Phenyldioxaborolane promoted synthesis of bisphosphine compounds

Article abstract of DOI:10.1016/j.tet.2012.09.088

Bisphosphine compounds have a wide range of applications. In this paper, we reported that bisphosphine compounds could be prepared in moderate to good yields from dialkyl acylphosphonates under mild conditions in the presence of phenyldioxaborolane and potassium hydroxide via a C-P bond cleavage and a subsequent 1,2-migration of phosphoryl group.

Full text of DOI:10.1016/j.tet.2012.09.088

Tetrahedron 68 (2012) 9924e9929
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Phenyldioxaborolane promoted synthesis of bisphosphine compounds
,
a,
b
, ,
y
Yin-Wei Sun a, Peng-Long Zhu a, Qin Xu a , Min Shi
*
*
a Key Laboratory for Advanced Materials and Institute of Fine Chemicals, School of Chemistry & Molecular Engineering, East China University of Science and Technology,
130 Mei-Long Road, Shanghai 200237, China
b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Road, Shanghai 200032, China
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 7 August 2012
Received in revised form 18 September 2012
Accepted 21 September 2012
Available online 26 September 2012
Bisphosphine compounds have a wide range of applications. In this paper, we reported that bisphosphine
compounds could be prepared in moderate to good yields from dialkyl acylphosphonates under mild
conditions in the presence of phenyldioxaborolane and potassium hydroxide via a CeP bond cleavage
and a subsequent 1,2-migration of phosphoryl group.
Ó 2012 Elsevier Ltd. All rights reserved.
Keywords:
Phenyldioxaborolane
Arylboronic acids
Bisphosphine compounds
Phosphoryl group migration
1. Introduction
found that ethyl benzoylphosphonate 1 can react with Yb metal in
THF/hexamethylphosphoramide (HMPA) to produce a mixture of
Organic compounds containing PeC and PeO bonds are not
particularly frequent in nature, but, many of them have diverse
biological activities and have been widely used in pharmacology.1
Bisphosphines are important classes of organic compounds, for
example, bisphosphonates have been used in the treatment of
diseases of bone and calcium metabolism of which osteoporosis
was the most common form.2 More importantly, they can act as
inhibitors of proteolytic enzymes, such as rennin,3 as agents af-
fecting the growth of plants,4 or as haptens for the development of
catalytic antibodies.5 Besides their valuable applications, the use of
them in the production of the dangerous compounds, such as sarin-
and soman-type chemical warfare agents must be also noted.6
Since the last 20 years, many synthetic methods have been de-
veloped for the synthesis of these target compounds in a one-pot
manner.2a,7 But these methods usually need harsh reaction condi-
tions, such as at very high temperatures. The synthesis of these
compounds under mild conditions is still highly desirable.
diethyl 1,2-diphenyl-2-oxoethyl phosphate 6 and diethyl l,l-
(diethylphosphoryloxy)-l-phenylmethylphosphonate 5 in moder-
ate yields at ꢀ35 ꢁC (Scheme 1, Eq. 2).9 However, these reactions are
not very efficient, giving the corresponding diphosphine com-
pounds only in moderate yields via a PeC(OH)eP to PeCHeOeP
rearrangement.10
Early in 1980, Hata and co-workers have reported that the CeP
bond of dialkyl acylphosphonates 1 can be cleaved by amines 2,
affording amides 3 and phosphates 4 in moderate yields (Scheme 1,
Scheme 1. Hata’s and Taniguchi’s previous work on the preparation of bisphosphines.
Based on these previous reports, we envisaged to use in-
expensive reagents to synthesize bisphosphine compounds under
mild conditions. Herein, we wish to report the CeP bond cleavage
of dialkyl alkenylphosphonates or dialkyl arylallylphosphonates
and the subsequent rearrangement in the presence of base and
phenyldioxaborolane or phenyl boronic acid to give the corre-
sponding bisphosphine compounds under mild conditions.
Eq. 1).8 In this process a small amount of
a-(phosphoryloxy)ben-
zylphosphonates 5 have been isolated. Late, Taniguchi’s group
* Corresponding authors. E-mail address: mshi@mail.sioc.ac.cn (M. Shi).
y
Fax: þ86 21 64166128.
0040-4020/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tet.2012.09.088

Y.-W. Sun et al. / Tetrahedron 68 (2012) 9924e9929
9925
2. Results and discussion
We also found the water has great influence on the yield of 8a.
The influence of water content on the yield of 8a in this reaction has
We initially used (E)-dimethyl cinnamoylphosphonate 7a as the
substrate in the presence of a weak Lewis acid phenyldioxaborolane
9 and an inorganic base potassium hydroxide (KOH) to examine the
reaction outcome and found that (E)-1-(dimethoxyphosphoryl)-3-
phenylallyl dimethyl phosphate 8a was formed (Table 1, entry 1).
