR (121.5 MHz, CDCl3)
d
20.4; MS(ESI) m/z(%) 559 (Mþ(82Se37Cl)þK,
4.66), 557 (Mþ(82Se35Cl)þK or Mþ(80Se37Cl)þK, 21.51), 555
(Mþ(80Se35Cl)þK or Mþ(78Se37Cl)þK, 46.59), 553 (Mþ(76Se37Cl)þK or
Mþ(78Se35Cl)þK, 19.35), 551 (Mþ(76Se35Cl)þK or Mþ(74Se37Cl)þK,
6.09), 558 (Mþ(82Se35Cl)þKþ1 or Mþ(80Se37Cl)þKþ1, 5.73), 556
Mþ(77Se)þ1, 21.55); IR
n
(KBr, cmꢁ1) 3431, 3055, 3022, 2926, 1577,
1560, 1474, 1439, 1388, 1311, 1252, 1138, 1116, 1088, 1064, 1021.
HRMS calcd for C27H24O18OPSeþ (Mþþ1): 493.07161. Found:
493.07115.
(Mþ(80Se35Cl)þKþ1
or
Mþ(78Se37Cl)þKþ1,
13.26),
554
According to the MS spectrum of this product (page S113, in
Supplementary data), the relative abundances of 489.05, 490.06,
491.04, 492.06, 493.02, 494.04, 495.02 are 20.64, 21.55, 56.66,
18.08, 100, 28.07, 22.58; according to the simulated MS spectrum
(Mþ(77Se37Cl)þK or Mþ(78Se35Cl)þKþ1 or Mþ(76Se37Cl)þKþ1, 8.60),
552 (Mþ(77Se35Cl)þK or Mþ(76Se35Cl)þKþ1 or Mþ(74Se37Cl)þKþ1,
7.53), 543 (Mþ(82Se37Cl)þNa, 3.58), 541 (Mþ(82Se35Cl)þNa or
Mþ(80Se37Cl)þNa, 20.43), 539 (Mþ(80Se35Cl)þNa or Mþ(78Se37Cl)þNa,
41.94), 537 (Mþ(76Se37Cl)þNa or Mþ(78Se35Cl)þNa, 22.58), 535
(Mþ(76Se35Cl)þNa or Mþ(74Se37Cl)þNa, 7.17), 542 (Mþ(82Se35Cl)þ
Naþ1 or Mþ(80Se37Cl)þNaþ1, 5.38), 540 (Mþ(80Se35Cl)þNaþ1 or
Mþ(78Se37Cl)þNaþ1, 11.47), 538 (Mþ(77Se37Cl)þNa or Mþ(78Se35Cl)þ
Naþ1 or Mþ(76Se37Cl)þNaþ1, 7.89), 536 (Mþ(77Se35Cl)þNa or
Mþ(76Se35Cl)þNaþ1 or Mþ(74Se37Cl)þNaþ1, 7.89), 521 (Mþ(82Se37Cl)þ1,
of E-2h
with 100% of 18O (page S112, in Supplementary data),
*
their relative abundances should be 18.561, 20.515, 52.147,
14.585, 100, 29.099, 21.547; according to the simulated MS
spectrum of E-2h (page S111, in Supplementary data) their rel-
ative abundances should be 52.134, 14.631, 100, 29.134, 21.739,
5.580, 0.837. If x and y represent the amount of E-2h and E-2h,
*
respectively, then

G. He et al. / Tetrahedron 65 (2009) 4877–4889
4887
0:2064 ¼ 0:18561x þ 0:52134y
0:2155 ¼ 0:20515x þ 0:14631y
0:5666 ¼ 0:52147x þ 1:00000y
0:1808 ¼ 0:14585x þ 0:29134y
1:0000 ¼ 1:00000x þ 0:21739y
0:6309 ¼ 0:52147x þ 1:00000y
0:1978 ¼ 0:14585x þ 0:29134y
1:0000 ¼ 1:00000x þ 0:21739y
0:2885 ¼ 0:29099x þ 0:05580y
0:2314 ¼ 0:21547x þ 0:00837y
Similarly, by using MATLAB 5.3 (by the MathWorks), we know
that x¼0.9759, y¼0.1282. Thus incorporation of 18O % in the
product¼x/(xþy)¼0.884.
