Efficient synthesis of 2-methylene-3phosphorylalkanoates: Phosphorylation of baylis-hillman bromides via an SN2-SN2' strategy

Article abstract of DOI:10.1080/10426500802418545

A novel synthesis of 2-methylene-3-phosphorylalkanoates under mild conditions is described. Thus, Balyis-Hillman bromides react with secondary phosphine oxides or H-phosphonites in the presence of DABCO via an S _N2-S_N2' protocol to p

Full text of DOI:10.1080/10426500802418545

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Efficient Synthesis of 2-
Methylene-3phosphorylalkanoates:
Phosphorylation of
Baylis–Hillman Bromides via an
S N 2-S N 2′ Strategy
Liancheng Yang a , Longhe Xu a & Chunrui Yu b
a State Key Laboratory of Fine Chemicals , Dalian
University of Technology , Dalian, China
b National Pesticide Engineering Research Center ,
Shenyang Research Institute of Chemical Industry ,
Shenyang, China
Published online: 22 Jul 2009.
To cite this article: Liancheng Yang , Longhe Xu & Chunrui Yu (2009) Efficient
Synthesis of 2-Methylene-3phosphorylalkanoates: Phosphorylation of Baylis–Hillman
Bromides via an S N 2-S N 2′ Strategy, Phosphorus, Sulfur, and Silicon and the Related
Elements, 184:8, 2049-2057, DOI: 10.1080/10426500802418545
To link to this article: http://dx.doi.org/10.1080/10426500802418545
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Phosphorus, Sulfur, and Silicon, 184:2049–2057, 2009
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500802418545
Efficient Synthesis of 2-Methylene-3-
phosphorylalkanoates: Phosphorylation of
Baylis–Hillman Bromides via an SN2-SN2ꢀ Strategy
Liancheng Yang,1 Longhe Xu,1 and Chunrui Yu2
1State Key Laboratory of Fine Chemicals, Dalian University of
Technology, Dalian, China
2National Pesticide Engineering Research Center, Shenyang Research
Institute of Chemical Industry, Shenyang, China
A novel synthesis of 2-methylene-3-phosphorylalkanoates under mild conditions is
described. Thus, Balyis–Hillman bromides react with secondary phosphine oxides
or H-phosphonites in the presence of DABCO via an SN2-SN2ꢀ protocol to produce
the target compounds in good yields.
Keywords Baylis–Hillman bromides; DABCO; nucleophilic substitution; phosphoryla-
tion
INTRODUCTION
The Morita–Baylis–Hillman reaction produces highly functionalized
molecules, which have been widely used for the synthesis of vari-
ous biologically active molecules and natural products.1–10 Recently,
the Baylis–Hillman bromides 1, (Z)-allyl bromides obtained from the
Baylis–Hillman adducts, have attracted much attentions as synthetic
intermediates.4 Nucleophiles can substitute the bromide atom of 1 to
give 2 (SN2)11–13 or attack the vinyl carbon of 1 to give 4 (SN2ꢀ)14,15 de-
pending on the starting materials and reaction conditions (Scheme 1).
In many cases, the SN2 and SN2ꢀ reactions compete and lead to mix-
tures of 2 and 4. Selective preparation of 4 can be achieved via the
successive SN2–SN2ꢀ reaction of Baylis–Hillman bromides 1 via 3 as
shown in Scheme 1. However, the first SN2 type reaction leading to
3 by the first nucleophile, Nuꢀ, must occur completely in order to
Received 14 May 2008; accepted 12 August 2008.
We thank Shenyang BMD Chemical Co., Ltd. (China) for funding this project.
Address correspondence to Liancheng Yang, Room 213, Petrochemical Department,
Liaoning Petrochemical Vocational Technology College, Jinzhou, 121001, China. E-mail:
ylc94@163.com
2049

