Highly selective synthesis of [(Z)-3-chloro-2-(phenylselanyl)-1-alkenyl] phosphonates and 2-ethoxy-4-(phenylselanyl)-2,5-dihydro-1,2-oxaphosphole 2-oxides by electrophilic reaction of 1,2-alkadienylphosphonates with PhSeCl

Article abstract of DOI:10.1002/ejoc.200900913

The reactions of monosubstituted 1,2-alkadienylphosphonates with PhSeCl in THF or dioxane/H₂O (10:1) at 70 °C afforded the selenochlorination products [(Z)-3-chloro-2-(phenylselanyl)-1-alkenyl] phosphonates with very high chemo-and stereoselect

Full text of DOI:10.1002/ejoc.200900913

FULL PAPER
DOI: 10.1002/ejoc.200900913
Highly Selective Synthesis of [(Z)-3-Chloro-2-(phenylselanyl)-1-
alkenyl]phosphonates and 2-Ethoxy-4-(phenylselanyl)-2,5-dihydro-1,2-
oxaphosphole 2-Oxides by Electrophilic Reaction of 1,2-
Alkadienylphosphonates with PhSeCl
Guangke He,[a] Yihua Yu,[b] Chunling Fu,*[a] and Shengming Ma*[a]
Keywords: Allenes / Phosphorus / Selenium / Electrophilic addition / Cyclization
The reactions of monosubstituted 1,2-alkadienylphosphon-
ates with PhSeCl in THF or dioxane/H2O (10:1) at 70 °C af-
forded the selenochlorination products [(Z)-3-chloro-2-
(phenylselanyl)-1-alkenyl]phosphonates with very high
chemo- and stereoselectivity, whereas the same reaction with
di- and trisubstituted allenylphosphonates afforded 2-
ethoxy-4-(phenylselanyl)-2,5-dihydro-1,2-oxaphosphole 2-
oxides exclusively. It was interesting to note that the stereo-
selctivity for the selenochlorination reaction is opposite to
that of the iodo- and selenohydroxylation reactions of (al-
lenyl)diphenylphosphane oxides with Cl– acting as the nu-
cleophile. The stereoselectivity of the cyclization reaction is
clearly different from that of the selenochlorination reaction.
stead of the usual hydroxy group, which opens up new op-
portunities for the introduction of other nucleophiles with
different stereoselectivity in this type of transformation
(Scheme 1).[10]
Introduction
Recently, we observed that in the halo- and seleno-
hydroxylation reactions of allenylphosphane oxides,[1–3] the
electrophilic moiety was added to the central carbon atom
of the allene moiety with the hydroxy group always attached
to the 3-position with respect to the phosphorus atom; the
excellent regio- and (E) stereoselectivity of the reactions has
been rationalized in terms of the neighbouring-group par-
ticipation ability of phosphane oxide.[1,2] However, when
1,2-alkadienylphosphonates were used, the chemistry was
different: Angelov and co-workers reported that the reac-
tions of allenylphosphonates with RSeCl led to (E)/(Z) mix-
tures of [2-(alkyl- or phenylseleno)-3-chloro-1-alkenyl]-
phosphonates.[4] Macomber et al. reported that dimethyl
(propa-1,2-dienyl)phosphonate reacted with 1.0 equiv.
PhSeCl in anhydrous chloroform to afford dimethyl [(E)-3-
chloro-2-(phenylselanyl)-1-propenyl]phosphonate.[5] In this
paper, we wish to report the unexpected reactions of 1- and
3-monosubstituted allenylphosphonates[6–9] with PhSeCl,
which afforded [(Z)-3-chloro-2-(phenylselanyl)-1-alkenyl]-
phosphonates with (Z) stereoselectivity and the chloro sub-
stituent at the 3-position of the starting phosphonates in-
Scheme 1.
Results and Discussion
The reaction of diethyl hepta-1,2-dienylphosphonate (1a)
with 2.0 equiv. of PhSeCl was conducted in CH3CN/H2O
(40:1) at room temperature and afforded diethyl [(Z)-3-
chloro-2-(phenylselanyl)-1-heptenyl]phosphonate [(Z)-2a] in
33% isolated yield, unexpectedly together with the electro-
philic cyclization reaction product, that is, 5-(n-butyl)-2-
ethoxy-4-(phenylselanyl)-2,5-dihydro-1,2-oxaphosphole 2-
oxide (3a; Entry 1, Table 1).[4,5,11] The reaction in MeCN/
H2O (3:1) afforded the cyclization product 3a with a much
higher selectivity (Entry 2, Table 1). Further studies re-
vealed that in CH3CN/H2O (10:1) the products were
formed with an interesting (Z)-2a/3a selectivity. The reac-
[a] Laboratory of Molecular Recognition and Synthesis, Depart-
ment of Chemistry, Zhejiang University,
Hangzhou 310027, Zhejiang, P. R. China
Fax: +86-216-260-9305
E-mail: masm@mail.sioc.ac.cn
[b] Shanghai Key Laboratory of Magnetic Resonance, Department
of Physics, East China Normal University,
Shanghai 200062, P. R. China
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.200900913.
Eur. J. Org. Chem. 2010, 101–110
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
101

G. He, Y. Yu, C. Fu, S. Ma
FULL PAPER
Table 1. Selenochlorination of diethyl hepta-1,2-dienylphosphonate (1a) with PhSeCl.[a]
Entry
PhSeCl [equiv.]
Solvent/H2O (ratio)
Temp. [°C]
Time [h]
Isolated yield of (Z)-2a/3a [%]
(Z)-2a/3a[b]
1
2
3
4
5
6
7
8
9
2.0
2.0
2.0
1.5
2.0
1.5
1.5
1.5
1.2
1.5
2.0
MeCN (40:1)
MeCN (3:1)
MeCN (10:1)
MeCN (10:1)
MeCN (10:1)
dioxane (10:1)
DMF (10:1)
MeOH (10:1)
THF (10:1)
r.t.
r.t.
r.t.
70
50
70
70
70
70
70
70
2.3
2
23
3.5
11.3
4
4
2
2
2.5
2
33:36
18:49
37:3
42:6
44:0
48:52
27:73
Ͼ92:8[c]
Ͼ88:12[c]
99:1
69:0
99:1
48:28
15:20
62:0
69:0
64:0
Ͼ63:37[c]
Ͼ43:57[c]
99:1
10
11
THF (10:1)
THF (10:1)
99:1
99:1
[a] The reaction was carried out by using 0.2 mmol of 1a and 1.5–2.0 equiv. of PhSeCl in 4.0 mL of solvent. [b] The ratio of (Z)-2a/3a
was determined by isolation. [c] Another impurity was formed in this reaction, which could not be separated from 3a.
tion in CH3CN/H2O (10:1) at 50 °C afforded (Z)-2a exclu- Table 2. Selenochlorination of diethyl (3-monosubstituted 1,2-alka-
dienyl)phosphonates with PhSeCl.[a]
sively in an isolated yield of 44% (Entry 5, Table 1),
whereas the reaction in aqueous DMF or CH3OH was poor
(Entries 7 and 8, Table 1). However, the reaction in THF/
H2O (10:1) or dioxane/H2O (10:1) at 70 °C with 1.5 equiv.
of PhSeCl afforded (Z)-2a exclusively in yields of 69% (En-
tries 6 and 10, Table 1). After screening for the effect of the
amount of PhSeCl on the reaction, we finally chose THF/
H2O (10:1) or dioxane/H2O (10:1) as the best media for the
selenochlorination reaction (Entries 6 and 10, Table 1).
Although the yield in dioxane was the same as that in
THF, due to the lower boiling point of THF, the reactions
of the diethyl (3-monosubstituted alka-1,2-dienyl)phos-
phonates 1a–1g and diethyl propa-1,2-dienylphosphonate
(1h) were conducted in THF. The yields of (Z)-2 ranged
from 52 to 81% (Table 2).
Entry
R
Time [h]
Isolated yield of (Z)-2 [%]
1
2[b]
3
n-C4H9 (1a)
n-C4H9 (1a)
Me (1b)
Me (1b)
nPr (1c)
n-C5H11 (1d)
n-C6H13 (1e)
iPr (1f)
Bn (1g)
H (1h)
2.5
4.0
1.0
5.0
1.5
1.0
1.0
1.5
3.3
3.0
69 (2a)
69 (2a)
52 (2b)
53 (2b)
64 (2c)
66 (2d)
68 (2e)
74 (2f)
78 (2g)
81 (2h)
4[b]
5
6
7
8
9
To further confirm the stereochemistry of this seleno-
chlorination reaction, the reaction of diethyl propa-1,2-di-
enylphosphonate with 4-BrC6H4SeCl was conducted. How-
ever, the corresponding product (Z)-2i was a liquid [Equa-
tion (1), Scheme 2]. Thus, the cyclic phosphonate 1j was
prepared and its reaction with 4-BrC6H4SeCl afforded (Z)-
2j, which is fortunately a solid with a melting point of
125.9–126.4 °C. The configuration of the carbon–carbon
double bond in 2j was then determined by its X-ray diffrac-
10
[a] The reactions were carried out by using 0.3 mmol of 1 and
0.45 mmol of PhSeCl in 6.0 mL of THF and 0.6 mL of H2O. [b]
Dioxane/H2O (10:1) was used as the solvent.
The reaction may be easily extended to a scale of 4.8 or
tion study (Figure 1).[12] Note that Macomber et al. as- 5.5 mmol of the substrates 1a and 1j (Scheme 3).
signed the stereochemistry of dimethyl [3-chloro-(2-phen-
For the diethyl (1-monosubstituted alka-1,2-dienyl)phos-
ylselanyl)-1-propenyl]phosphonate formed from the reac- phonates, dioxane/H2O is clearly superior to THF/H2O
tion of dimethyl propa-1,2-dienylphosphonate and (compare Entries 1 and 2 in Table 3). All the selenochlori-
1.0 equiv. of PhSeCl in anhydrous chloroform to an (E) nation reactions proceeded smoothly to afford the products
1
configuration based on the allylic H-1H coupling and its (Z)-2m–(Z)-2o in moderate yields. The configuration of the
similarity with certain sulfur analogues.[5] However, when C=C bond in these products was determined by the NOE
we conducted the reaction of dimethyl propa-1,2-dienyl- study of (Z)-2m (Figure 2). Note that the electrophilic cycli-
phosphonate with PhSeCl under both our conditions and zation products 2-ethoxy-4-(phenylselanyl)-2,5-dihydro-1,2-
those of Macomber et al., the same product (Z)-2k was oxaphosphole 2-oxides 3m–3o were also formed in 6–12%
isolated. Thus, we reasoned that (Z)-2k was misassigned as yields. However, the selenochlorination reaction became
(E)-2k in the literature (Scheme 2).[5]
complicated when diethyl (1-phenyl- and 3-phenylpropa-
102
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Electrophilic Reaction of 1,2-Alkadienylphosphonates with PhSeCl
Scheme 2.
Figure 2. NOE study of (Z)-2m.
Figure 1. ORTEP representation of (Z)-2j.
It is interesting to observe that the stereoselectivity is dif-
ferent from that of the iodo- and selenohydroxylation reac-
tions of (1,2-alkadienyl)diphenylphosphane oxides.[1,2] In
our previous studies of the halohydroxylation reaction we
also observed (Z) stereoselectivity, which was rationalized
in terms of a steric effect[13] or a soft Lewis acid/base inter-
action.[14] It is proposed that the reaction proceeds through
an equilibrium between the three-membered selenonium in-
termediates (E)-4 and (Z)-5. Owing to the steric repulsion
between the relatively bulky Cl– and the PO(OEt)2 group
and the carbon atom with R2 and R3 in (E)-4, intermediate
5 is more favored in the nucleophilic attack of Cl– than
Scheme 3.