0:2807 ¼ 0:29099x þ 0:05580y
0:2258 ¼ 0:21547x þ 0:00837y
4.3.20. Synthesis of 18O-labeled 3-hydroxy-2-phenylselanyl-3-
which can be written as
propyl-1(E)-hexenyl diphenyl phosphine oxide (E-2e )
*
2
3
2
3
7
0:2064
0:2155
0:5666
0:1808
1:0000
0:2807
0:2258
0:18561 0:52134
0:20515 0:14631
0:52147 1:00000
0:14585 0:29134
1:00000 0:21739
0:29099 0:05580
0:21547 0:00837
The reaction of 1e (97.2 mg, 0.30 mmol) and PhSeCl (85.9 mg,
6
7
6
0.45 mmol) in 0.3 mL of H128O and 6 mL of anhydrous CH3CN for
6
6
6
6
6
6
7
7
7
7
7
7
6
6
6
6
6
6
7
7ꢀ
7
ꢁ
41 min afforded 127.7 mg (85%) of E-2e
*
(69.5% of 18O in-
x
y
7
corporation) as a liquid. 1H NMR (300 MHz, CDCl3)
d
7.52–7.42 (m,
¼
7
7
6
4
7
5
6
4
7
5
2H), 7.42–7.20 (m, 13H), 5.75 (br, 1H), 5.62 (d, J¼18.3 Hz, 1H), 1.85–
1.58 (m, 4H), 1.47–1.23 (m, 4H), 0.83 (t, J¼7.2 Hz, 6H); 13C NMR
(75 MHz, CDCl3)
d
172.2 (d, Jpc¼1.4 Hz), 137.2, 134.0 (d,
Jpc¼107.4 Hz), 131.2 (d, Jpc¼2.9 Hz), 130.7 (d, Jpc¼9.7 Hz), 129.9,
By using MATLAB 5.3 (by the MathWorks), we know that
x¼0.9873, y¼0.0573. Thus, the incorporation of 18O % in the
product¼x/(xþy)¼0.945.
129.3, 128.6, 128.2 (d, Jpc¼11.9 Hz), 115.7 (d, Jpc¼98.0 Hz), 80.7 (d,
Jpc¼5.5 Hz), 44.4, 16.7, 14.4; 31P NMR (121.5 MHz, CDCl3)
d 24.9; MS
(ESI) m/z (%) 503 (Mþ(82Se)þ1, 19.12), 501 (Mþ(80Se)þ1, 100), 499
(Mþ(78Se)þ1, 86.67), 497 (Mþ(77Se) or Mþ(76Se)þ1, 37.28), 495
(Mþ(74Se)þ1, 9.41), 502 (Mþ(82Se), 28.34), 500 (Mþ(80Se), 27.52),
498 (Mþ(78Se) or Mþ(77Se)þ1, 25.25), 496 (Mþ(76Se), 8.78), 483
The following compounds were prepared according to this
procedure.
4.3.19. Synthesis of 18O-labeled 3-hydroxy-3-phenyl-2-
phenylselanyl-1(E)-propenyl diphenyl phosphine oxide (E-2c )
(Mþ(82Se)ꢁOH, 8.88),
481 (Mþ(80Se)ꢁOH, 13.03), 479
*
(Mþ(78Se)ꢁOH or Mþ(77Se)þ1ꢁOH, 5.58), 482 (Mþ(80Se)þ1ꢁOH,
The reaction of 1c (94.8 mg, 0.30 mmol) and PhSeCl (87.2 mg,
n
(neat, cmꢁ1) 3336, 1580, 1556, 1462, 1437, 1376, 1337,
0.45 mmol) in 0.3 mL of H128O and 6 mL of anhydrous CH3CN for 37 min
3.65); IR
afforded 126.0 mg (85%) of E-2c
(88.4% of 18O incorporation) as a solid.
*
1306, 1274, 1154, 1140, 1115, 1088, 1067, 1021. HRMS calcd for
C27H32O18OPSeþ (Mþþ1): 501.13421. Found: 501.13349.