Next, we attempted to optimize the reaction conditions and the
results are summarized in Table 1. The diphosphine compound 8a
could be afforded in 87% yield based on two molecules of com-
pound 7a to generate one product of 8a in THF in the presence of
2.0 equiv of KOH and 2.0 equiv of 9 (Table 1, entry 4). Reducing the
employed amount of KOH or 9 could significantly decrease the yield
of 8a (Table 1, entries 3e6) and the addition of electrophilic re-
agents, such as benzaldehyde and benzyl alcohol reduced the yield
of 8a (Table 1, entries 1 and 2). The use of strong Lewis acid Yb(OTf)3
gave complex product mixtures (Table 1, entry 7). On the compar-
ison of weak Lewis acids Si(OEt)4, Al(OH)3 or B(OH)3 and PhB(OH)2,
the use of 2.0 equiv of boronic acid gave the better results (Table 1,
entries 8e13). None of 8a could be formed either in the absence of
a Lewis acid or in the absence of a base (Table 1, entries 14 and 15).
The examination of base revealed that KOH is the best one to give
8a in higher yield (Table 1, entries 16e18). THF is the most suitable
solvent for this transformation (Table 1, entries 19e22). We finally
determined optimal conditions of the reaction is using 2.0 equiv of
2-phenyl-1,3,2-dioxaborolane 9 as an additive, 2.0 equiv of potas-
sium hydroxide as a base, and carrying out the reaction in THF
for 12 h.
been shown in Table 2. Adding 8.0 equiv (15
drous THF produced 8a in 87% yield (Table 2, entry 4). The addition
of water >8.0 equiv (15 L) or <8.0 equiv (15 L) all decreased the
yield of 8a (Table 2, entries 1e3 and 5e11). When the water content
increased to more than 22 equiv (40 L), the influence of water
mL) of water in anhy-
m
m
m
content on the yield was not obvious (Table 2, entries 8e11).
Table 2
The influence of water on the yield of 8a
Entrya
H2O (equiv)
Yield of 8a (%)b
1
2
3
4
5
6
7
8
None
1.1
5.6
8.0
11
14
22
33
44
52
50c
64
87
80
77
61
62
62
60
60
9
10
11
56
111
a
Reaction was carried out with 0.1 mmol 7a, 2.0 equiv 2-phenyl-1,3,2-
dioxaborolane and 2.0 equiv KOH in 1.0 mL THF.
Table 1
b
Isolate yield based on two molecules of compound 7a generating one product
Optimization of the reaction conditions
8a.
c
61% 2-hydroxyethyl cinnamate 10 was observed (see Supplementary data).
Having identified the optimal conditions, we next examined
the substrate generality in the reaction. We found that increasing
the steric bulkiness of ester moiety of phosphate group on the
substrate decreased the yield of 8 (Table 3, entries 1e3). The
Entrya
Additive (equiv)
Base (equiv)
Solvent
Yield (%)b
Table 3
Synthesis of bisphosphine compounds 8 with dialkyl acylphosphonates 7 and
phenyldioxaborolane
1c
2e
3
4
5
6
7
8
9
10
11
12g
13
14
15
16
17
18
19
20
21
22
9d (2.0)
9 (0.1)
9 (0.1)
9 (2.0)
9 (2.0)
9 (0.2)
Yb(OTf)3 (2.0)
Si(OEt)4 (2.0)
Al(OH)3 (2.0)
B(OH)3(0.1)
B(OH)3 (0.5)
B(OH)3 (2.0)
PhB(OH)2 (2.0)
None
9 (2.0)
9 (2.0)
9 (2.0)
9 (2.0)
KOH (2.0)
KOH (0.1)
KOH (0.1)
KOH (2.0)
KOH (0.2)
KOH (2.0)
KOH (2.0)
KOH (2.0)
KOH (2.0)
KOH (0.1)
KOH (0.5)
KOH (2.0)
KOH (2.0)
KOH (2.0)
None
K2CO3 (2.0)
Et3N (2.0)
DIEA (2.0)
KOH (2.0)
KOH (2.0)
KOH (2.0)
KOH (2.0)
THF
THF
THF
THF
THF
THF
THF
THF
THF
THF
THF
THF
THF
THF
THF
THF
THF
THF
DCM
Toluene
CH3CN
Et2O
54
22
45
87
84
14
Complex
67
Complex
59f
Entrya
No.
R3
R4
R5
Yield (%)b
67
84
86
Complex
N.R.
83
62
64
72
53
77
52
8
1
2
3
4
5
6
7
8
7a
7b
7c
7d
7e
7f
7g
7h
7i
7j
7k
7l
7m
7n
7o
Me
Et
H
H
H
Me
H
H
H
H
H
H
H
H
H
H
H
C6H5
C6H5
C6H5
C6H5
8a, 87
8b, 58
8c, 47
8d, 84
8e, 77
8f, 85
8g, 75
8h, 56
8i, 51
Complex
8k, 83
8l, 73
iPr
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
o-BrC6H4
p-ClC6H4
p-MeC6H4
m-MeC6H4
o-F, p-BrC6H3
p-NO2C6H4
o-MeO, p-BrC6H3
m-MeOC6H4
p-MeOC6H4
CO
9 (2.0)
9 (2.0)
9 (2.0)
9 (2.0)
9
10
11
12
13
14
15
a
Reaction was carried out with 0.1 mmol 7a in 1.0 mL solvent.
Isolate yield based on two molecules of compound 7a generating one product
b
8a.