1,2-dienyl)phosphonate were subjected to the optimum con- intermediate (E)-4. Thus, the (Z) selenochorination prod-
ditions with 1.5 equiv. of PhSeCl in THF/H2O (10:1) at ucts (Z)-2 were formed with high stereoselectivity
70 °C.
(Scheme 4).[15]
Table 3. Selenochlorination of diethyl (1-substituted 1,2-alkadienyl)phosphonates with PhSeCl.[a]
Entry
R
Time [h]
Isolated yield of (Z)-2 [%]
Isolated yield of 3 [%]
1
2[b]
3
n-C4H9 (1m)
n-C4H9 (1m)
Me (1n)
3.0
2.0
3.0
3.0
74 (2m)
57 (2m)
63 (2n)
69 (2o)
12 (3m)
7 (3m)
6 (3n)
4
n-C7H15 (1o)
9 (3o)
[a] The reaction was carried out by using 0.3 mmol of 1 and 0.45 mmol of PhSeCl in 6.0 mL of dioxane and 0.6 mL of H2O. [b] THF/
H2O (10:1) was used as the solvent.
Eur. J. Org. Chem. 2010, 101–110
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103

G. He, Y. Yu, C. Fu, S. Ma
FULL PAPER
served also provides new information on the control of
selectivity in this type of transformation. Further studies in
this area are being conducted in our laboratory.
Experimental Section
Starting Materials: Compounds 1a–d, 1f, 1h–p, 1r and new com-
pounds 1e, 1g, and 1q were prepared according to the reported
procedure.[20]
Diethyl Nona-1,2-dienylphosphonate (1e). Typical Procedure I: An
oven-dried three-necked round-bottomed flask was charged with
non-1-yn-3-ol (2.0943 g, 15 mmol), triethylamine (2.80 mL, d =
0.7275 g/mL, 2.04 g, 20 mmol), and THF (60 mL). After cooling
the mixture to –78 °C in a dry ice/acetone bath, a solution of di-
ethyl chlorophosphite (3.5282 g, 22.5 mmol) in THF (15 mL) was
added dropwise at –78 °C with stirring over 15 min. Then the re-
sulting mixture was warmed up naturally to room temperature and
heated at reflux. After complete conversion of the propargylic
alcohol, as monitored by TLC (petroleum/ethyl acetate, 2:1), the
mixture was quenched with water (20 mL). The organic layer was
separated, and the aqueous layer was extracted with Et2O
(3ϫ30 mL). The combined organic extracts were washed with
brine (20 mL) and dried with anhydrous Na2SO4. After filtration
and evaporation of the solvent, chromatography of the crude prod-
uct on silica gel (petroleum ether/ethyl acetate, 2:1) afforded 1e
(2.8568 g, 73%) as a liquid. 1H NMR (400 MHz, CDCl3): δ = 5.43–
5.32 (m, 1 H), 5.27–5.20 (m, 1 H), 4.11–3.99 (m, 4 H), 2.09–1.96
(m, 2 H), 1.44–1.33 (m, 2 H), 1.33–1.15 (m, 12 H), 0.82 (t, J =
6.8 Hz, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 211.8, 92.3
(d, JPC = 16.3 Hz), 79.8 (d, JPC = 198.5 Hz), 62.2 (d, JPC = 6.0 Hz),
31.5, 28.8 (d, JPC = 3.5 Hz), 28.6, 27.3 (d, JPC = 6.6 Hz), 22.5, 16.2
(d, JPC = 6.3 Hz), 14.0 ppm. 31P NMR (121.5 MHz, CDCl3): δ =
17.2 ppm. MS (ESI): m/z (%) = 543 [2 M + Na]+ (15.06), 522 [2 M
+ H]+ (26.78), 521 [2 M + H]+ (100), 261 [M + 1]+ (5.02). IR
Scheme 4.
The reactions of (1,3-di-, 3,3-di-, and fully substituted
allenyl)phosphonates under the standard conditions all af-
forded the cyclic 2-ethoxy-4-(phenylselanyl)-2,5-dihydro-
1,2-oxaphosphole 2-oxides 3p–3r as the only products (En-
tries 1–3, Table 4), as reported previously.[4,5,11] Interest-
ingly, these cyclic products must be formed by O-attack of
intermediate (E)-4, which indicates the coexistence of both
intermediates (E)-4 and (Z)-5 in this transformation
(Scheme 4).
Table 4. Reaction of multisubstituted diethyl allenylphosphonates
with PhSeCl.[a]
(neat): ν = 2958, 2929, 2858, 1956, 1459, 1388, 1259, 1164, 1098,
˜
1028 cm–1. HRMS: calcd. for C13H26O3P+ [M + H]+ 261.1614;
found 261.1619.
The following compounds were also prepared according to Typical
Procedure I.
Entry
R1
R2
Me Me (1p)
Et (1q)
R3
Time [h] Isolated yield of 3 [%]
Diethyl (4-Phenylbuta-1,2-dienyl)phosphonate (1g): The reaction of
1-phenylbut-3-yn-2-ol (1.1690 g, 8.0 mmol), Et3N (1.65 mL, d =
0.7275 g/mL, 1.20 g, 11.9 mmol), THF (30 mL), and ClP(OEt)2
(1.9000 g, 12.1 mmol)/THF (5 mL) afforded 1g (1.0919 g, 46%; pu-
rity: 91%) as a liquid. 1H NMR (300 MHz, CDCl3): δ = 7.37–7.18
(m, 5 H), 5.69–5.56 (m, 1 H), 5.35–5.28 (m, 1 H), 4.13–3.91 (m, 4
H), 3.51–3.32 (m, 2 H), 1.31 (t, J = 7.1 Hz, 3 H), 1.30 (t, J =
7.1 Hz, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 212.1, 138.6
(d, JPC = 4.7 Hz), 128.5, 128.4, 126.5, 91.7 (d, JPC = 15.7 Hz), 80.4
(d, JPC = 196.4 Hz), 62.1 (d, JPC = 7.0 Hz), 33.7 (d, JPC = 6.4 Hz),
16.2 (d, JPC = 1.7 Hz), 16.1 (d, JPC = 2.0 Hz) ppm. 31P NMR
(121.5 MHz, CDCl3): δ = 16.4 ppm. MS (EI, 70 eV): m/z (%) = 266
1
2[b]
3
H
n-C4H9
n-C4H9 Me Me (1r)
3.0
0.3
4.0
55 (3p)
92 (3q)
87 (3r)
H
[a] The reaction was carried out by using 0.3 mmol of 1, 0.45 mmol
of PhSeCl, 6.0 mL of THF, and 0.6 mL of H2O. [b] The reaction
was conducted at 70 °C.
Conclusions
We have developed a convenient and practical method
for the synthesis of [(Z)-3-chloro-2-(phenylselanyl)-1-alk-
enyl]phosphonates with high regio- and (Z) stereoselectivity
from (1- and 3-monosubstituted 1,2-allenyl)phosphonates.
2-Ethoxy-4-(phenylselanyl)-2,5-dihydro-1,2-oxaphosphole
2-oxides were formed from (1,3-di-, 3,3-di-, and fully substi-
tuted allenyl)phosphonates. As a result of the presence of a
carbon–carbon double bond, carbon–selenium bond, and a
carbon–phosphorus bond, these compounds will be useful
[M]+ (0.62), 128 (100). IR (neat): ν = 3028, 2983, 2906, 1956, 1603,
˜
1496, 1454, 1390, 1256, 1221, 1164, 1098 cm–1. HRMS: calcd. for
C14H19O3P [M]+ 266.1072; found 266.1080.
Diethyl Nona-3,4-dien-5-ylphosphonate (1q): The reaction of non-4-
yn-3-ol (1.3951 g, 10.0 mmol), Et3N (2.0 mL, d = 0.7275 g/mL,
1.46 g, 14.4 mmol), THF (40 mL), and ClP(OEt)2 (2.3572 g,
15.0 mmol)/THF (10 mL) afforded 1q (1.7718 g, 68%) as a liquid.
1H NMR (400 MHz, CDCl3): δ = 5.44–5.31 (m, 1 H), 4.10–3.91
(m, 4 H), 2.13–1.94 (m, 4 H), 1.46–1.17 (m, 10 H), 1.02–0.91 (m,
in organic synthesis.[16–19] The unique stereoselectivity ob- 3 H), 0.88–0.76 (m, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
104
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Electrophilic Reaction of 1,2-Alkadienylphosphonates with PhSeCl
207.9 (d, JPC = 5.0 Hz), 94.8 (d, JPC = 16.0 Hz), 94.4 (d, JPC
186.9 Hz), 61.9, 61.8, 30.1 (d, JPC = 6.8 Hz), 28.0 (d, JPC = 7.5 Hz),
22.0, 21.0 (d, JPC = 7.9 Hz), 16.14 (d, JPC = 2.1 Hz), 16.08 (d, JPC
=
silica gel (petroleum ether/ethyl acetate, 3:1 to 2:1) afforded (Z)-2a
(1.4637 g, 72%) as a liquid. 1H NMR (300 MHz, CDCl3): δ = 7.64–
7.57 (m, 2 H), 7.43–7.28 (m, 3 H), 6.54 (d, J = 12.9 Hz, 1 H), 4.27–
= 2.0 Hz), 13.7, 13.1 (d, JPC = 4.1 Hz) ppm. 31P NMR (121.5 MHz, 4.08 (m, 5 H), 2.00–1.86 (m, 1 H), 1.75–1.60 (m, 1 H), 1.40–1.22
CDCl3): δ = 20.1 ppm. MS (EI, 70 eV): m/z (%) = 260 [M]+ (1.42), (m, 1 H), 1.36 (t, J = 7.2 Hz, 6 H), 1.20–1.00 (m, 3 H), 0.79 (t, J
43 (100). IR (neat): ν = 2963, 2933, 2873, 1951, 1458, 1391, 1247, = 7.0 Hz, 3 H) ppm.
˜
1164, 1098, 1059, 1028 cm–1. HRMS: calcd. for C13H25O3P [M]+
260.1541; found 260.1545.