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L. Yang et al.
SCHEME 1
synthesize 4 in a pure state. Otherwise, the competing SN2 reaction by
the second nucleophile, NuH, leading to 2, can occur along with the next
SN2ꢀ reaction. In such a situation, mixtures might be obtained. An addi-
tional requirement for the effective preparation of type 4 compounds is
that the first nucleophile should be exchanged by a second nucleophile
effectively. Transformation of 1 to 3 could be possible with DABCO16
or DBU.17,18 Some nucleophiles have been used in the next SN2ꢀ step,
which includes LiBEt3H,19 NaBH4,16 nitroalkenes,17 hydroperoxides,20
and zwitterion derived from DABCO and acrylonitrile.18,21
In connection to our ongoing research program in bioactive
chemistry,15 we directed our studies towards phosphorylation of Baylis–
Hillman bromides 1 to produce 2-methylene-3-phosphorylalkanoates
(type 4 compounds) as lead compounds. The target compounds con-
tain active methylene and P-C bond, and will be versatile intermedi-
ates in bioorganic chemistry. Thus we aimed to prepare the intended
compounds by the successive SN2–SN2ꢀ strategy from the Baylis–
Hillman bromides 1. To the best of our knowledge, there has been
no reported use of any nucleophilic RꢀRꢀꢀP(O)H in these transforma-
tions. Although Du et al.22 have reported the preparation of one of
2-methylene-3-phosphorylalkanoates via tert-butyl carbonate of the
Morita–Baylis–Hillman products, the use of cheap and easily obtained
Baylis–Hillman bromides 1 as electrophiles provided a promising way
to get 2-methylene-3-phosphorylalkanoates.
In this article, we would like to describe the results on the reaction of
RꢀRꢀꢀP(O)H, involving secondary phosphine oxides or H-phosphonites,
with some DABCO salts of Baylis–Hillman bromides derived from ary-
laldehydes.

Efficient Synthesis of 2-Methylene-3-phosphorylalkanoates
2051
TABLE I Synthesis of 2-Methylene-3-phosphorylalkanoates (4a–i)
Entry
RꢀRꢀꢀP(O)H
Baylis–Hillman bromides
Product
Yield (%)a
1
2
3
4
5
6
7
8
9
10
11
12
13
14
5a
5a
5a
5a
5a
5a
5a
5a
5a
5b
5c
5c
5c
5c
1a
1a
1b
1b
1c
1c
1d
1e
1f
1f
1f
1f
1g
1g
4a
4a
4b
4b
4c
4c
4d
4e
4f
4g
4h
4h
4i
82
83b
79
81b
80
82b
81
75
85
84
32
61b
34
4i
63b
aIsolated yields.
bToluene as solvent.
RESULTS AND DISCUSSION
Accordingly, we have first examined the reaction of (Z)-methyl 2-
(bromomethyl)-3-phenylacrylate (1a)23,24 with diphenylphosphine ox-
ide (5a) in acetonitrile under various conditions. The best results
were obtained when (Z)-methyl 2-(bromomethyl)-3-phenylacrylate (1a)
(1 mmol) was treated with DABCO (2 mmol) in acetonitrile at room
temperature for 15 min, followed by treatment with diphenylphosphine
oxide (5a) (1 mmol) for 12 h at 80◦C under nitrogen, thus providing the
desired methyl 2-((diphenylphosphoryl) (phenyl)methyl)acrylate (4a)
after the usual work-up, followed by column chromatography in 82%
yield (Table I, Entry 1). However, when K2CO3 or Et3N was added as
base, mixture of 2a and 4a were obtained with the ratio of 2a/4a 3/7
and 4/6 respectively (Scheme 2).
SCHEME 2
This methodology was then extended to a representative class of
the Baylis–Hillman bromides (1b–g)23,24; a variety of 2-methylene-3-
phosphoryl-alkanoates (4b–i) have been synthesized in good to high