Complex
Complex
8o, 71
c
1.0 equiv of benzaldehyde was added.
9 was 2-phenyl-1,3,2-dioxaborolane.
1.0 equiv of benzyl alcohol was added.
91% cinnamic acid was observed.
d
e
f
Me
a
Reaction was carried out with 0.1 mmol 7 in 1.0 mL solvent.
Isolate yield based on two molecules of compound 7 generating one product 8.
g
b
Reaction was carried out within 3 h.

9926
Y.-W. Sun et al. / Tetrahedron 68 (2012) 9924e9929
electronic property of aromatic R5 group also has significant im-
pact on the yield of 8. When aromatic R5 group has a strongly
electron-withdrawing group (such as NO2) or a strongly electron-
donating group (such as MeO) at the para-position or R5 group is
a hetero aromatic group, none of the desired product could be
obtained (Table 3, entries 10, 13, and 14). In other cases, the re-
actions proceeded smoothly to give the desired products in
moderate to good yields (Table 3, entries 4e9 and 11e12). The use
of substrate 7o, in which R5 is a methyl group, afforded the cor-
responding diphosphine compound 8o in 71% yield (Table 3, entry
15).
To clarify the reaction mechanism, a deuterium labeling exper-
iment has been carried out using D2O instead of H2O, we found that
the corresponding d-8a was formed in 77% yield with 99% D con-
tent at the C1 position (Scheme 2). Based on the deuterium labeling
experiment and Fitch’s previous work,10a a plausible reaction
mechanism is proposed in Scheme 3 although it has not been un-
equivocally established. Initially, the in situ generated OHꢀ acts as
a nucleophilic trigger to cleave the CeP bond of 7 to give an anionic
intermediate I and compound II. Compound II has been identified
by spectroscopic data (see Supplementary data along with the
formation of 2-hydroxyethyl cinnamate if using phenyl-
dioxaborolane as a weak Lewis acid). Intermediate I attacks another
molecule of dimethyl acryloylphosphonate 7 to give the corre-
sponding intermediate III, which subsequently undergoes 1,2-
migration of phosphoryl group to produce bisphosphine com-
pound 8. In this process, weak Lewis acid phenyldioxaborolane can
stabilize the in situ generated anionic intermediate I through the
coordination with the boron atom, which may play an important in
this transformation.
Scheme 4. Synthesis of 1-(dimethoxyphosphoryl)-3-phenylpropa-1,2-dienyl dimethyl
phosphate.
For the substrates of simple acylphosphonates, none of the de-
sired products could be obtained under the optimal conditions and
the reaction gave complex product mixtures (Scheme 5).
Scheme 5. Simple acylphosphonate 7p as the substrate in this reaction.
3. Conclusion
In summary, we have reported a novel method to synthesize
bisphosphoryl group containing compounds from dialkyl alkenyl-
phosphonates or dialkyl arylallylphosphonates in the presence of
phenyldioxaborolane and potassium hydroxide via a CeP bond
cleavage and a subsequent 1,2-migration of phosphoryl group. In
this reaction, we used phenyldioxaborolane as a weak Lewis acid as
a promoting agent to give the products in moderate to good yields
under mild conditions.
4. Experimental section
4.1. General remarks
All reactions and manipulations were performed using standard
Schlenk techniques. NMR spectra were recorded with a Varian
Mercury vx or Bruker spectrometer at 400 MHz (1H NMR), 100 MHz
Scheme 2. Experiment of using D2O as an additive.
(
13C NMR), 162 MHz (31P NMR), 376 MHz (19F NMR) in CDCl3, re-
Furthermore, we found that treatment of substrate 7p under
the standard conditions gave allenic compound 9 in 56% yield
(Scheme 4).
spectively. Internal TMS (
d
¼0.0 ppm) was used as the reference for
1H NMR. 31P NMR spectra were referenced to external 85% H3PO4.
19F NMR spectra were referenced to external CF3CCl3. Mass spectra
Scheme 3. A plausible mechanism for the formation of bisphosphine compound 8.

Y.-W. Sun et al. / Tetrahedron 68 (2012) 9924e9929
9927
were recorded on the HP-5989 instrument by EI/ESI methods. In-
frared spectra were recorded on a PerkineElmer PE-983 spec-
trometer with absorption in cmꢀ1. Organic solvents used were
dried by standard methods when necessary. Commercially ob-
tained reagents were used without further purification. All re-
actions were monitored by TLC with Huanghai GF254 silica gel
coated plates. Flash column chromatography was carried out using
by using 300e400 mesh silica gel at increased pressure.
J¼4.4 Hz), 126.7 (d, J¼2.8 Hz), 127.4, 128.2, 128.5, 134.2, 135.3 (d,
J¼13.3 Hz), 135.7 (d, J¼50.9 Hz); IR (CH2Cl2):
n 2980, 1715, 1496,
1467, 1385, 1257, 1178, 1142, 976, 898, 746, 665 cmꢀ1; MS (EI) m/z
(%): 462 [Mþ] (6.5), 378 (9.6), 336 (14.7), 294 (38.0), 197 (22.4), 196
(18.1), 125 (15.9), 116 (12.6), 115 (100), 99 (16.8); HRMS (EI) calcd for
C21H36O7P2 [M]þ requires: 462.1936, found: 462.1941.