Diethyl
[(Z)-3-Chloro-2-(phenylselanyl)-1-heptenyl]phosphonate
[(Z)-2a] and 5-(n-Butyl)-2-ethoxy-4-(phenylselanyl)-2,5-dihydro-1,2-
oxaphosphole 2-Oxide (3a): H2O (1.6 mL) was added to a solution
of PhSeCl (115.4 mg, 0.6 mmol) in MeCN (3.3 mL) at room tem-
perature. Then a solution of 1a (70.6 mg, 0.3 mmol) in MeCN
(1.5 mL) was subsequently added, and the resulting mixture was
stirred at room temp. for 2 h. The mixture was worked up with
H2O (5 mL) and extracted with diethyl ether (3ϫ20 mL), washed
with brine (5 mL), and dried with anhydrous Na2SO4. Filtration,
concentration, and flash chromatography on silica gel (petroleum
ether/ethyl acetate, 3:1) afforded (Z)-2a (22.8 mg, 18%) and 3a
(53.3 mg, 49%). 3a: Liquid. 1H NMR (300 MHz, CDCl3): δ =
7.63–7.55 (m, 2 H), 7.48–7.33 (m, 3 H), [5.42 (dd, J1 = 29.5, J2 =
1.6, 0.34 H), 5.40 (dd, J1 = 29.5, J2 = 1.6 Hz, 0.64 H), dr = 35:65],
4.97–4.85 (m, 1 H), 4.14–3.93 (m, 2 H), 1.97–1.81 (m, 1 H), 1.77–
1.21 (m, 8 H), 0.90 (t, J = 7.2 Hz, 3 H) ppm. MS (EI, 70 eV): m/z
(%) = 362 [M(82Se)]+ (3.7), 360 [M(80Se)]+ (22.1), 358 [M(78Se)]+
or [M(77Se) + 1]+ (12.1), 357 [M(77Se)]+ or [M (76Se) + 1]+ (5.1),
356 [M(76Se)]+ (4.8), 361 [M(80Se) + 1]+ (4.8), 359 [M(78Se) + 1]+
Reaction of Diethyl (3-Substituted allenyl)phosphonates with PhSeCl
Diethyl
[(Z)-3-Chloro-2-(phenylselanyl)-1-heptenyl]phosphonate
[(Z)-2a]. Typical Procedure II: H2O (0.4 mL) was added to a solu-
tion of PhSeCl (57.0 mg, 0.3 mmol) in THF (3.0 mL) at room tem-
perature. Then a solution of 1a (46.4 mg, 0.2 mmol) in THF
(1.0 mL) was added, and the resulting mixture was stirred at 70 °C
for 2.5 h. The mixture was quenched with H2O (5 mL) and ex-
tracted with diethyl ether (3ϫ20 mL), washed with brine (5 mL),
and dried with anhydrous Na2SO4. Filtration, concentration, and
flash chromatography on silica gel (petroleum ether/ethyl acetate,
2:1) afforded (Z)-2a (58.8 mg, 69%) as a liquid. 1H NMR
(300 MHz, CDCl3): δ = 7.64–7.57 (m, 2 H), 7.43–7.28 (m, 3 H),
6.54 (d, J = 12.9 Hz, 1 H), 4.27–4.08 (m, 5 H), 2.00–1.86 (m, 1 H),
1.75–1.60 (m, 1 H), 1.40–1.22 (m, 1 H), 1.36 (t, J = 7.2 Hz, 6 H),
1.20–1.00 (m, 3 H), 0.79 (t, J = 7.0 Hz, 3 H) ppm. 13C NMR
(75 MHz, CDCl3): δ = 156.5 (d, JPC = 5.6 Hz), 136.0, 129.5, 129.1,
126.7, 117.6 (d, JPC = 195.8 Hz), 63.2 (d, JPC = 20.8 Hz), 62.3 (d,
JPC = 5.4 Hz), 61.8 (d, JPC = 5.5 Hz), 38.0 (d, JPC = 1.1 Hz), 28.2,
21.7, 16.4, 16.3, 13.7 ppm. 31P NMR (121.5 MHz, CDCl3): δ =
16.1 ppm. MS (EI, 70 eV): m/z (%) = 429 [M(82Se37Cl) + 1]+ (0.23),
428 [M(82Se37Cl)]+ (1.23), 427 [M(82Se35Cl) + 1]+ or [M(80Se37Cl)
+ 1]+ (1.90), 426 [M(82Se35Cl)]+ or [M(80Se37Cl)]+ (9.09), 425
[M(80Se35Cl) + 1]+ or [M(78Se37Cl) + 1]+ (4.21), 424 [M(80Se35-
(2.6), 355 [M(74Se) + 1]+ (1.9), 93 (100). IR (neat): ν = 3057, 2957,
˜
2932, 2871, 1558, 1476, 1439, 1389, 1328, 1262, 1200, 1163, 1041,
1002 cm–1. C15H21O3PSe (359.26): calcd. C 50.15, H 5.89; found C
50.15, H 5.92.
Diethyl [(Z)-3-Chloro-2-(phenylselanyl)-1-butenyl]phosphonate [(Z)-
2b]: According to the typical procedure III, the reaction of 1b
(57.8 mg, 0.30 mmol) and PhSeCl (86.1 mg, 0.45 mmol) in H2O
(0.6 mL) and dioxane (6 mL) at 70 °C for 5 h afforded (Z)-2b
(62.0 mg, 53%) as a liquid. 1H NMR (300 MHz, CDCl3): δ = 7.61–
7.55 (m, 2 H), 7.41–7.28 (m, 3 H), 6.57 (dd, J1 = 12.9, J2 = 0.6 Hz,
Cl)]+ or [M(78Se37Cl)]+ or [M(77Se37Cl)
+
1]+ (20.21), 423
[M(77Se37Cl)]+ or [M(78Se35Cl) + 1]+ or [M(76Se37Cl) + 1]+ (3.01),
422 [M(78Se35Cl)]+ or [M(76Se37Cl)]+ or [M(77Se35Cl) + 1]+ (9.76),
421 [M(77Se35Cl)]+ or [M(76Se35Cl) + 1]+ or [M(74Se37Cl) + 1]+
(3.44), 420 [M(76Se35Cl)]+ or [M(74Se37Cl)]+ (3.36), 418 1 H), 4.33 (q, J = 6.7 Hz, 1 H), 4.24–4.09 (m, 4 H), 1.55 (d, J =
[M(74Se35Cl)]+ (0.33), 267 (100). IR (neat): ν = 3057, 2959, 2931,
6.6 Hz, 3 H), 1.35 (t, J = 7.1 Hz, 6 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 157.3 (d, JPC = 5.4 Hz), 135.7, 129.6, 129.1, 126.8,
˜
2872, 1576, 1476, 1439, 1391, 1368, 1250, 1163, 1097, 1053,
1025 cm–1. HRMS: calcd. for C17H2735ClO3P80Se [M + H]+
425.0552; found 425.0548.
117.8 (d, JPC = 195.0 Hz), 62.4 (d, JPC = 5.7 Hz), 61.9 (d, JPC
=
6.4 Hz), 58.3 (d, JPC = 21.4 Hz), 25.6, 16.4, 16.3 ppm. 31P NMR
(121.5 MHz, CDCl3): δ = 15.9 ppm. MS (EI, 70 eV): m/z (%) = 384
[M(82Se35Cl)]+ or [M(80Se37Cl)]+ (0.68), 383 [M(80Se35Cl) + 1]+ or
[M(78Se37Cl) + 1]+ (3.57), 382 [M(80Se35Cl)]+ or [M(78Se37Cl)]+ or
[M(77Se37Cl) + 1]+ (1.87), 381 [M(77Se37Cl)]+ or [M(78Se35Cl) +
Reaction in Dioxane/H2O. Typical Procedure III: H2O (0.4 mL) was
added to a solution of PhSeCl (58.2 mg, 0.3 mmol) in dioxane
(3.0 mL) at room temperature. Then a solution of 1a (45.5 mg,
0.2 mmol) in dioxane (1.0 mL) was subsequently added, and the
resulting mixture was stirred at 70 °C for 4 h. The mixture was
quenched with H2O (5 mL) and extracted with diethyl ether
(3ϫ20 mL), washed with brine (5 mL), and dried with anhydrous
Na2SO4. Filtration, concentration, and flash chromatography on
silica gel (petroleum ether/ethyl acetate, 2:1) afforded (Z)-2a
(57.6 mg, 69%) as a liquid. 1H NMR (300 MHz, CDCl3): δ = 7.64–
7.57 (m, 2 H), 7.43–7.28 (m, 3 H), 6.54 (dd, J1 = 12.9, J2 = 0.8 Hz,
1 H), 4.27–4.09 (m, 5 H), 2.00–1.85 (m, 1 H), 1.75–1.60 (m, 1 H),
1.40–1.22 (m, 1 H), 1.37 (t, J = 7.2 Hz, 6 H), 1.20–1.00 (m, 3 H),
0.80 (t, J = 7.1 Hz, 3 H) ppm.
1]+ or [M(76Se37Cl)
+
1]+ (9.84), 380 [M(78Se35Cl)]+ or
[M(76Se37Cl)]+ or [M(77Se35Cl) + 1]+ (0.74), 379 [M(77Se35Cl)]+ or
[M(76Se35Cl) + 1]+ or [M(74Se37Cl) + 1]+ (3.95), 378 [M(76Se35-
Cl)]+ or [M(74Se37Cl)]+ (0.30), 377 [M(74Se35Cl) + 1]+ (1.57), 133
(100). IR (neat): ν = 3057, 2982, 2930, 2901, 1576, 1477, 1439,
˜
1391, 1368, 1248, 1163, 1097, 1051, 1024 cm–1. HRMS: calcd. for
C14H2035ClO3P80Se [M]+ 382.0004; found 382.0010.
Diethyl [(Z)-3-Chloro-2-(phenylselanyl)-1-butenyl]phosphonate [(Z)-
2b]: According to the typical procedure II, the reaction of 1b
(56.4 mg, 0.30 mmol) and PhSeCl (86.4 mg, 0.45 mmol) in H2O
(0.6 mL) and THF (6 mL) at 70 °C for 1 h afforded (Z)-2b
(58.6 mg, 52%) as a liquid. 1H NMR (300 MHz, CDCl3): δ = 7.61–
7.55 (m, 2 H), 7.41–7.28 (m, 3 H), 6.58 (d, J = 12.8 Hz, 1 H), 4.33
(q, J = 6.6 Hz, 1 H), 4.24–4.09 (m, 4 H), 1.55 (d, J = 6.6 Hz, 3 H),
1.34 (t, J = 7.1 Hz, 6 H) ppm.
Larger Scale Reaction of 1a: H2O (2.4 mL) was added to a solution
of PhSeCl (1.3802 g, 7.2 mmol) in dioxane (36 mL) at room tem-
perature. Then a solution of 1a (1.1134 g, 4.8 mmol) in dioxane
(12 mL) was subsequently added dropwise over 3 min, and the re-
sulting mixture was stirred at 70 °C for 5.5 h. The mixture was
quenched with H2O (10 mL) and extracted with diethyl ether
(3ϫ30 mL), washed with brine (10 mL), and dried with anhydrous
Na2SO4. Filtration, concentration, and flash chromatography on
Diethyl [(Z)-3-Chloro-2-(phenylselanyl)-1-hexenyl]phosphonate [(Z)-
2c]: According to the typical procedure II, the reaction of 1c
(64.9 mg, 0.30 mmol) and PhSeCl (86.8 mg, 0.45 mmol) in H2O
Eur. J. Org. Chem. 2010, 101–110
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
105

G. He, Y. Yu, C. Fu, S. Ma
FULL PAPER
(0.6 mL) and THF (6 mL) at 70 °C for 1.5 h afforded (Z)-2c
[M(77Se37Cl) + 1]+ (13.88), 451 [M(77Se37Cl)]+ or [M(78Se35Cl) +
1
(77.7 mg, 64%) as a liquid. H NMR (400 MHz, CDCl3): δ = 7.58 1]+ or [M(76Se37Cl)
+
1]+ (48.16), 450 [M(78Se35Cl)]+ or
(d, J = 7.6 Hz, 2 H), 7.40–7.28 (m, 3 H), 6.52 (d, J = 12.8 Hz, 1
[M(76Se37Cl)]+ or [M(77Se35Cl) + 1]+ (14.69), 449 [M(77Se35Cl)]+ or
H), 4.24–4.09 (m, 5 H), 1.91–1.81 (m, 1 H), 1.71–1.60 (m, 1 H), [M(76Se35Cl) + 1]+ or [M(74Se37Cl) + 1]+ (16.73). IR (neat): ν =
˜
1.40–1.25 (m, 1 H), 1.34 (t, J = 7.4 Hz, 6 H), 1.16–1.04 (m, 1 H),
0.67 (t, J = 7.4 Hz, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
2961, 2956, 2929, 2858, 1577, 1477, 1439, 1386, 1249, 1158, 1095,
1053, 1024 cm–1. HRMS: calcd. for C19H3135ClO3P80Se [M + H]+
453.0859; found 453.0856.