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L. Yang et al.
SCHEME 3
yields (Scheme 3, Table I). Changing R from Me to Et had little effect
on yields of the desired product (Table I, Entries 3, 5). However, when
5c was used as nucleophile under similar conditions, only moderate
yields of 4h and 4i were obtained (Entries 11, 13); presumably side
reactions took place via the cleavage of P-O bonds. When toluene was
used as solvent, higher yields of 4h and4i were achieved (Entries 12,
14). Toluene was also a suitable solvent in the preparation of other
2-methylene-3-phosphoryl-alkanoates (Entries 2, 4, 6).
CONCLUSION
A new and convenient protocol for the synthesis of 2-methylene-3-
phosphorylalkanoates involving successive SN2–SN2ꢀ reaction of the
Baylis–Hillman bromides with secondary phosphine oxides or H-
phosphonites was developed.
EXPERIMENTAL
General
All reactions were carried out under nitrogen atmosphere.
Diphenylphosphine oxide (1a),25 dibenzylphosphine oxide (1b),26 and
(Z)-allyl bromides (2a–f)23,24 were prepared according to the reported
procedures. Other reagents and solvents were commercially available
and distilled, recrystallized, or dehydrated thoroughly. Melting points
were determined on a Buchi melting point apparatus and are uncor-
1
rected. H NMR and 13C NMR spectra were performed on a Mercury
1
300 spectrometer (Varian, H: 300 MHz, 13C: 75 MHz) with CDCl3 as
the solvent and TMS as the internal standard. 31P NMR spectra were
obtained on the Mercury 300 (Varian, 121 MHz) spectrometer using
H3PO4 as an internal standard. Infrared spectra were recorded with

Efficient Synthesis of 2-Methylene-3-phosphorylalkanoates
2053
a PE-983G instrument (Perkin-Elmer). Mass spectra were recorded on
FTICR-MS (Ionspec 7.0T). Combustion analyses for C and H elemental
composition were made with a Vario EL III analyzer (Elementar). Phos-
phorus contents were determined by oxygen flask method. All reactions
were monitored by TLC.
General Procedure for the Preparation of
2-Methylene-3-phosphorylalkanoates
To a flask purged with N2 containing acetonitrile or toluene (3 mL),
Baylis–Hillman bromides (1a–g) (1mmol) and DABCO (2 mmol) were
added. The reaction mixture was stirred at room temperature for
15min, then RꢀRꢀꢀP(O)H (5a–c) (1 mmol) was added and stirred at 80◦C
for 8–16 h under nitrogen. The reaction was continued until complete
consumption of the RꢀRꢀꢀP(O)H, which is monitored by TLC or HPLC,
then diluted with CH2Cl2 (15 mL), washed with water and brine, dried
over anhydrous sodium sulphate, and concentrated under reduced pres-
sure. Subsequent flash column chromatography over silica gel gave
products 4a–i.
Methyl 2-((Diphenylphosphoryl)(phenyl) methyl)acrylate (4a)
White solid: mp 146–147◦C, IR (KBr): 3421, 3055, 2947, 1718, 1620,
1
1491, 1437, 1323, 1242, 1184, 1128 cm−1; H NMR (300 MHz, CDCl3,
TMS): δ 3.62 (s, 3H), 5.04 (d, J = 8.4 Hz, 1H), 6.43 (d, J = 1.8 Hz, 1H),
6.82 (d, J = 2.4 Hz, 1H), 7.16–7.23 (m, 3H), 7.25–7.28 (m, 2H), 7.32–
7.37 (m, 3H), 7.44–7.50 (m, 5H), 7.50–7.91 (m, 2H); 13C NMR (75 MHz,
CDCl3, TMS): δ 45.61 (d, J = 67.3 Hz), 52.24, 127.14 (d, J = 2.0 Hz),
127.97, 128.13, 128.23, 128.46, 128.53, 128.61, 130.00, 130.08, 130.90,
131.02, 131.11, 131.23, 131.36(d, J = 2.6 Hz), 131.66 (d, J = 2.6 Hz),
132.84 (d, J = 5.4 Hz), 134.70 (d, J = 5.2 Hz), 136.45 (d, J = 2.0 Hz),
166.73 (d, J = 9.5 Hz); 31P NMR (121 MHz, CDCl3, H3PO4): δ 31.55;
Anal. calcd for C23H21O3P: C, 73.39; H, 5.62; P, 8.23; found: C, 73.37;
H, 5.65; P, 8.20.
Methyl 2-((4-Chlorophenyl)(diphenylphosphoryl)
methyl)acrylate (4b)
White solid: mp 186–187◦C, IR (KBr): 3429, 3055, 2951, 1724, 1614,
1489, 1437, 1309, 1244, 1180, 1130 cm−1; 1H NMR (300 MHz, CDCl3):
δ 3.63 (s, 3H), 5.01 (d, J = 8.4 Hz, 1H), 6.43 (s, 1H), 6.79 (s, 1H), 7.15
(d, J = 8.4 Hz, 2H), 7.28–7.31 (m, 4H), 7.36–7.52 (m, 6H), 7.86 (t, J =
8.1 Hz, 2H);13C NMR (75 MHz, CDCl3, TMS): δ 45.04 (d, J = 69.2 Hz),
52.33, 128.16, 128.31, 128.42, 128.54, 128.69, 130.43, 130.51, 130.85,