Mp 163.2–163.6 ꢀC (ethyl acetate). 1H NMR (300 MHz, CDCl3)
d 7.51–
7.09 (m, 20H), 6.00 (s, 1H), 5.79 (br, 1H), 5.68 (d, J¼20.1 Hz, 1H); 13C
According to the MS spectrum of this product (page S125, in
Supplementary data), the relative abundances of 495.04, 496.06,
497.02, 498.04, 498.99, 500.03, 500.98, 502.00, 502.98 are 9.41,
8.78, 37.28, 25.25, 86.67, 27.52, 100, 28.34, 19.12; according to the
NMR (75 MHz, CDCl3)
d
168.3, 140.7, 136.7, 133.0 (d, Jpc¼105.4 Hz), 132.9
(d, Jpc¼107.9 Hz), 131.8 (d, Jpc¼2.5 Hz), 131.6 (d, Jpc¼2.9 Hz), 130.8 (d,
Jpc¼14.9 Hz), 130.7 (d, Jpc¼15.6 Hz), 129.8, 129.3, 128.5 (d, Jpc¼11.8 Hz),
128.4 (d, Jpc¼12.2 Hz), 128.1, 128.0, 127.8, 127.0, 115.3 (d, Jpc¼94.3 Hz),
simulated MS spectrum of E-2e
with 100% of 18O (page S124, in
*
74.7; 31P NMR (121.5 MHz, CDCl3)
d 23.9; MS (ESI) m/z (%) 515
Supplementary data), their relative abundances should be 1.755,
0.520, 18.559, 20.529, 52.158, 14.631, 100.00, 29.187, 21.571;
according to the simulated MS spectrum of E-2e (page S123, in
Supplementary data) their relative abundances should be 18.542,
20.514, 52.146,14.677, 100.00, 29.222, 21.763, 5.999, 0.842. If x and y
(Mþ(80Se)þNa, 20.60), 513 (Mþ(78Se)þNa or Mþ(77Se)þNaþ1, 14.05),
511 (Mþ(76Se)þNa,11.07), 512 (Mþ(77Se)þNa or Mþ(76Se)þNaþ1, 8.61),
495 (Mþ(82Se)þ1, 23.14), 493 (Mþ(80Se)þ1, 100), 491 (Mþ(78Se)þ1,
63.09), 489 (Mþ(77Se) or Mþ(76Se)þ1, 25.10), 494 (Mþ(82Se), 28.85),
492 (Mþ(80Se), 19.78), 490 (Mþ(78Se) or Mþ(77Se)þ1, 22.01), 476
(Mþ(80Se)þ1ꢁOH, 6.07), 475 (Mþ(80Se)ꢁOH, 20.55), 473
represent the amount of E-2e and E-2e, respectively, then
*
(Mþ(78Se)ꢁOH or Mþ(77Se)þ1ꢁOH,14.54); IR
n
(KBr, cmꢁ1) 3274,1592,
0:0941 ¼ 0:01755x þ 0:18542y
0:0878 ¼ 0:00520x þ 0:20514y
0:3728 ¼ 0:18559x þ 0:52146y
0:2525 ¼ 0:20529x þ 0:14677y
0:8667 ¼ 0:52158x þ 1:00000y
0:2752 ¼ 0:14631x þ 0:29222y
1:0000 ¼ 1:00000x þ 0:21763y
0:2834 ¼ 0:29187x þ 0:05999y
1571,1474,1439,1332,1274,1157,1147,1117,1093,1047. HRMS calcd for
C27H24O18OPSeþ (Mþþ1): 493.07161. Found: 493.07085.
According to the MS spectrum of this product (page S119, in
Supplementary data), the relative abundances of 488.96, 489.98,
490.93, 491.98, 492.91, 493.94, 494.93 are 25.10, 22.01, 63.09,
19.78, 100, 28.85, 23.14; according to the simulated MS spectrum
of E-2c
with 100% of 18O (page S118, in Supplementary data), their
*
relative abundances should be 18.561, 20.515, 52.147, 14.585, 100,
29.099, 21.547; according to the simulated MS spectrum of E-2c
(page S117, in Supplementary data) their relative abundances
should be 52.134, 14.631, 100, 29.134, 21.739, 5.580, 0.837. If x and
y represent the amount of E-2c and E-2c, respectively, then
*
0:2510 ¼ 0:18561x þ 0:52134y
0:2201 ¼ 0:20515x þ 0:14631y
0:1912 ¼ 0:21571x þ 0:00842y

4888
G. He et al. / Tetrahedron 65 (2009) 4877–4889
Similarly, by using MATLAB 5.3 (by the MathWorks), we know
4.5.2. S-3-Hydroxy-1-phenyl-2-phenylselanyl-1(E)-pentenyl
diphenyl phosphine oxide (S-2j)
The reaction of S-(þ)-1j (103.8 mg, 0.30 mmol, 99% ee) and
PhSeCl (88.5 mg, 0.45 mmol) of in 0.3 mL of H2O and 6 mL of CH3CN
for 8 min afforded S-(þ)-2j (146.8 mg, 94%, 99% ee) as a liquid. 1H
that x¼0.9100, y¼0.3994. Thus incorporation of 18O %¼x/
(xþy)¼0.695.