4.5. (E)-1-(Dimethoxyphosphoryl)-2-methyl-3-phenylallyl di-
methyl phosphate (Table 3, entry 4, 8d)
4.2. The typical reaction procedure and the spectroscopic
data of the product (E)-1-(dimethoxyphosphoryl)-3-
phenylallyl dimethyl phosphate (Table 3, entry 1, 8a)
A new compound, a colorless liquid (45.7 mg, 84% yield). 1H
NMR (CDCl3, 400 MHz, TMS)
d
2.01 (dd, 3H, J1¼0.8 Hz, J2¼1.6 Hz,
CH3), 3.68 (dd, 3H, J1¼0.8 Hz, J2¼11.6 Hz, CH3), 3.74e3.81 (m, 9H,
CH3), 5.10 (dd, 1H, J1¼10.4 Hz, J2¼14.0 Hz, CH), 6.65 (d, 1H, J¼3.2 Hz,
]CH), 7.17e7.30 (m, 5H, Ar); 31P NMR (CDCl3, 162 MHz, 85% H3PO4)
Into an oven-dried reaction flask under Ar gas protection were
added phosphate 7a (0.3 mmol), phenyl borate esters (0.6 mmol),
potassium hydroxide (0.6 mmol), THF (3.0 mL), and H2O (0.045 mL,
8.0 equiv). The reaction mixture was stirred at room temperature
for 12 h, then the solvent was removed under reduced pressure and
the residue was purified by a flash column chromatography. This is
a new compound, a colorless liquid (301 mg, 87% yield). 1H NMR
d
1.34 (d, J¼34.3 Hz), 19.05 (d, J¼34.5 Hz); 13C NMR (CDCl3,
100 MHz, TMS)
d 14.71, 14.72, 53.79, 53.86, 53.88, 53.95, 54.40,
54.46, 54.51, 54.57, 78.0 (dd, J1¼6.8 Hz, J2¼171 Hz), 127.3, 128.2,
129.0 (d, J¼1.6 Hz), 130.3 (d, J¼2.9 Hz), 131.5 (d, J¼12.5 Hz), 136.0 (d,
J¼1.6 Hz); IR (CH2Cl2):
n 2980, 1467, 1451, 1385, 1257, 1179, 1106,
(CDCl3, 400 MHz, TMS)
d
3.68 (d, 3H, J¼11.6 Hz, CH3), 3.74e3.80 (m,
976, 899, 820, 746, 694 cmꢀ1; MS (EI) m/z (%): 364 [Mþ] (2.7), 239
(9.4), 238 (73.4), 223 (15.6), 206 (8.4), 130 (8.4), 129 (100), 128
(56.6), 127 (10.0), 109 (8.9); HRMS (EI) calcd for C14H22O7P2 [M]þ
requires: 364.0841, found: 364.0843.
9H, CH3), 5.18e5.26 (m, 1H, CH), 6.21e6.28 (m, 1H, ]CH), 6.78 (dd,
1H, J1¼7.6 Hz, J2¼15.6 Hz, ]CH), 7.21e7.29 (m, 3H, Ar), 7.36 (d, 2H,
J¼7.2 Hz, Ar); 31P NMR (CDCl3, 162 MHz, 85% H3PO4)
d 1.31 (d,
J¼29.0 Hz), 18.99 (d, J¼31.4 Hz); 13C NMR (CDCl3, 100 MHz, TMS)
d
53.85, 53.92, 53.96, 54.03, 54.44, 54.51, 54.52, 54.58, 73.8 (dd,
4.6. (E)-3-(2-Bromophenyl)-1-(dimethoxyphosphoryl)allyl
J1¼6.7 Hz, J2¼173.9 Hz), 120.1 (dd, J1¼2.3 Hz, J2¼4.3 Hz), 126.9 (d,
J¼1.6 Hz),128.7, 135.4 (d, J¼2.1 Hz), 136.0, 136.1; IR (CH2Cl2): 2958,
2856, 1648, 1496, 1374, 1261, 1184, 1025, 850, 829, 753, 694 cmꢀ1
dimethyl phosphate (Table 3, entry 5, 8e)
n
;
A new compound, a colorless liquid (49.4 mg, 77% yield). 1H
MS (EI) m/z (%): 350 [Mþ] (12.0), 224 (10.3), 115 (100), 97 (7.5), 85
(7.3), 83 (6.4), 71 (10.0), 57 (11.7), 55 (6.7); HRMS (EI) calcd for
C13H20O7P2 [M]þ requires: 350.0684, found: 350.0685.
Compounds 8be8o were synthesized by adopting the same
procedure described for 8a, using 0.1 mmol of dialkyl acylphos-
phonates.