156.6 (d, JPC = 5.5 Hz), 136.0, 129.5, 129.1, 126.6, 117.4 (d, JPC
=
194.8 Hz), 62.8 (d, JPC = 20.5 Hz), 62.3 (d, JPC = 5.5 Hz), 61.8
(d, JPC = 5.6 Hz), 40.1, 19.3, 16.34, 16.28, 12.9 ppm. 31P NMR
(121.5 MHz, CDCl3): δ = 17.2 ppm. MS (EI, 70 eV): m/z (%) = 378
[M(82Se35Cl) + 1 – 35Cl]+ or [M(80Se37Cl) + 1 – 35Cl]+ (0.75), 377
Diethyl [(Z)-3-Chloro-4-methyl-2-(phenylselanyl)-1-pentenyl]phos-
phonate [(Z)-2f]: According to the typical procedure II, the reaction
of 1f (64.1 mg, 0.30 mmol) and PhSeCl (85.9 mg, 0.45 mmol) in
H2O (0.6 mL) and THF (6 mL) at 70 °C for 1.5 h afforded (Z)-2f
(89.6 mg, 74%) as a liquid. 1H NMR (400 MHz, CDCl3): δ = 7.60–
7.56 (m, 2 H), 7.39–7.29 (m, 3 H), 6.50 (d, J = 13.6 Hz, 1 H), 4.24–
4.08 (m, 5 H), 2.31–2.20 (m, 1 H), 1.334 (t, J = 7.2 Hz, 3 H), 1.332
(t, J = 7.2 Hz, 3 H), 0.79 (d, J = 7.0 Hz, 3 H), 0.73 (d, J = 7.0 Hz,
[M(82Se35Cl)
– –
35Cl]+ or [M(80Se37Cl) 35Cl]+ (3.96), 376
[M(80Se35Cl) + 1 – 35Cl]+ or [M(78Se37Cl) + 1 – 35Cl]+ (4.61), 375
[M(80Se35Cl) – 35Cl]+ or [M(78Se37Cl) – 35Cl]+ or [M(77Se37Cl) +
1 – 35Cl]+ (18.61), 374 [M(77Se37Cl) – 35Cl]+ or [M(78Se35Cl) + 1 –
35Cl]+ or [M(76Se37Cl) + 1 – 35Cl]+ (2.11), 373 [M(78Se35Cl) –
35Cl]+ or [M(76Se37Cl) – 35Cl]+ or [M(77Se35Cl) + 1 – 35Cl]+ (11.32),
372 [M(77Se35Cl) – 35Cl]+ or [M(76Se35Cl) + 1 – 35Cl]+ or
[M(74Se37Cl) + 1 – 35Cl]+ (4.23), 371 [M(76Se35Cl) – 35Cl]+ or
3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 155.2 (d, JPC
=
6.0 Hz), 136.0, 129.5, 129.1, 126.6, 118.4 (d, JPC = 194.1 Hz), 69.6
(d, JPC = 20.1 Hz), 62.3 (d, JPC = 5.4 Hz), 61.7 (d, JPC = 5.5 Hz),
32.4, 20.6, 16.34, 16.27, 15.1 ppm. 31P NMR (121.5 MHz, CDCl3):
δ = 17.0 ppm. MS (EI, 70 eV): m/z (%) = 412 [M(82Se35Cl)]+ or
[M(80Se37Cl)]+ (10.56), 411 [M(80Se35Cl) + 1]+ or [M(78Se37Cl) +
1]+ (5.21), 410 [M(80Se35Cl)]+ or [M(78Se37Cl)]+ or [M(77Se37Cl) +
1]+ (23.50), 408 [M(78Se35Cl)]+ or [M(76Se37Cl)]+ or [M(77Se35Cl) +
[M(74Se37Cl) – 35Cl]+ (4.24), 79 (100). IR (neat): ν = 3056, 2962,
˜
2933, 2873, 1576, 1476, 1439, 1391, 1250, 1163, 1097, 1053,
1023 cm–1. C16H24ClO3PSe (409.75): calcd. C 46.90, H 5.90; found
C 46.86, H 5.93.
1]+ (12.07), 407 [M(77Se35Cl)]+ or [M(76Se35Cl)
+
1]+ or
Diethyl [(Z)-3-Chloro-2-(phenylselanyl)-1-octenyl]phosphonate [(Z)-
2d]: According to the typical procedure II, the reaction of 1d
(74.4 mg, 0.30 mmol) and PhSeCl (85.5 mg, 0.45 mmol) in H2O
(0.6 mL) and THF (6 mL) at 70 °C for 1 h afforded (Z)-2d
[M(74Se37Cl) + 1]+ (4.41), 406 [M(76Se35Cl)]+ or [M(74Se37Cl)]+
(4.15), 253 (100). IR (neat): ν = 3055, 2974, 2932, 2905, 2873, 1575,
˜
1473, 1440, 1389, 1368, 1250, 1164, 1097, 1053, 1024 cm–1. HRMS:
calcd. for C16H2435ClO3P80Se [M]+ 410.0317; found 410.0321.
1
(87.8 mg, 66%) as a liquid. H NMR (400 MHz, CDCl3): δ = 7.58
(d, J = 7.2 Hz, 2 H), 7.40–7.28 (m, 3 H), 6.51 (d, J = 13.2 Hz, 1
H), 4.27–4.08 (m, 5 H), 1.94–1.84 (m, 1 H), 1.70–1.58 (m, 1 H),
1.34 (t, J = 7.0 Hz, 6 H), 1.34–1.25 (m, 1 H), 1.22–1.10 (m, 2 H),
1.10–0.97 (m, 3 H), 0.78 (t, J = 7.0 Hz, 3 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 156.6 (d, JPC = 5.6 Hz), 136.0, 129.5, 129.1,
126.6, 117.4 (d, JPC = 196.5 Hz), 63.1 (d, JPC = 20.6 Hz), 62.2 (d,
JPC = 5.4 Hz), 61.8 (d, JPC = 5.4 Hz), 38.2, 30.6, 25.7, 22.2, 16.32,
16.26, 13.8 ppm. 31P NMR (121.5 MHz, CDCl3): δ = 16.1 ppm.
MS (EI, 70 eV): m/z (%) = 441 [M(82Se35Cl) + 1]+ or [M(80Se37Cl)
+ 1]+ (1.50), 440 [M(82Se35Cl)]+ or [M(80Se37Cl)]+ (6.90), 439
[M(80Se35Cl) + 1]+ or [M(78Se37Cl) + 1]+ (3.97), 438 [M(80Se35-
Diethyl
[(Z)-3-Chloro-4-phenyl-2-(phenylselanyl)-1-butenyl]phos-
phonate [(Z)-2g]: According to the typical procedure II, the reac-
tion of 1g (54.1 mg, 0.20 mmol, purity: 91%) and PhSeCl (59.1 mg,
0.30 mmol) in H2O (0.4 mL) and THF (4 mL) at 70 °C for 3.3 h
afforded (Z)-2g (66.1 mg, 78%) as a liquid. 1H NMR (300 MHz,
CDCl3): δ = 7.67–7.60 (m, 2 H), 7.47–7.36 (m, 3 H), 7.23–7.14 (m,
3 H), 6.86–6.79 (m, 2 H), 6.56 (d, J = 12.6 Hz, 1 H), 4.51 (dd, J1
= 9.0, J2 = 3.9 Hz, 1 H), 4.23–4.08 (m, 4 H), 3.34 (dd, J1 = 14.4,
J2 = 3.9 Hz, 1 H), 2.86 (dd, J1 = 14.4, J2 = 9.0 Hz, 1 H), 1.38 (t, J
= 6.9 Hz, 3 H), 1.37 (t, J = 6.9 Hz, 3 H) ppm. 13C NMR (75 MHz,
CDCl3): δ = 155.6 (d, JPC = 6.0 Hz), 136.4, 136.3, 129.8, 129.4,
129.2, 128.1, 126.9, 126.6, 118.1 (d, JPC = 194.4 Hz), 63.5 (d, JPC
= 20.9 Hz), 62.3 (d, JPC = 5.6 Hz), 61.9 (d, JPC = 5.5 Hz), 44.2 (d,
JPC = 1.4 Hz), 16.4, 16.3 ppm. 31P NMR (121.5 MHz, CDCl3): δ
= 15.9 ppm. MS (EI, 70 eV): m/z (%) = 461 [M(82Se35Cl) + 1]+ or
[M(80Se37Cl) + 1]+ (1.72), 460 [M(82Se35Cl)]+ or [M(80Se37Cl)]+
(7.38), 459 [M(80Se35Cl) + 1]+ or [M(78Se37Cl) + 1]+ (4.23), 458
[M(80Se35Cl)]+ or [M(78Se37Cl)]+ or [M(77Se37Cl) + 1]+ (16.45), 456
[M(78Se35Cl)]+ or [M(76Se37Cl)]+ or [M(77Se35Cl) + 1]+ (8.20), 455
[M(77Se35Cl)]+ or [M(76Se35Cl) + 1]+ or [M(74Se37Cl) + 1]+ (3.27),
Cl)]+ or [M(78Se37Cl)]+ or [M(77Se37Cl)
+
1]+ (15.28), 436
[M(78Se35Cl)]+ or [M(76Se37Cl)]+ or [M(77Se35Cl) + 1]+ (7.63), 435
[M(77Se35Cl)]+ or [M(76Se35Cl) + 1]+ or [M(74Se37Cl) + 1]+ (3.35),
434 [M(76Se35Cl)]+ or [M(74Se37Cl)]+ (2.73), 281 (100). IR (neat): ν
˜
= 2930, 2860, 1576, 1476, 1439, 1391, 1368, 1249, 1164, 1097,
1024 cm–1. HRMS: calcd. for C18H2835ClO3P80Se [M]+ 438.0630;
found 438.0639.
Diethyl [(Z)-3-Chloro-2-(phenylselanyl)-1-nonenyl]phosphonate [(Z)-
2e]: According to the typical procedure II, the reaction of 1e
(51.6 mg, 0.20 mmol) and PhSeCl (58.0 mg, 0.30 mmol) in H2O
(0.4 mL) and THF (4 mL) at 70 °C for 1 h afforded (Z)-2e
(60.7 mg, 68%) as a liquid. 1H NMR (400 MHz, CDCl3): δ = 7.63–
7.57 (m, 2 H), 7.40–7.29 (m, 3 H), 6.53 (d, J = 13.2 Hz, 1 H), 4.24–
4.09 (m, 5 H), 1.95–1.86 (m, 1 H), 1.73–1.61 (m, 1 H), 1.35 (d, J
= 7.2 Hz, 6 H), 1.35–1.25 (m, 1 H), 1.25–0.95 (m, 7 H), 0.83 (t, J
454 [M(76Se35Cl)]+ or [M(74Se37Cl)]+ (2.81), 128 (100). IR (neat): ν
= 3060, 2982, 2930, 2905, 1574, 1476, 1439, 1391, 1249, 1163, 1097,
1024 cm–1. HRMS: calcd. for C20H2435ClO3P80Se [M]+ 458.0317;
found 458.0315.
˜
Diethyl
[(Z)-3-Chloro-2-(phenylselanyl)-1-propenyl]phosphonate
= 7.2 Hz, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 156.7 (d, [(Z)-2h]: According to the typical procedure II, the reaction of 1h
JPC = 5.4 Hz), 136.1, 129.5, 129.2, 126.7, 117.6 (d, JPC = 196.1 Hz), (52.6 mg, 0.30 mmol) and PhSeCl (85.5 mg, 0.45 mmol) in H2O
63.2 (d, JPC = 20.6 Hz), 62.3 (d, JPC = 6.5 Hz), 61.8 (d, JPC
=
(0.6 mL) and THF (6 mL) at 70 °C for 3 h afforded (Z)-2h
5.3 Hz), 38.3 (d, JPC = 1.6 Hz), 31.4, 28.2, 26.0, 22.4, 16.4, 16.3,
13.9 ppm. 31P NMR (121.5 MHz, CDCl3): δ = 17.3 ppm. MS (ESI)
m/z (%) = 457 [M(82Se37Cl) + 1]+ (4.08), 456 [M(82Se37Cl)]+ (9.39),
455 [M(82Se35Cl) + 1]+ or [M(80Se37Cl) + 1]+ (44.49), 454
[M(82Se35Cl)]+ or [M(80Se37Cl)]+ (19.18), 453 [M(80Se35Cl) + 1]+ or
[M(78Se37Cl) + 1]+ (100), 452 [M(80Se35Cl)]+ or [M(78Se37Cl)]+ or
(89.2 mg, 81%) as a liquid.[4a] 1H NMR (400 MHz, CDCl3): δ =
7.67–7.62 (m, 2 H), 7.44–7.28 (m, 3 H), 6.46 (dt, J1 = 13.2, J2
=
1.6 Hz, 1 H), 4.23–4.10 (m, 4 H), 3.96 (t, J = 1.6 Hz, 2 H), 1.36 (t,
J = 7.0 Hz, 6 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 151.5 (d,
JPC = 6.4 Hz), 136.7, 129.44, 129.38, 125.4, 116.5 (d, JPC
=
194.5 Hz), 62.0 (d, JPC = 5.6 Hz), 48.4 (d, JPC = 22.7 Hz), 16.3 (d,
106
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© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2010, 101–110

Electrophilic Reaction of 1,2-Alkadienylphosphonates with PhSeCl
JPC = 6.3 Hz) ppm. 31P NMR (121.5 MHz, CDCl3): δ = 16.8 ppm.