4.4. Reaction of mono-substituted 1,2-allenyl phosphine
oxides with PhSeCl
NMR (300 MHz, CDCl3)
d
7.75 (dd, J1¼12.3 Hz, J2¼7.2 Hz, 2H), 7.54
(dd, J1¼17.1 Hz, J2¼6.9 Hz, 3H), 7.48–7.22 (m, 10H), 7.16–7.07 (m,
2H), 7.00–6.90 (m, 1H), 6.89–6.80 (m, 1H), 6.75 (d, J¼11.4 Hz, 1H),
6.52 (d, J¼6.9 Hz, 1H), 4.24 (t, J¼9.8 Hz, 1H), 2.22–2.05 (m, 1H),
1.98–1.83 (m, 1H), 0.80 (t, J¼7.2 Hz, 3H); HPLC conditions: Chiralcel
4.4.1. 3-Hydroxy-4-methyl-2-phenylselanyl-1(E)-pentenyl diphenyl
phosphine oxide (E-2l)
Typical procedure IV. To a solution of PhSeCl (55.6 mg, 0.2 mmol)
in 2 mL of MeCN and 1.5 mL of H2O was added a solution of 1l
(57.3 mg, 0.3 mmol) in 1 mL of MeCN at room temperature. Then
the resulting mixture was stirred at 70 ꢀC for 34 min. After com-
plete consumption of the starting material as monitored by TLC
(eluent: dichloromethane/ethyl acetate¼10:1), the mixture was
quenched with 5 mL of H2O, extracted with 20ꢂ3 mL of diethyl
ether, washed with 5 mL of brine, and dried over anhydrous
Na2SO4. Filtration and evaporation afforded the crude product,
which was analyzed by 1H NMR study to show an E-2l/Z-3l ratio of
97:3. Flash chromatography on silica gel (dichloromethane/ethyl
acetate¼10:1, then 5:1) afforded E-2l (73.8 mg, 82%) (E-2l/Z-
3l¼97:3).
AD-H, hexane/i-PrOH¼90:10, 0.7 mL/min, n¼230 nm, tR¼25.7;
20
[a
]
þ103.1 (c 0.96, CHCl3).
D
4.5.3. R-3-Hydroxy-2-phenylselanyl-1(E)-nonenyl diphenyl
phosphine oxide (R-2o)
The reaction of R-(ꢁ)-1o (97.6 mg, 0.30 mmol, 97% ee) and
PhSeCl (86.9 mg, 0.45 mmol) in 1.5 mL of H2O and 3 mL of CH3CN at
70 ꢀC for 30 min afforded R-(ꢁ)-2o (118.2 mg, 79%, 97% ee) as
a liquid. 1H NMR (300 MHz, CDCl3)
d 7.64–7.31 (m, 15H), 5.78–5.57
(m, 2H), 4.70–4.58 (m, 1H), 1.97–1.73 (m, 2H), 1.66–1.45 (m, 1H),
1.44–1.13 (m, 7H), 0.86 (t, J¼6.2 Hz, 3H); HPLC conditions: Chiralcel
OD-H, hexane/i-PrOH¼95:5, 0.7 mL/min, n¼230 nm, tR 11.7 (ma-
20
jor), 13.5 (minor); [
a
]
ꢁ25.15 (c 1.05, CHCl3).