NMR (CDCl3, 400 MHz, TMS) d 3.80e3.89 (m, 12H, CH3), 5.32e5.40
(m,1H, CH), 6.25e6.33 (m,1H, ]CH), 7.14e7.18 (m,1H, Ar), 7.20 (dd,
1H, J1¼4.4 Hz, J2¼16.0 Hz, ]CH), 7.28e7.32 (m, 1H, Ar), 7.54e7.60
(m, 2H, Ar); 31P NMR (CDCl3, 162 MHz, 85% H3PO4)
d 1.22 (d,
J¼29.6 Hz), 18.39 (d, J¼27.7 Hz); 13C NMR (CDCl3, 100 MHz, TMS)
d
53.86, 53.93, 54.10, 54.17, 54.57, 54.58, 54.63, 54.64, 73.2 (dd,
J1¼6.6 Hz, J2¼171 Hz), 123.3 (dd, J1¼2.1 Hz, J2¼4.3 Hz), 123.8 (d,
4.3. (E)-1-(Diethoxyphosphoryl)-3-phenylallyl diethyl phos-
phate (Table 3, entry 2, 8b)
J¼2.1 Hz), 127.3 (d, J¼2.5 Hz), 127.6, 129.7, 132.9, 133.7 (d,
J¼12.0 Hz), 135.4 (d, J¼2.6 Hz); IR (CH2Cl2):
n 2957, 2855, 1465,
1263, 1185, 1021, 897, 850, 828, 753 cmꢀ1; MS (EI) m/z (%): 428 [Mþ]
(16.8), 430 (17.8), 304 (11.0), 302 (11.8), 196 (6.3), 195 (93.2), 194
(6.9), 193 (100), 187 (6.5), 109 (13.7); HRMS (EI) calcd for
C13H19O7P2Br [M]þ requires: 427.9789, found: 427.9793.
A known compound,11 a colorless liquid (35.4 mg, 58% yield). 1H
NMR (CDCl3, 400 MHz, TMS)
d 1.26e1.36 (m, 12H, CH3), 4.05e4.29
(m, 8H, CH), 5.22e5.30 (m, 1H, CH), 6.27e6.35 (m, 1H, ]CH), 6.84
(dd, 1H, J1¼3.6 Hz, J2¼15.6 Hz, ]CH), 7.23e7.38 (m, 3H, Ar), 7.42 (d,
2H, J¼7.2 Hz, Ar); 31P NMR (CDCl3, 162 MHz, 85% H3PO4)
d
ꢀ1.13 (d,
4.7. (E)-3-(4-Chlorophenyl)-1-(dimethoxyphosphoryl)allyl di-
methyl phosphate (Table 3, entry 6, 8f)
J¼33.2 Hz), 16.76 (d, J¼30.6 Hz); 13C NMR (CDCl3, 100 MHz, TMS)
d
15.68, 15.75, 16.09, 16.14, 16.15, 16.19, 63.14, 63.20, 63.22, 63.30,
63.79, 63.85, 63.89, 63.94, 73.7 (dd, J1¼7.3 Hz, J2¼172.6 Hz), 120.4
A new compound, a colorless liquid (48.9 mg, 85% yield). 1H
(d, J¼2.6 Hz), 126.55, 126.57, 128.3, 128.4, 135.3 (dd, J1¼12.1 Hz,
NMR (CDCl3, 400 MHz, TMS)
d
3.76 (d, 3H, J¼11.2 Hz, CH3),
J2¼15.7 Hz); IR (CH2Cl2):
n
2984, 2911, 1448, 1393, 1258, 1164, 1099,
3.82e3.88 (m, 9H, CH3), 5.28 (ddd, 1H, J1¼8.4 Hz, J2¼13.6 Hz,
1016, 966, 885, 825, 750 cmꢀ1; MS (EI) m/z (%): 406 [Mþ] (13.2), 254
(5.2), 197 (6.0), 196 (6.2), 127 (4.6), 117 (5.4), 116 (8.7), 115 (100), 99
(6.9), 81 (4.5); HRMS (EI) calcd for C17H28O7P2 [M]þ requires:
406.1310, found: 406.1312.
J3¼21.6 Hz, CH), 6.26e6.33 (m, 1H, ]CH), 6.81 (dd, 1H, J1¼3.6 Hz,
J2¼16.0 Hz, ]CH), 7.31 (d, 2H, J¼8.4 Hz), 7.37 (d, 2H, J¼8.0 Hz); 31
P
NMR (CDCl3, 162 MHz, 85% H3PO4)
d
1.24 (d, J¼31.8 Hz), 18.74 (d,
J¼30.9 Hz); 13C NMR (CDCl3, 100 MHz, TMS)
d 53.71, 53.78, 53.86,
53.93, 54.34, 54.40, 54.42, 54.48, 73.4 (dd, J1¼6.5 Hz, J2¼173 Hz),
120.6 (dd, J1¼1.6 Hz, J2¼4.4 Hz), 128.0 (d, J¼1.3 Hz), 128.7, 133.7 (d,
4.4. (E)-1-(Diisopropoxyphosphoryl)-3-phenylallyl diiso-
propyl phosphate (Table 3, entry 3, 8c)
J¼2.4 Hz), 134.2, 134.4 (d, J¼13.1 Hz); IR (CH2Cl2):
n 2957, 2855,
1492, 1459, 1261, 1185, 1025, 894, 848, 832, 796 cmꢀ1; MS (EI) m/z
(%): 384 [Mþ] (19.6), 260 (7.8), 259 (6.2), 258 (18.9), 243 (7.0), 151
(29.6), 150 (9.3), 149 (100), 109 (10.5); HRMS (EI) calcd for
C13H19O7P2Cl [M]þ requires: 384.0295, found: 384.0297.