(1.3 mL), was placed in a dried Schlenk tube under nitrogen at
room temperature. A solution of p-bromophenylselanyl chloride
(108.5 mg, 0.40 mmol) in anhydrous chloroform (1.1 mL) was then
added dropwise to the reaction mixture at room temp. within
5 min. Then the resulting mixture was stirred at 46 °C for 26 h.
After evaporation and flash chromatography on silica gel (petro-
MS (EI, 70 eV): m/z (%)
=
372 [M(82Se37Cl)]+ (0.80), 371
[M(82Se35Cl) + 1]+ or [M(80Se37Cl) + 1]+ (1.00), 370 [M(82Se35-
Cl)]+ or [M(80Se37Cl)]+ (5.38), 369 [M(80Se35Cl)
+
1]+ or
[M(78Se37Cl) + 1]+ (2.43), 368 [M(80Se35Cl)]+ or [M(78Se37Cl)]+ or
[M(77Se37Cl) + 1]+ (11.70), 367 [M(77Se37Cl)]+ or [M(78Se35Cl) +
1]+ or [M(76Se37Cl)
+
1]+ (1.84), 366 [M(78Se35Cl)]+ or leum ether/ethyl acetate, 3:2), (Z)-2j (98.7 mg, 54%) was obtained
[M(76Se37Cl)]+ or [M(77Se35Cl) + 1]+ (5.26), 365 [M(77Se35Cl)]+ or
as a white solid. H NMR (300 MHz, CDCl3): δ = 7.56–7.50 (m,
2 H), 7.49–7.43 (m, 2 H), 6.54 (dt, J1 = 15.0, J2 = 1.5 Hz, 1 H),
4.20–4.09 (m, 2 H), 3.99 (t, J = 1.5 Hz, 2 H), 3.96–3.86 (m, 2 H),
1.13 (s, 3 H), 1.05 (s, 3 H) ppm. 13% of 1j was recovered, as deter-
1
[M(76Se35Cl) + 1]+ or [M(74Se37Cl) + 1]+ (1.98), 364 [M(76Se35-
Cl)]+ or [M(74Se37Cl)]+ (2.05), 211 (100). IR (neat): ν = 3054, 2982,
˜
2937, 2905, 1576, 1477, 1439, 1391, 1246, 1163, 1097, 1021 cm–1.
1
mined by H NMR analysis of the crude product.
Diethyl
[(Z)-2-(4-Bromophenylselanyl)-3-chloro-1-propenyl]phos-
phonate [(Z)-2i]: According to the typical procedure II, the reaction
of 1h (52.3 mg, 0.30 mmol) and p-bromophenylselanyl chloride
(163.1 mg, 0.60 mmol) in H2O (0.6 mL) and THF (6 mL) at 70 °C
Dimethyl [(Z)-3-Chloro-2-(phenylselanyl)-1-propenyl]phosphonate
[(Z)-2k]: According to the typical procedure II, the reaction of 1k
(59.5 mg, 0.40 mmol) and PhSeCl (114.8 mg, 0.60 mmol) in H2O
for 3.5 h afforded (Z)-2i (98.6 mg, 74%) as a liquid. 1H NMR (0.6 mL) and THF (6 mL) at 70 °C for 4 h afforded (Z)-2k
(300 MHz, CDCl3): δ = 7.55–7.41 (m, 4 H), 6.45 (dt, J1 = 12.6, J2 (108.9 mg, 80%) as a liquid.[5] 1H NMR (300 MHz, CDCl3): δ =
= 1.4 Hz, 1 H), 4.22–4.07 (m, 4 H), 3.95 (t, J = 1.4 Hz, 2 H), 1.35 7.68–7.62 (m, 2 H), 7.44–7.29 (m, 3 H), 6.44 (dt, J1 = 13.5, J2
(t, J = 7.2 Hz, 6 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 150.9
1.5 Hz, 1 H), 3.96 (t, J = 1.5 Hz, 2 H), 3.82 (s, 3 H), 3.78 (s, 3 H)
(d, JPC = 5.9 Hz), 138.2, 132.7, 124.41, 124.37, 117.5 (d, JPC
ppm. 13C NMR (75 MHz, CDCl3): δ = 152.7 (d, JPC = 6.9 Hz),
=
=
194.3 Hz), 62.2 (d, JPC = 5.7 Hz), 48.3 (d, JPC = 22.8 Hz), 16.4 (d,
JPC = 6.4 Hz) ppm. 31P NMR (121.5 MHz, CDCl3): δ = 15.4 ppm.
MS (EI, 70 eV): m/z (%) = 450 [M(82Se81Br35Cl)]+ or [M(82Se79-
136.8, 129.5, 125.2, 115.0 (d, JPC = 195.1 Hz), 52.6 (d, JPC =
5.8 Hz), 48.4 (d, JPC = 23.9 Hz) ppm. 31P NMR (121.5 MHz,
CDCl3): δ = 18.5 ppm. MS (EI, 70 eV): m/z (%) = 345 [M(82Se37Cl)
Br37Cl)]+ or [M(80Se81Br37Cl)]+ (2.85), 448 [M(82Se79Br35Cl)]+ or + 1]+ (0.07), 344 [M(82Se37Cl)]+ (0.48), 343 [M(82Se35Cl) + 1]+ or
[M(80Se81Br35Cl)]+ or [M(80Se79Br37Cl)]+ or [M(78Se81Br37Cl)]+ [M(80Se37Cl) + 1]+ (0.45), 342 [M(82Se35Cl)]+ or [M(80Se37Cl)]+
(7.67), 446 [M(80Se79Br35Cl)]+ or [M(78Se79Br37Cl)]+ or [M(78Se81-
(3.76), 341 [M(80Se35Cl) + 1]+ or [M(78Se37Cl) + 1]+ (1.16), 340
Br35Cl)]+ or [M(76Se81Br37Cl)]+ (7.27), 444 [M(78Se79Br35Cl)]+ or [M(80Se35Cl)]+ or [M(78Se37Cl)]+ or [M(77Se37Cl) + 1]+ (8.67), 339
[M(76Se81Br35Cl)]+ or [M(76Se79Br37Cl)]+ or [M(74Se81Br37Cl)]+ [M(77Se37Cl)]+ or [M(78Se35Cl) + 1]+ or [M(76Se37Cl) + 1]+ (1.03),
(2.98), 447 [M(80Se79Br35Cl) + 1]+ or [M(78Se79Br37Cl) + 1]+ or
[M(78Se81Br35Cl) + 1]+ or [M(76Se81Br37Cl) + 1]+ (1.74), 445
[M(78Se79Br35Cl) + 1]+ or [M(76Se81Br35Cl) + 1]+ or [M(76Se79-
338 [M(78Se35Cl)]+ or [M(76Se37Cl)]+ or [M(77Se35Cl) + 1]+ (4.16),
337 [M(77Se35Cl)]+ or [M(76Se35Cl) + 1]+ or [M(74Se37Cl) + 1]+
(1.35), 336 [M(76Se35Cl)]+ or [M(74Se37Cl)]+ (1.43), 183 (100). IR
Br37Cl) + 1]+ or [M(74Se81Br37Cl) + 1]+ (1.36), 211 (100). IR (neat): (neat): ν = 3055, 2992, 2951, 2849, 1585, 1576, 1470, 1439, 1414,
˜
ν = 2982, 2936, 2904, 1585, 1568, 1467, 1441, 1381, 1245, 1163, 1249, 1183, 1028 cm–1. HRMS: calcd. for C11H1435ClO3P80Se
˜
1095,
1051,
1024,
1007 cm–1.
HRMS:
calcd.
for [M]+ 339.9534; found 339.9524.
C13H1779Br35ClO3P80Se [M]+ 445.8952; found 445.8954.
Reaction of 1k and PhSeCl in Anhydrous Chloroform:[5] Compound
2-[(1Z)-2-(4-Bromophenylselanyl)-3-chloro-1-propenyl]-5,5-dimeth- 1k (103.3 mg, 0.70 mmol), followed by anhydrous chloroform
yl-1,3,2-dioxaphosphorinane 2-Oxide [(Z)-2j]: According to the typ-
ical procedure II, the reaction of 1j (56.5 mg, 0.30 mmol) and p-
bromophenylselanyl chloride (161.9 mg, 0.60 mmol) in H2O
(0.6 mL) and THF (6 mL) at 70 °C for 2 h afforded (Z)-2j (99.6 mg,
72%) as a white solid; m.p. 125.9–126.4 °C (n-hexane/ethyl acetate).
(2.0 mL), was placed in a dried Schlenk tube under nitrogen at
room temperature. A solution of phenylselanyl chloride (134.8 mg,
0.70 mmol) in anhydrous chloroform (2.4 mL) was then added
dropwise to the reaction mixture at room temp. within 5 min. Then
the resulting mixture was stirred at 46 °C for 19 h. After concentra-
1H NMR (300 MHz, CDCl3): δ = 7.55–7.49 (m, 2 H), 7.48–7.42 tion and flash chromatography on silica gel (petroleum ether/ethyl