D
4.4.2. 3-Hydroxy-2-phenylselanyl-1(E)-propenyl diphenyl
phosphine oxide (E-2m)
Acknowledgements
The reaction of 1m (72.5 mg, 0.30 mmol) and PhSeCl
(86.4 mg, 0.45 mmol) in 3.0 mL of H2O and 3.0 mL of CH3CN at
70 ꢀC for 9 h afforded E-2m (65.6 mg, 52.5%) and Z-3m (17.8 mg,
14%) (E-2m/Z-3m¼79:21 by 1H NMR analysis of the crude
product).
Financial support from the National Natural Science Foundation
of China (No. 20572093) and the Major State Basic Research De-
velopment Program (Grant No. 2009CB825300) is greatly appre-
ciated. S.M. is a Qiu Shi Adjunct Professor at Zhejiang University. We
thank Bo Lu¨ in our research group for reproducing the results
presented in entries 7 and 12 in Table 2, entry 4 in Table 4, and the
second equation in Scheme 2.
4.4.3. 3-Hydroxy-2-phenylselanyl-1(E)-pentenyl diphenyl
phosphine oxide (E-2n)
The reaction of 1n (81.1 mg, 0.30 mmol) and PhSeCl (86.8 mg,
0.45 mmol) in 1.5 mL of H2O and 3 mL of CH3CN at 70 ꢀC for 21 min
afforded E-2n (104.6 mg, 78%) as a solid (E-2n/Z-3n>99:1 by 1H
NMR analysis of the crude product).
Supplementary data
The 1H, 13C, 31P spectra for all the new compounds, the MS
spectra for E-2h
*
, E-2c
*
, and E-2e , the simulated MS spectra for E-
*
4.4.4. 3-Hydroxy-2-phenylselanyl-1(E)-nonenyl diphenyl
phosphine oxide (E-2o)
The reaction of 1o (96.8 mg, 0.30 mmol) and PhSeCl (85.5 mg,
0.45 mmol) in 1.5 mL of H2O and 3 mL of CH3CN at 70 ꢀC for 70 min
afforded E-2o (110.6 mg, 74%) (E-2o/Z-3o¼98:2 by 1H NMR analysis
of the crude product).
2h , E-2c , and E-2e
*
*
*
and the simulated MS spectra for E-2h, E-2c,
and E-2e are included in Supplementary data. This material is
available free of charge via the Internet. Supplementary data as-
sociated with this article can be found in the online version, at
doi:10.1016/j.tet.2009.04.023.
References and notes
4.4.5. 3-Hydroxy-4-phenyl-2-phenylselanyl-1(E)-butenyl diphenyl
phosphine oxide (E-2p)
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4.5. Reaction of optically active 1,2-allenyl phosphine oxides
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phosphine oxide (S-2b)
The reaction of S-(þ)-1b (76.2 mg, 0.30 mmol) and PhSeCl
(86.7 mg, 0.45 mmol) in 0.3 mL of H2O and 6 mL of CH3CN for
12 min afforded S-(þ)-2b (110.5 mg, 86%) as a solid. Mp 150–151 ꢀC
(n-hexane/ethyl acetate). 1H NMR (300 MHz, CDCl3)
d 7.62–7.28 (m,
6. Ma, S.; Hao, X.; Huang, X. Chem. Commun. 2003, 1082.
15H), 5.88 (d, J¼8.4 Hz, 1H), 5.62 (d, J¼20.1 Hz, 1H), 4.96–4.82 (m,
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1H), 1.58 (d, J¼6.6 Hz, 3H); HPLC conditions: Chiralcel AD-H, hex-
ane/i-PrOH¼80:20, 0.8 mL/min, n¼230 nm, tR 12.6 (major), 17.3
20
(minor); [
a
]
þ22.5 (c 1.01, CHCl3).
D

G. He et al. / Tetrahedron 65 (2009) 4877–4889
4889
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m(Mo K
a
)¼1.892 mmꢁ1, R¼0.051, Rw¼0.121, a¼14.
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s(I)), 2410;
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thorhombic, space group P2(1)2(1)2(1),
m(Mo
Ka
)¼1.870 mmꢁ1
R¼0.053,
,
Rw¼0.105, a¼10.978(10), b¼18.258(16), c¼21.023(18) Å, V¼4213.5(6) Å3,
T¼293 K, Z¼8; no. of reflections measured, total 8264; number of observations
(I>2.00s(I)), 3612; number of variables, 479. CCDC: 702218.
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