A new compound, a colorless liquid (32.3 mg, 47% yield). 1H
NMR (CDCl3, 400 MHz, TMS)
d 1.15e1.29 (m, 24H, CH3), 4.50e4.57
(m, 1H, CH), 4.63e4.75 (m, 3H, CH), 5.07e5.15 (m, 1H, CH),
6.16e6.24 (m, 1H, ]CH), 6.73 (dd, 1H, J1¼4.0 Hz, J2¼15.6 Hz, ]CH),
7.19e7.33 (m, 5H, Ar); 31P NMR (CDCl3, 162 MHz, 85% H3PO4)
4.8. (E)-1-(Dimethoxyphosphoryl)-3-p-tolylallyl dimethyl
phosphate (Table 3, entry 7, 8g)
d
ꢀ2.71 (d, J¼36.9 Hz), 15.14 (d, J¼37.4 Hz); 13C NMR (CDCl3,
100 MHz, TMS)
d 23.47, 23.52, 23.55, 23.61, 23.70, 23.75, 23.83,
23.88, 23.99, 24.02, 24.11, 24.14, 71.95, 72.02, 72.06, 72.14, 72.76,
A new compound, a colorless liquid (40.8 mg, 75% yield). 1H
72.82, 72.83, 72.9, 74.4 (dd, J1¼7.4 Hz, J2¼175.3 Hz), 121.2 (d,
NMR (CDCl3, 400 MHz, TMS)
d
2.35 (s, 3H, CH3), 3.74 (d, J¼11.6 Hz,

9928
Y.-W. Sun et al. / Tetrahedron 68 (2012) 9924e9929
CH3), 3.81e3.87 (m, 9H, CH3), 5.23e5.31 (m, 1H, CH), 6.23e6.30 (m,
1H, ]CH), 6.82 (dd, 1H, J1¼3.6 Hz, J2¼15.6 Hz, ]CH), 7.15 (d, 2H,
J¼8.0 Hz, Ar), 7.33 (d, 2H, J¼8.0 Hz, Ar); 31P NMR (CDCl3, 162 MHz,
4.12. (E)-1-(Dimethoxyphosphoryl)-3-(3-methoxyphenyl)allyl
dimethyl phosphate (Table 3, entry 12, 8l)
85% H3PO4)
d
1.32 (d, J¼30.8 Hz), 19.15 (d, J¼31.3 Hz); 13C NMR
A new compound, a colorless liquid (41.6 mg, 73% yield). 1H NMR
(CDCl3, 100 MHz, TMS)
d
21.1, 53.78, 53.85, 53.88, 53.95, 54.35,
(CDCl3, 400 MHz, TMS)
d
3.75 (d, 3H, J¼11.6 Hz, CH3), 3.82e3.88 (m,
54.41, 54.42, 54.49, 73.9 (dd, J1¼6.7 Hz, J2¼173 Hz), 118.8 (dd,
12H, CH3), 5.25e5.32 (m, 1H, CH), 6.28e6.35 (m, 1H, ]CH),
6.80e6.87 (m, 2H, ]CH, Ar), 6.96 (s, 1H, Ar), 7.03 (d, 1H, J¼7.6 Hz,
Ar), 7.24e7.30 (m, 1H, Ar); 31P NMR (CDCl3, 162 MHz, 85% H3PO4)
J1¼2.0 Hz, J2¼4.2 Hz), 126.8 (d, J¼1.7 Hz), 129.3, 132.5 (d, J¼1.7 Hz),
136.2 (d, J¼13.1 Hz), 138.7; IR (CH2Cl2):
n 2957, 2855, 1454, 1262,
1185, 1031, 895, 849, 770 cmꢀ1; MS (EI) m/z (%): 364 [Mþ] (20.5),
239 (10.6), 238 (22.0), 223 (16.6), 130 (9.5), 129 (100), 128 (14.2),
127 (6.0), 109 (6.7); HRMS (EI) calcd for C14H22O7P2 [M]þ requires:
364.0841, found: 364.0844.
d
1.30 (d, J¼31.3 Hz),18.92 (d, J¼30.6 Hz); 13C NMR (CDCl3,100 MHz,
TMS) d 53.84, 53.90, 53.96, 54.03, 54.43, 54.49, 54.56, 55.2, 73.7 (dd,
J1¼6.7 Hz, J2¼173.1 Hz), 112.0, 114.4, 119.5 (d, J¼1.3 Hz), 120.3 (dd,
J1¼2.6 Hz, J2¼4.6 Hz), 129.6, 135.9 (d, J¼13.6 Hz), 136.7 (d, J¼2.4 Hz),
159.7; IR (CH2Cl2):
n 2957, 2854, 1599, 1581, 1457, 1263, 1030, 848,
4.9. (E)-1-(Dimethoxyphosphoryl)-3-m-tolylallyl dimethyl
phosphate (Table 3, entry 8, 8h)
778, 748 cmꢀ1; MS (EI) m/z (%): 380 [Mþ] (16.6), 255 (4.7), 254
(17.3), 239 (11.5), 222 (3.9), 146 (8.4), 145 (100), 115 (8.2), 109 (4.6);
HRMS (EI) calcd for C14H22O8P2 [M]þ requires: 380.0790, found:
380.0794.