(m, 2 H), 6.53 (dt, J1 = 15.0, J2 = 1.5 Hz, 1 H), 4.19–4.08 (m, 2
H), 3.98 (t, J = 1.5 Hz, 2 H), 3.96–3.85 (m, 2 H), 1.13 (s, 3 H), 1.04
acetate, 3:1 to 2:1), (Z)-2k (167.5 mg, 71%) was obtained as a li-
quid. H NMR (300 MHz, CDCl3): δ = 7.66–7.60 (m, 2 H), 7.42–
7.28 (m, 3 H), 6.43 (dt, J1 = 13.5, J2 = 1.5 Hz, 1 H), 3.95 (t, J =
1
(s, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 153.0 (d, JPC
=
7.3 Hz), 138.3, 132.8, 124.5, 124.1, 115.1 (d, JPC = 191.0 Hz), 75.9,
75.8, 48.3 (d, JPC = 22.9 Hz), 32.4 (d, JPC = 6.0 Hz), 21.5,
21.3 ppm. 31P NMR (121.5 MHz, CDCl3): δ = 10.3 ppm. MS (EI,
70 eV): m/z (%) = 462 [M(82Se81Br35Cl)]+ or [M(82Se79Br37Cl)]+ or
[M(8 0 Se8 1 Br3 7 Cl)]+ (3.30), 460 [M(8 2 Se7 9 Br3 5 Cl)]+ or
[M(80Se81Br35Cl)]+ or [M(80Se79Br37Cl)]+ or [M(78Se81Br37Cl)]+
(8.15), 458 [M(80Se79Br35Cl)]+ or [M(78Se79Br37Cl)]+ or
[M(7 8 Se8 1 Br3 5 Cl)]+ or [M(7 6 Se8 1 Br3 7 Cl)]+ (9.17), 457
[M(7 8 Se7 9 Br3 5 C l) + 1 ]+ or [M(7 6 Se8 1 Br3 5 C l) + 1 ]+ or
[M(76Se79Br37Cl) + 1]+ or [M(74Se81Br37Cl) + 1]+ (3.41), 456
[M(78Se79Br35Cl)]+ or [M(76Se81Br35Cl)]+ or [M(76Se79Br37Cl)]+ or
1.5 Hz, 2 H), 3.80 (s, 3 H), 3.76 (s, 3 H) ppm.
2-[(1Z)-3-Chloro-2-(phenylselanyl)-1-propenyl]-5,5-dimethyl-1,3,2-di-
oxaphosphorinane 2-Oxide [(Z)-2l). Large-Scale Reaction: Accord-
ing to the typical procedure II, the reaction of 1j (1.0336 g,
5.5 mmol)/THF (13 mL), PhSeCl (2.1070 g, 11.0 mmol)/THF
(39 mL), and H2O (5.2 mL) at 70 °C for 2 h afforded (Z)-2l
(1.6716 g, 80%) as a white solid; m.p. 126.6–127.4 °C (n-hexane/
ethyl acetate). 1H NMR (300 MHz, CDCl3): δ = 7.71–7.60 (m, 2
H), 7.45–7.29 (m, 3 H), 6.52 (d, J = 15.0 Hz, 1 H), 4.13 (dd, J1 =
13.8, J2 = 11.1 Hz, 2 H), 3.99 (t, J = 1.5 Hz, 2 H), 3.92 (t, J =
10.4 Hz, 2 H), 1.14 (s, 3 H), 1.04 (s, 3 H) ppm. 13C NMR (75 MHz,
CDCl3): δ = 153.6 (d, JPC = 7.4 Hz), 136.8, 129.6, 129.5, 125.0,
114.0 (d, JPC = 190.7 Hz), 75.9, 75.8, 48.4 (d, JPC = 22.7 Hz), 32.4
(d, JPC = 6.5 Hz), 21.5, 21.2 ppm. 31P NMR (121.5 MHz, CDCl3):
δ = 10.6 ppm. MS (EI, 70 eV): m/z (%) = 385 [M(82Se37Cl) + 1]+
(0.13), 384 [M(82Se37Cl)]+ (0.86), 383 [M(82Se35Cl) + 1]+ or
[M(80Se37Cl) + 1]+ (1.09), 382 [M(82Se35Cl)]+ or [M(80Se37Cl)]+
[M(74Se81Br37Cl)]+ (4.21), 223 (100). IR (KBr): ν = 3067, 2958,
˜
2883, 1568, 1466, 1379, 1255, 1228, 1061, 1053 cm– 1
.
C14H17BrClO3PSe (458.57): calcd. C 36.67, H 3.74; found C 36.95,
H 3.88.
Reaction of 1j and p-BrC6H4SeCl in Anhydrous Chloroform:[5] Com-
pound 1j (75.4 mg, 0.40 mmol), followed by anhydrous chloroform
Eur. J. Org. Chem. 2010, 101–110
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
107

G. He, Y. Yu, C. Fu, S. Ma
FULL PAPER
(6.59), 381 [M(80Se35Cl) + 1]+ or [M(78Se37Cl) + 1]+ (2.54), 380 5:1, twice) to afford pure (Z)-2m (72.2 mg, 57%) and 3m (7.5 mg,
1
[M(80Se35Cl)]+ or [M(78Se37Cl)]+ or [M(77Se37Cl) + 1]+ (15.37), 378
[M(78Se35Cl)]+ or [M(76Se37Cl)]+ or [M(77Se35Cl) + 1]+ (7.48), 377
[M(77Se35Cl)]+ or [M(76Se35Cl) + 1]+ or [M(74Se37Cl) + 1]+ (2.45),
376 [M(76Se35Cl)]+ or [M(74Se37Cl)]+ (2.51), 374 [M(74Se35Cl)]+
7%). (Z)-2m: Liquid. H NMR (300 MHz, CDCl3): δ = 7.72–7.65
(m, 2 H), 7.44–7.28 (m, 3 H), 4.28–4.12 (m, 4 H), 4.03 (s, 2 H),
2.52–2.38 (m, 2 H), 1.60–1.46 (m, 2 H), 1.43–1.30 (m, 2 H), 1.38
(t, J = 7.1 Hz, 6 H), 0.93 (t, J = 7.2 Hz, 3 H) ppm. 3m: Liquid. 1H
(0.24), 223 (100). IR (KBr): ν = 3072, 3012, 2971, 2894, 1575, 1471, NMR (300 MHz, CDCl3): δ = 7.62–7.55 (m, 2 H), 7.45–7.29 (m, 3
˜
1439, 1262, 1057, 1008 cm–1. C14H18ClO3PSe (379.68): calcd. C
44.29, H 4.78; found C 44.35, H 4.89.
H), 4.34–4.27 (m, 2 H), 4.16–4.04 (m, 2 H), 2.52–2.30 (m, 2 H),
1.68–1.52 (m, 2 H), 1.47–1.31 (m, 2 H), 1.33 (t, J = 7.1 Hz, 3 H),
0.96 (t, J = 7.5 Hz, 3 H) ppm.
Reaction of Diethyl (1-Substituted allenyl)phosphonates with PhSeCl
Diethyl [(Z)-1-Chloro-2-(phenylselanyl)-2-buten-3-yl]phosphonate
[(Z)-2n] and 2-Ethoxy-3-methyl-4-(phenylselanyl)-2,5-dihydro-1,2-
oxaphosphole 2-Oxide (3n): According to the typical procedure III,
the reaction of 1n (57.7 mg, 0.30 mmol) and PhSeCl (86.5 mg,
0.45 mmol) in H2O (0.6 mL) and dioxane (6.0 mL) at 70 °C for 3 h
afforded a mixture of (Z)-2n and 3n, which were separated by re-
peated chromatography on silica gel (petroleum ether/ethyl acetate,
2:1, twice) to afford pure (Z)-2n (72.9 mg, 63%) and 3n (5.7 mg,
Diethyl [(Z)-1-Chloro-2-(phenylselanyl)-2-hepten-3-yl]phosphonate
[(Z)-2m] and 3-(n-Butyl)-2-ethoxy-4-(phenylselanyl)-2,5-dihydro-1,2-
oxaphosphole 2-Oxide (3m): According to the typical procedure III,
the reaction of PhSeCl (85.5 mg, 0.45 mmol) and 1m (69.2 mg,
0.30 mmol) in H2O (0.6 mL) and dioxane (6.0 mL) at 70 °C for 3 h
afforded a mixture of (Z)-2m and 3m, which was separated by
double chromatography on silica gel to afford (Z)-2m (93.3 mg,
74%) and 3m (12.6 mg, 12%) [petroleum ether/ethyl acetate, 5:1
(first round) to 4:1 (second round)]. (Z)-2m: Liquid. 1H NMR
(300 MHz, CDCl3): δ = 7.70–7.63 (m, 2 H), 7.42–7.28 (m, 3 H),
4.26–4.10 (m, 4 H), 4.00 (s, 2 H), 2.50–2.35 (m, 2 H), 1.58–1.44 (m,
2 H), 1.44–1.28 (m, 2 H), 1.36 (t, J = 7.1 Hz, 6 H), 0.91 (t, J =
7.2 Hz, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 144.9 (d, JPC
= 9.2 Hz), 136.5, 134.1 (d, JPC = 178.3 Hz), 129.2, 129.0, 128.0 (d,
JPC = 1.3 Hz), 62.1 (d, JPC = 6.4 Hz), 42.4 (d, JPC = 20.2 Hz), 32.3
1
6%). (Z)-2n: Liquid. H NMR (300 MHz, CDCl3): δ = 7.73–7.65
(m, 2 H), 7.43–7.28 (m, 3 H), 4.24–4.08 (m, 4 H), 4.02 (s, 2 H),
2.06 (d, J = 13.5 Hz, 3 H), 1.38 (t, J = 6.9 Hz, 6 H) ppm. 13C NMR
(75 MHz, CDCl3): δ = 145.0 (d, JPC = 9.5 Hz), 136.8, 129.2, 129.1,
127.7, 127.2 (d, JPC = 181.8 Hz), 62.1 (d, JPC = 5.9 Hz), 42.6 (d,
JPC = 21.1 Hz), 17.8 (d, JPC = 9.3 Hz), 16.3 (d, JPC = 6.1 Hz) ppm.