A new compound, a colorless liquid (30.6 mg, 56% yield). 1H
NMR (CDCl3, 400 MHz, TMS) d 2.35 (s, 3H, CH3), 3.73e3.87 (m, 12H,
CH3), 5.24e5.32 (m, 1H, CH), 6.30 (ddd, 1H, J1¼5.6 Hz, J2¼7.6 Hz,
J3¼15.6 Hz, ]CH), 6.82 (dd, 1H, J1¼3.6 Hz, J2¼15.6 Hz, ]CH),
7.12e7.13 (m, 1H, Ar), 7.23e7.30 (m, 3H, Ar); 31P NMR (CDCl3,
4.13. (E)-1-(Dimethoxyphosphoryl)but-2-enyl dimethyl phos-
phate (Table 3, entry 15, 8o)
162 MHz, 85% H3PO4)
d
1.28 (d, J¼31.1 Hz), 19.05 (d, J¼31.3 Hz); 13
C
A new compound, a colorless liquid (30.7 mg, 71% yield). 1H
NMR (CDCl3,100 MHz, TMS)
d
21.2, 53.77, 53.84, 53.88, 53.94, 54.35,
NMR (CDCl3, 400 MHz, TMS)
d
1.73 (t, 3H, J¼4.8 Hz, CH3), 3.67e3.79
54.42, 54.48, 73.7 (dd, J1¼6.7 Hz, J2¼172.8 Hz), 119.6 (dd, J1¼1.6 Hz,
(m, 12H, CH3), 4.95e5.02 (m, 1H, CH), 5.53e5.61 (m, 1H, ]CH),
J2¼3.2 Hz), 124.0 (d, J¼1.5 Hz), 127.4 (d, J¼1.4 Hz), 128.5, 129.4, 135.1
5.92e6.01 (m, 1H, ]CH); 31P NMR (CDCl3, 162 MHz, 85% H3PO4)
(d, J¼1.8 Hz), 136.2 (d, J¼13.4 Hz), 138.2; IR (CH2Cl2):
n
2958, 2855,
d
1.06 (d, J¼32.7 Hz), 19.69 (d, J¼33.0 Hz); 13C NMR (CDCl3,
1603, 1455, 1261, 1185, 1025, 882, 847, 776, 746 cmꢀ1; MS (EI) m/z
(%): 364 [Mþ] (20.6), 239 (8.4), 238 (18.5), 223 (8.1), 206 (5.4), 130
(10.2), 129 (100), 128 (13.7), 127 (6.2); HRMS (EI) calcd for
C14H22O7P2 [M]þ requires: 364.0841, found: 364.0843.
100 MHz, TMS) d 17.9, 53.55, 53.62, 53.66, 53.73, 54.21, 54.28, 54.34,
73.5 (dd, J1¼6.7 Hz, J2¼174 Hz), 122.4 (dd, J1¼1.2 Hz, J2¼3.6 Hz),
134.2 (d, J¼13.1 Hz); IR (CH2Cl2):
n 2959, 2856, 1450, 1257, 1185,
1025, 999, 881, 848, 782 cmꢀ1; MS (EI) m/z (%): 288 [Mþ] (5.2), 180
(6.3), 179 (100), 163 (6.4), 162 (11.7), 127 (55.1), 109 (15.3), 93 (6.0),
79 (5.5); HRMS (EI) calcd for C8H18O7P2 [M]þ requires: 288.0528,
found: 288.0531.