31P NMR (121.5 MHz, CDCl3): δ = 18.2 ppm. MS (EI, 70 eV): m/z
(%) = 386 [M(82Se37Cl)]+ (0.49), 385 [M(82Se35Cl) + 1]+ or
[M(80Se37Cl) + 1]+ (0.77), 384 [M(82Se35Cl)]+ or [M(80Se37Cl)]+
(3.38), 383 [M(80Se35Cl) + 1]+ or [M(78Se37Cl) + 1]+ (1.43), 382
[M(80Se35Cl)]+ or [M(78Se37Cl)]+ or [M(77Se37Cl) + 1]+ (7.53), 381
[M(77Se37Cl)]+ or [M(78Se35Cl) + 1]+ or [M(76Se37Cl) + 1]+ (1.18),
380 [M(78Se35Cl)]+ or [M(76Se37Cl)]+ or [M(77Se35Cl) + 1]+ (3.72),
379 [M(77Se35Cl)]+ or [M(76Se35Cl) + 1]+ or [M(74Se37Cl) + 1]+
(1.37), 378 [M(76Se35Cl)]+ or [M(74Se37Cl)]+ (1.31), 225 (100). IR
(d, JPC = 9.2 Hz), 32.0 (d, JPC = 1.4 Hz), 22.8, 16.3 (d, JPC
=
6.4 Hz), 13.7 ppm. 31P NMR (121.5 MHz, CDCl3): δ = 17.8 ppm.
MS (EI, 70 eV): m/z (%) = 429 [M(82Se37Cl) + 1]+ (0.13), 428
[M(82Se37Cl)]+ (0.50), 427 [M(82Se35Cl) + 1]+ or [M(80Se37Cl) +
1]+ (0.84), 426 [M(82Se35Cl)]+ or [M(80Se37Cl)]+ (3.29), 425
[M(80Se35Cl) + 1]+ or [M(78Se37Cl) + 1]+ (2.04), 424 [M(80Se35
-
Cl)]+ or [M(78Se37Cl)]+ or [M(77Se37Cl) + 1]+ (7.08), 423
[M(77Se37Cl)]+ or [M(78Se35Cl) + 1]+ or [M(76Se37Cl) + 1]+ (1.40),
422 [M(78Se35Cl)]+ or [M(76Se37Cl)]+ or [M(77Se35Cl) + 1]+ (3.50),
421 [M(77Se35Cl)]+ or [M(76Se35Cl) + 1]+ or [M(74Se37Cl) + 1]+
(1.35), 420 [M(76Se35Cl)]+ or [M(74Se37Cl)]+ (1.21), 419
[M(74Se35Cl) + 1]+ (0.10), 418 [M(74Se35Cl)]+ (0.11), 267 (100). IR
(neat): ν = 3056, 2980, 2930, 2905, 1569, 1475, 1440, 1391, 1247,
˜
1192, 1162, 1096, 1049 cm–1. HRMS: calcd. for C14H2035ClO3P80Se
[M]+ 382.0004; found 382.0018. 3n: Liquid. 1H NMR (300 MHz,
CDCl3): δ = 7.61–7.55 (m, 2 H), 7.45–7.30 (m, 3 H), 4.38–4.31 (m,
2 H), 4.18–4.04 (m, 2 H), 1.99 (dt, J1 = 14.4, J1 = 2.0 Hz, 3 H),
1.34 (t, J = 7.2 Hz, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ =
144.9 (d, JPC = 33.3 Hz), 135.9, 129.8, 129.5, 123.4, 122.6 (d, JPC
= 158.2 Hz), 71.8 (d, JPC = 8.9 Hz), 63.2 (d, JPC = 6.5 Hz), 16.6 (d,
JPC = 5.3 Hz), 11.7 (d, JPC = 14.3 Hz) ppm. 31P NMR (121.5 MHz,
CDCl3): δ = 39.6 ppm. MS (EI, 70 eV): m/z (%) = 321 [M(82Se) +
1]+ (2.69), 319 [M(80Se) + 1]+ (14.40), 317 [M(78Se) + 1]+ (10.27),
320 [M(82Se)]+ (19.09), 318 [M(80Se)]+ (100), 316 [M(78Se)]+ or [M
(77Se) + 1]+ (50.29), 315 [M(77Se)]+ or [M(76Se) + 1]+ (19.40), 314
(neat): ν = 3057, 2959, 2930, 2872, 1560, 1476, 1438, 1390, 1247,
˜
1220, 1163, 1097, 1051, 1022 cm– 1 . HRMS: calcd. for
C17H2635ClO3P74Se [M]+ 418.0533; found 418.0531. 3m: Liquid. 1H
NMR (300 MHz, CDCl3): δ = 7.62–7.55 (m, 2 H), 7.45–7.29 (m, 3
H), 4.34–4.27 (m, 2 H), 4.16–4.04 (m, 2 H), 2.56–2.26 (m, 2 H),
1.68–1.52 (m, 2 H), 1.47–1.31 (m, 2 H), 1.33 (t, J = 7.1 Hz, 3 H),
0.95 (t, J = 7.5 Hz, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ =
145.0 (d, JPC = 33.8 Hz), 136.0 (d, JPC = 4.5 Hz), 129.7, 129.5,
127.0 (d, JPC = 154.9 Hz), 123.4, 71.4 (d, JPC = 9.7 Hz), 63.0 (d,
JPC = 7.0 Hz), 30.1 (d, JPC = 2.1 Hz), 27.2 (d, JPC = 13.4 Hz), 22.6,
16.5 (d, JPC = 5.1 Hz), 13.8 ppm. 31P NMR (121.5 MHz, CDCl3):
δ = 39.4 ppm. MS (EI, 70 eV): m/z (%) = 363 [M(82Se) + 1]+ (0.73),
361 [M(80Se) + 1]+ (3.38), 359 [M(78Se) + 1]+ (2.09), 357
[M(77Se)]+ or [M (76Se) + 1]+ (2.89), 362 [M(82Se)]+ (3.22), 360
[M(80Se)]+ (15.05), 358 [M(78Se)]+ or [M (77Se) + 1]+ (7.86), 356
[M(76Se)]+ (19.40), 312 [M(74Se)]+ (1.92). IR (neat): ν = 3056, 2979,
˜
2928, 2877, 2853, 1609, 1577, 1476, 1439, 1390, 1344, 1261, 1198,
1162, 1097, 1045, 1024 cm–1. HRMS: calcd. for C12H15O3P80Se
[M]+ 317.9924; found 317.9915.
Diethyl [(Z)-1-Chloro-2-(phenylselanyl)-2-decen-3-yl]phosphonate
[(Z)-2o] and 2-Ethoxy-3-(n-heptyl)-4-(phenylselanyl)-2,5-dihydro-
1,2-oxaphosphole 2-Oxide (3o): According to the typical procedure
III, the reaction of 1o (81.6 mg, 0.30 mmol) and PhSeCl (85.7 mg,
0.45 mmol) in H2O (0.6 mL) and dioxane (6 mL) at 70 °C for 3 h
afforded a mixture of (Z)-2o and 3o, which were separated by re-
peated chromatography on silica gel (petroleum ether/ethyl acetate,
5:1, twice) to afford pure (Z)-2o (95.5 mg, 69%) and 3o (11.0 mg,
9%). (Z)-2o: Colorless liquid. 1H NMR (300 MHz, CDCl3): δ =
7.71–7.65 (m, 2 H), 7.42–7.28 (m, 3 H), 4.26–4.07 (m, 4 H), 4.01
(s, 2 H), 2.49–2.35 (m, 2 H), 1.57–1.44 (m, 2 H), 1.39–1.19 (m, 8
H), 1.37 (t, J = 7.2 Hz, 6 H), 0.87 (t, J = 6.6 Hz, 3 H) ppm. 13C
NMR (75 MHz, CDCl3): δ = 144.9 (d, JPC = 9.1 Hz), 136.6, 134.3
(d, JPC = 178.9 Hz), 129.2, 129.0, 128.1, 62.1 (d, JPC = 5.1 Hz),
[M(76Se)]+ (3.01), 93 (100). IR (neat): ν = 3056, 2958, 2931, 2872,
˜
1601, 1578, 1464, 1440, 1388, 1344, 1264, 1163, 1100, 1044,
1009 cm–1. HRMS: calcd. for C15H21O3P80Se [M]+ 360.0394; found
360.0396.
Diethyl [(Z)-1-Chloro-2-(phenylselanyl)-2-hepten-3-yl]phosphonate
[(Z)-2m] and 3-(n-Butyl)-2-ethoxy-4-(phenylselanyl)-2,5-dihydro-1,2-
oxaphosphole 2-Oxide (3m): According to the typical procedure II,
the reaction of 1m (68.8 mg, 0.30 mmol) and PhSeCl (86.5 mg,
0.45 mmol) in THF (6 mL) and H2O (0.6 mL) at 70 °C for 2 h af-
forded a mixture of (Z)-2m and 3m, which were separated by re-
peated chromatography on silica gel (petroleum ether/ethyl acetate,
108
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© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2010, 101–110

Electrophilic Reaction of 1,2-Alkadienylphosphonates with PhSeCl
42.5 (d, JPC = 20.3 Hz), 32.7 (d, JPC = 9.4 Hz), 31.7, 29.9, 29.7,
28.9, 22.6, 16.4 (d, JPC = 5.8 Hz), 14.1 ppm. 31P NMR (121.5 MHz,
CDCl3): δ = 17.9 ppm. MS (EI, 70 eV): m/z (%) = 470 [M(82Se37-
Cl)]+ (0.47), 469 [M(82Se35Cl) + 1]+ or [M(80Se37Cl) + 1]+ (0.72),
468 [M(82Se35Cl)]+ or [M(80Se37Cl)]+ (2.66), 467 [M(80Se35Cl) +
7.37–7.25 (m, 3 H), 4.57–4.47 (m, 1 H), 4.23–4.03 (m, 2 H), 2.59–
2.30 (m, 2 H), 1.93–1.82 (m, 1 H), 1.62–1.44 (m, 3 H), 1.40–1.28
(m, 5 H), 0.94–0.87 (m, 3 H), 0.87–0.78 (m, 3 H) ppm. MS (EI,
70 eV): m/z (%) = 390 [M(82Se)]+ (3.37), 388 [M(80Se)]+ (13.22), 386
[M(78Se)]+ or [M (77Se) + 1]+ (7.35), 384 [M(76Se)]+ (2.39), 389
1]+ or [M(7 8 Se3 7 Cl) + 1]+ (1.66), 466 [M(8 0Se3 5Cl)]+ or [M(80Se) + 1]+ (5.42), 387 [M(78Se) + 1]+ (2.76), 385 [M(77Se)]+ or
[M(78Se37Cl)]+ or [M(77Se37Cl) + 1]+ (6.12), 465 [M(77Se37Cl)]+ or
[M (76Se) + 1]+ (3.21), 189 (100). IR (neat): ν = 3057, 2961, 2932,
˜
[M(78Se35Cl) + 1]+ or [M(76Se37Cl) + 1]+ (1.23), 464 [M(78Se35
-
2873, 1597, 1577, 1477, 1439, 1386, 1324, 1262, 1163, 1141, 1097,
1039 cm–1. C17H25O3PSe (387.31): calcd. C 52.72, H 6.51; found C
52.69, H 6.60.
Cl)]+ or [M(76Se37Cl)]+ or [M(77Se35Cl) + 1]+ (3.16), 463
[M(77Se35Cl)]+ or [M(76Se35Cl) + 1]+ or [M(74Se37Cl) + 1]+ (1.18),
462 [M(76Se35Cl)]+ or [M(74Se37Cl)]+ (1.05), 309 (100). IR (neat): ν
˜
3-(n-Butyl)-2-ethoxy-5,5-dimethyl-4-(phenylselanyl)-2,5-dihydro-1,2-
oxaphosphole 2-Oxide (3r): According to the typical procedure IV,
the reaction of 1r (77.9 mg, 0.3 mmol) and PhSeCl (86.6 mg,
0.45 mmol) in H2O (0.4 mL) and THF (4 mL) at room temp. for
4 h afforded 3r (101.2 mg, 87%) (petroleum/ethyl acetate, 5:2) as a
liquid. 1H NMR (400 MHz, CDCl3): δ = 7.43–7.38 (m, 2 H), 7.28–
7.22 (m, 3 H), 4.18–4.08 (m, 2 H), 2.40–2.17 (m, 2 H), 1.49 (s, 3
H), 1.46 (s, 3 H), 1.42–1.34 (m, 2 H), 1.32 (t, J = 7.0 Hz, 3 H),
1.23–1.17 (m, 2 H), 0.79 (t, J = 7.4 Hz, 3 H) ppm. 13C NMR
= 3056, 2956, 2927, 2856, 1560, 1469, 1439, 1390, 1248, 1197, 1163,
1097, 1051, 1024 cm–1. HRMS: calcd. for C20H3235ClO3P80Se
[M]+ 466.0943; found 466.0966. 3o: Colorless liquid. 1H NMR
(300 MHz, CDCl3): δ = 7.62–7.55 (m, 2 H), 7.45–7.30 (m, 3 H),
4.38–4.25 (m, 2 H), 4.17–4.04 (m, 2 H), 2.58–2.28 (m, 2 H), 1.70–
1.55 (m, 2 H), 1.43–1.20 (m, 11 H), 0.90 (t, J = 6.3 Hz, 3 H) ppm.
13C NMR (75 MHz, CDCl3): δ = 144.9 (d, JPC = 33.6 Hz), 136.0,
129.7, 129.5, 127.1 (d, JPC = 154.4 Hz), 123.5, 71.5 (d, JPC
=
9.1 Hz), 63.0 (d, JPC = 7.1 Hz), 31.8, 29.6 (d, JPC = 13.5 Hz), 29.0,
28.0 (d, JPC = 2.1 Hz), 27.5 (d, JPC = 12.6 Hz), 22.6, 16.5 (d, JPC
= 6.3 Hz), 14.1 ppm. 31P NMR (121.5 MHz, CDCl3): δ =
39.4 ppm. MS (EI, 70 eV): m/z (%) = 405 [M(82Se) + 1]+ (1.04),
403 [M(80Se) + 1]+ (6.43), 401 [M(78Se) + 1]+ (4.59), 404
[M(82Se)]+ (4.97), 402 [M(80Se)]+ (24.04), 400 [M(78Se)]+ or [M
(77Se) + 1]+ (11.82), 399 [M(77Se)]+ or [M(76Se) + 1]+ (5.35), 398
(100 MHz, CDCl3): δ = 151.7 (d, JPC = 31.1 Hz), 134.8 (d, JPC
=
145.0 Hz), 132.2, 129.5, 128.5 (d, JPC = 1.5 Hz), 127.7, 87.9 (d, JPC
= 8.1 Hz), 62.7 (d, JPC = 7.8 Hz), 29.6 (d, JPC = 1.4 Hz), 28.3 (d,
JPC = 11.7 Hz), 28.1 (d, JPC = 2.8 Hz), 27.4, 22.6, 16.5 (d, JPC
=
6.1 Hz), 13.6 ppm. 31P NMR (121.5 MHz, CDCl3): δ = 34.5 ppm.
MS (EI, 70 eV): m/z (%) = 390 [M(82Se)]+ (2.69), 388 [M(80Se)]+
(12.86), 386 [M(78Se)]+ or [M (77Se) + 1]+ (5.35), 384 [M(76Se)]+
(2.09), 389 [M(80Se) + 1]+ (4.58), 387 [M(78Se) + 1]+ (1.03), 121
[M(76Se)]+ (4.79), 245 (100). IR (neat): ν = 3057, 2927, 2855, 1601,
˜
1577, 1456, 1439, 1390, 1343, 1265, 1163, 1106, 1044 cm–1. HRMS:
calcd. for C18H27O3P80Se [M]+ 402.0863; found 402.0874.