4.10. (E)-3-(4-Bromo-2-fluorophenyl)-1-(dimethoxy-
phosphoryl)allyl dimethyl phosphate (Table 3, entry 9, 8i)
A new compound, a colorless liquid (34.0 mg, 51% yield). 1H
4.14. 1-(Dimethoxyphosphoryl)-3-phenylpropa-1,2-dienyl di-
methyl phosphate (Scheme 4, compound 9)
NMR (CDCl3, 400 MHz, TMS)
d 3.77e3.88 (m, 12H, CH3), 5.26e5.35
(m, 1H, CH), 6.38e6.45 (m, 1H, ]CH), 6.88e6.93 (m, 1H, ]CH),
7.24e7.31 (m, 2H, Ar), 7.33e7.37 (m, 1H, Ar); 31P NMR (CDCl3,
A new compound, a colorless liquid (31.1 mg, 56% yield). 1H NMR
(CDCl3, 400 MHz, TMS) d 3.71e3.80 (m, 12H, CH3), 6.99 (dd, 1H,
162 MHz, 85% H3PO4)
NMR (CDCl3, 376 MHz, CF3CCl3)
d
1.17 (d, J¼29.6 Hz), 18.35 (d, J¼29.5 Hz); 19
F
d
ꢀ116.4; 13C NMR (CDCl3,
J1¼3.6 Hz, J2¼10.0 Hz, ]CH), 7.23e7.32 (m, 3H, Ar), 7.40 (d, 2H,
100 MHz, TMS)
d
53.9, 54.0, 54.1, 54.2, 54.59, 54.64, 54.65, 54.72,
J¼7.2 Hz, Ar); 31P NMR (CDCl3, 162 MHz, 85% H3PO4)
d
ꢀ2.17 (d,
73.6 (dd, J1¼6.5 Hz, J2¼171.8 Hz), 119.4, 119.7, 122.3 (d, J¼1.4 Hz),
122.4 (d, J¼3.1 Hz), 122.6 (d, J¼2.5 Hz), 123.66, 123.70, 123.74,
123.76, 126.8 (dd, J1¼2.8 Hz, J2¼11.8 Hz), 127.7 (d, J¼3.9 Hz), 128.9
J¼25.4 Hz), 9.88 (d, J¼26.7 Hz); 13C NMR (CDCl3, 100 MHz, TMS)
d
53.57, 53.63, 53.67, 53.73, 54.69, 54.75, 54.77, 109.3, 109.4 (d,
J¼1.5 Hz), 115.1 (dd, J1¼11.1 Hz, J2¼253 Hz), 128.3 (d, J¼1.1 Hz),
(dd, J1¼1.9 Hz, J2¼3.6 Hz); IR (CH2Cl2):
n 2958, 2855, 1600, 1484,
128.9, 129.4, 130.9 (dd, J1¼1.2 Hz, J2¼6.3 Hz), 201.1 (dd, J1¼4.5 Hz,
1265, 1186, 1027, 850, 802, 731 cmꢀ1; MS (EI) m/z (%): 446 [Mþ]
(23.1), 448 (23.0), 322 (11.5), 320 (10.1), 213 (93.9), 211 (100), 187
(9.48), 132 (7.20), 109 (21.5); HRMS (EI) calcd for C13H18O7FP2Br
[M]þ requires: 445.9695, found: 445.9697.
J2¼25.2 Hz); IR (CH2Cl2):
n 3056, 2958, 2856, 1453, 1266, 1185, 1032,
878, 853, 731, 700 cmꢀ1; MS (EI) m/z (%): 348 [Mþ] (100), 333
(49.6), 239 (23.4), 207 (24.7), 192 (55.0), 129 (42.1), 115 (34.5), 114
(31.7), 109 (48.1), 93 (31.9); HRMS (ESI) calcd for C13H18O7P2Na
[MþNa]þ requires: 371.0425, found: 371.0439.
4.11. (E)-3-(4-Bromo-2-methoxyphenyl)-1-(dimethoxy-
phosphoryl)allyl dimethyl phosphate (Table 3, entry 11, 8k)
Acknowledgements
A new compound, a colorless liquid (57.2 mg, 83% yield). 1H
We thank the Shanghai Municipal Committee of Science and
Technology (11JC1402600), National Basic Research Program of
China (973)-2009CB825300, the Fundamental Research Funds for
the Central Universities and the National Natural Science Founda-
tion of China for financial support (21072206, 20472096, 20872162,
20672127, 21121062 and 20732008).
NMR (CDCl3, 400 MHz, TMS)
d
3.76 (d, 3H, J¼11.2 Hz, CH3),
3.81e3.87 (m, 12H, CH3), 5.23e5.31 (m, 1H, CH), 6.31e6.39 (m, 1H,
]CH), 7.01e7.08 (m, 3H, ]CH and Ar), 7.31 (d, 1H, J¼8.0 Hz, Ar); 31P
NMR (CDCl3, 162 MHz, 85% H3PO4)
d
1.26 (d, J¼30.7 Hz), 18.97 (d,
J¼28.8 Hz); 13C NMR (CDCl3, 100 MHz, TMS)
d 53.89, 53.96, 54.03,
54.10, 54.47, 54.52, 54.60, 55.7, 74.1 (dd, J1¼7.3 Hz, J2¼173.2 Hz),
114.5, 121.1 (d, J¼3.0 Hz), 123.1, 123.4 (d, J¼1.4 Hz), 123.7, 128.5,
Supplementary data
130.2 (d, J¼13.2 Hz), 157.6; IR (CH2Cl2):
n 2956, 2854, 1588, 1487,
1461, 1400, 1247, 1184, 1025, 849, 802 cmꢀ1; MS (EI) m/z (%): 458
[Mþ] (20.8), 460 (21.1), 334 (22.8), 332 (21.4), 319 (20.1), 225 (92.0),
224 (24.5), 223 (100), 109 (23.6); HRMS (EI) calcd for C14H21O8P2Br
[M]þ requires: 457.9895, found: 457.9900.
The NMR spectroscopic data and charts of the compounds
are included in the Supplementary data. Supplementary data
related to this article can be found at http://dx.doi.org/10.1016/
j.tet.2012.09.088.

Y.-W. Sun et al. / Tetrahedron 68 (2012) 9924e9929
9929
8711e8712; (c) Pachamuthu, K.; Schmidt, R. R. Chem. Commun. 2004,
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Harris, J. E.; Salt, M. C.; Taylor, H. V. Org. Biomol. Chem. 2008, 6, 577e585; (e)
Demir, A. S.; Aybey, A.; Emrullahoglu, M. Synthesis 2009, 10, 1655e1658; (f)
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