(100). IR (neat): ν = 3059, 2980, 2958, 2932, 2871, 1597, 1577,
˜
1477, 1460, 1439, 1365, 1267, 1224, 1144, 1041 cm–1. HRMS: calcd.
for C17H25O3P80Se [M]+ 388.0707; found 388.0712.
Reaction of Diethyl (Multisubstituted allenyl)phosphonates with
PhSeCl: The reactions of 1p and 1r with PhSeCl at 70 °C according
to the typical procedure II are complicated. Thus, an alternative
approach was used.
Supporting Information (see footnote on the first page of this arti-
1
cle): H, 13C, and 31P NMR spectra of all compounds.
2-Ethoxy-4-(phenylselanyl)-2,5-dihydro-5,5-dimethyl-1,2-oxaphos-
phole 2-Oxide (3p). Typical Procedure IV: H2O (0.6 mL) was added
to a solution of PhSeCl (87.6 mg, 0.45 mmol) in THF (4.5 mL) at
room temperature. Then a solution of 1p (62.9 mg, 0.3 mmol) in
THF (1.5 mL) was added and the resulting mixture was stirred at
room temp. for 3 h. The mixture was quenched with H2O (5 mL)
and extracted with diethyl ether (3ϫ20 mL), washed with brine
(5 mL), and dried with anhydrous Na2SO4. Filtration, concentra-
tion, and flash chromatography on silica gel (petroleum ether/ethyl
acetate, 3:2) afforded 3p (55.7 mg, 55%) as a liquid.[11] 1H NMR
(300 MHz, CDCl3): δ = 7.63–7.57 (m, 2 H), 7.48–7.35 (m, 3 H),
5.25 (d, J = 28.2 Hz, 1 H), 4.12–3.94 (m, 2 H), 1.64 (s, 3 H), 1.58 (s,
3 H), 1.26 (t, J = 7.1 Hz, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ
= 168.9 (d, JPC = 23.3 Hz), 136.5, 130.1, 129.9, 125.3, 109.2 (d, JPC
= 161.9 Hz), 87.2 (d, JPC = 8.3 Hz), 62.8 (d, JPC = 6.4 Hz), 29.1
(d, JPC = 2.9 Hz), 28.4 (d, JPC = 1.9 Hz), 16.4 (d, JPC = 5.9 Hz)
ppm. 31P NMR (121.5 MHz, CDCl3): δ = 34.7 ppm. MS (EI,
70 eV): m/z (%) = 335 [M(82Se) + 1]+ (4.08), 333 [M(80Se) + 1]+
(12.64), 329 [M(77Se)]+ or [M (76Se) + 1]+ (20.13), 334 [M(82Se)]+
(20.41), 332 [M(80Se)]+ (98.89), 330 [M(78Se)]+ or [M(77Se) + 1]+
(56.92), 328 [M(76Se)]+ (20.10), 326 [M(74Se)]+ (2.43), 223 (100). IR
Acknowledgments
Financial support from the Major State Basic Research Develop-
ment Program (Grant No. G2009CB825300) and the Science and
Technology Commission of Shanghai Municipality (No.
07DZ22937) is greatly appreciated. We thank Guofei Chen for re-
producing the results presented in Entries 3 and 10 of Table 2, En-
try 3 of Table 3, and Entry 1 of Table 4. S. M. is a Qiu Shi Adjunct
Professor at Zhejiang University.
[1] H. Guo, R. Qian, Y. Guo, S. Ma, J. Org. Chem. 2008, 73, 7934–
7938.
[2] G. He, H. Guo, R. Qian, Y. Guo, C. Fu, S. Ma, Tetrahedron
2009, 65, 4877–4889.
[3] For studies on allenyl sulfoxides and sulfones, see: a) S. Ma, Q.
Wei, H. Wang, Org. Lett. 2000, 2, 3893–3895; b) S. Ma, H.
Ren, Q. Wei, J. Am. Chem. Soc. 2003, 125, 4817–4830; c) G.
He, C. Zhou, C. Fu, S. Ma, Tetrahedron 2007, 63, 3800–3805;
d) C. Zhou, C. Fu, S. Ma, Tetrahedron 2007, 63, 7612–7616; e)
C. Zhou, C. Fu, S. Ma, Angew. Chem. Int. Ed. 2007, 46, 4379–
4381.
[4] a) C. M. Angelov, T. N. Tancheva, Zh. Obshch. Khim. 1985, 55,
53–57; b) D. M. Mondeshka, C. N. Eancheva, C. M. Angelov,
Phosphorus Sulfur 1987, 31, 89–99.
[5] R. S. Macomber, G. A. Krudy, K. Seff, L. E. Rendón-Diaz-
mirón, J. Org. Chem. 1983, 48, 1425–1430.
[6] For the electrophilic cyclization of allenylphosphonates, see: a)
C. Tancheva, M. Bogilova, D. Mondeshka, Phosphorus Sulfur
Silicon Relat. Elem. 2000, 157, 123–138; b) J. Yuan, X. Ruan,
Y. Yang, X. Huang, Synlett 2007, 18, 2871–2874; c) F. Yu, X.
(neat): ν = 3059, 2981, 2931, 1558, 1475, 1440, 1387, 1368, 1268,
˜
1186, 1141, 1096, 1041 cm–1.
3-(n-Butyl)-2-ethoxy-5-ethyl-4-(phenylselanyl)-2,5-dihydro-1,2-oxa-
phosphole 2-Oxide (3q): According to the typical procedure IV, the
reaction of 1q (77.4 mg, 0.3 mmol) and PhSeCl (86.8 mg,
0.45 mmol) in H2O (0.6 mL) and THF (6 mL) at 70 °C for 0.3 h
afforded 3q (106.5 mg, 92%) (petroleum/ethyl acetate, 5:1 to 3:1)
1
as a liquid. H NMR (400 MHz, CDCl3): δ = 7.53–7.46 (m, 2 H),
Eur. J. Org. Chem. 2010, 101–110
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
109

G. He, Y. Yu, C. Fu, S. Ma
FULL PAPER
Lian, J. Zhao, Y. Yu, S. Ma, J. Org. Chem. 2009, 74, 1130–
1134.
[14] a) S. Ma, X. Hao, X. Huang, Org. Lett. 2003, 5, 1217–1219;
b) S. Ma, X. Hao, X. Meng, X. Huang, J. Org. Chem. 2004,
69, 5720–5724; c) S. Ma, X. Hao, X. Huang, Chem. Commun.
2003, 1082–1083.
[15] Although we have not yet been able to realize such (Z)-seleno-
chlorination for 1,2-alkadienylphosphane oxides highly selec-
tively, the formation of (Z)-selenochlorination products from
allenylphosphane oxides as byproducts has been reported pre-
viously.[2]
[16] a) T. Wirth, “Organoselenium Chemistry” in Topics in Current
Chemistry 208, Springer, Heidelberg, 2000; b) A. Krief in Com-
prehensive Organometallic Chemistry II (Eds.: E. V. Abel,
F. G. A. Stone, G. Wilkinson), Pergamon Press, New York,
1995, vol. 11, chapter 13; c) C. Paulmier, “Selenium Reagents
and Intermediates in Organic Synthesis” in Organic Chemistry
Series 4 (Ed.: J. E. Baldwin), Pergamon Press, Oxford, 1986.
[17] a) C. W. Nogueira, G. Zeni, J. B. T. Rocha, Chem. Rev. 2004,
104, 6255–6285; b) G. Mugesh, W. du Mont, H. Sies, Chem.
Rev. 2001, 101, 2125–2179; c) M. J. Parnham, E. Graf, Prog.
Drug Res. 1991, 36, 9–47; d) C. W. Nogueira, E. B. Quinhones,
E. A. C. Jung, G. Zeni, J. B. T. Rocha, Inflammation Res. 2003,
52, 56–63.
[18] a) J. V. Comasseto, N. Petragnani, J. Organomet. Chem. 1978,
152, 295–304; b) J. V. Comasseto, L. W. Ling, N. Petragnani,
H. A. Stefani, Synthesis 1997, 373–403; c) J. V. Comasseto, J.
Organomet. Chem. 1983, 253, 131–181; d) G. Perin, E. J. Len-
ardão, R. G. Jacob, R. B. Panatieri, Chem. Rev. 2009, 109,
1277–1301.
[7] For the nucleophilic addition of allenylphosphonates with
amines, imidazole, and thiols, see: a) N. G. Khusainova, O. A.
Mostovaya, E. A. Berdnikov, I. A. Litvinov, D. B. Krivolapov,
R. A. Cherkasov, Russ. J. Org. Chem. 2005, 41, 1260–1264; b)
N. G. Khusainova, E. A. Berdnikov, O. A. Mostovaya, S. M.
Rybakov, R. A. Cherkasov, Russ. J. Org. Chem. 2007, 43, 1703–
1705; c) M. Chakravarty, K. C. K. Swamy, Synthesis 2007, 20,
3171–3178.
[8] For phosphane-catalyzed annulations of allenylphosphonates,
see: A. Panossian, N. Fleury-Brégeot, A. Marinetti, Eur. J. Org.
Chem. 2008, 3826–3833.
[9] For transition-metal-catalyzed reactions of allenylphosphon-
ates or -phosphonic acid monoesters, see: a) H. Guo, Z. Zheng,
F. Yu, S. Ma, Angew. Chem. Int. Ed. 2006, 45, 4997–5000; b)
S. Ma, F. Yu, J. Zhao, Synlett 2007, 4, 583–586; c) F. Yu, X.
Lian, S. Ma, Org. Lett. 2007, 9, 1703–1706; d) H. Guo, S. Ma,
Adv. Synth. Catal. 2008, 350, 1213–1217.
[10] a) S. Ma, Pure Appl. Chem. 2007, 79, 261–267; b) S. Ma, Acc.
Chem. Res. 2009, 1679–1688.
[11] a) C. M. Angelov, C. Z. Christov, Synthesis 1984, 664–667; b)
D. D. Enchev, Heteroat. Chem. 2005, 16, 156–158.
[12] Crystal data for (Z)-2j: C14H17BrClO3PSe, M = 458.57, mono-
clinic, space group P2(1)/c, final R indices [IϾ2σ(I)]: R1 =
0.0224, wR2 = 0.0515, R indices (all data): R1 = 0.0244, wR2
= 0.0523, a = 7.5062(2), b = 29.7734(7), c = 7.6014(2) Å, β =
104.1470(10)°, V = 1647.28(7) Å3, T = 173(2) K, Z = 4, reflec-
tions collected/unique: 18865/2881 (Rint = 0.0227), number of
observations [IϾ2σ(I)]: 2707, parameters: 190. CCDC-739001
contains the supplementary crystallographic data for this pa-
per. These data can be obtained free of charge from The Cam-
bridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
[19] a) T. Minami, J. Motoyoshiya, Synthesis 1992, 333–349; b) R.
Engel, Chem. Rev. 1977, 77, 349–367; c) R. R. Breaker, G. R.
Gough, P. T. Gilham, Biochemistry 1993, 32, 9125–9128; d)
M. R. Harnden, A. Parkin, M. J. Parratt, R. M. Perkins, J.
Med. Chem. 1993, 36, 1345–1355.
[20] H. Altenbach, R. Korff, Tetrahedron Lett. 1981, 22, 5175–5178.
[13] Z. Gu, Y. Deng, W. Shu, S. Ma, Adv. Synth. Catal. 2007, 349,
Received: August 12, 2009
Published Online: November 5, 2009
1653–1656.
110
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Eur. J. Org. Chem. 2010, 101–110