2054
L. Yang et al.
130.96, 131.05, 131.17, 131.29, 131.36, 131.59, 131.82, 136.30 (d, J =
1.1 Hz), 165.90 (d, J = 8.2 Hz); 31P NMR (121 MHz, CDCl3, H3PO4): δ
31.21. Anal. calcd for C23H20ClO3P: C, 67.24; H, 4.91; P, 7.54; found: C,
67.26; H, 4.94; P, 7.50.
Ethyl 2-((4-Chlorophenyl)(diphenylphosphoryl)
methyl)acrylate (4c)
White solid: mp 114–115◦C, IR (KBr): 3425, 3057, 2983, 1622, 1489,
1439, 1309, 1236, 1188, 1122 cm−1; 1H NMR (300 MHz, CDCl3): δ 1.18
(t, J = 6.9 Hz, 3H), 4.03–4.11 (m, 2H), 5.04 (d, J = 7.8 Hz, 1H), 6.44 (s,
1H), 6.77 (s, 1H), 7.13 (d, J = 7.8 Hz, 2H), 7.29–7.40 (m, 5H), 7.47–7.52
(m, 5H), 7.87 (t, J = 8.0 Hz, 2H);13C NMR (75 MHz, CDCl3, TMS): δ
13.97, 44.95 (d, J = 68.7 Hz), 61.40, 128.19, 128.34, 128.44, 128.56,
128.69, 130.31, 130.89, 131.00, 131.11, 131.23, 131.32, 131.38, 131.62,
131.84, 133.27, 133.41, 136.40, 166.12 (d, J = 9.2 Hz); 31P NMR (121
MHz, CDCl3, H3PO4): δ 31.60. Anal. calcd for C24H22ClO3P: C, 67.85;
H, 5.22; P, 7.29; found: C, 67.81; H, 5.24; Cl, 8.30; O, 11.35; P, 7.24.
Ethyl 2-((2,4-dichlorophenyl)(diphenylphosphoryl)
methyl)acrylate (4d)
White solid: mp 128–129◦C, IR (KBr): 3059, 2982, 1716, 1622, 1583,
1
1470, 1439, 1369, 1294, 1230, 1194, 1119, 1026 cm−1; H NMR (300
MHz, CDCl3): δ 1.17 (t, J = 7.2 Hz, 3H), 4.00–4.04 (m, 2H), 5.64 (d, J =
8.7 Hz, 1H), 6.50 (d, J = 2.4 Hz, 1H), 6.63 (d, J = 2.4 Hz, 1H), 7.19–7.33
(m, 4H), 7.39–7.53 (m, 6H), 7.83–7.90 (m, 2H), 7.98 (dd, J = 10.2 Hz, J
= 1.5 Hz, 1H); 13C NMR (75 MHz, CDCl3, TMS): δ 13.97, 40.65 (d, J =
66.4 Hz), 61.36, 127.30, 128.15, 128.31, 128.49, 128.65, 128.97, 130.98,
131.11, 131.37, 131.43, 131.49, 131.86 (d, J = 2.3 Hz), 131.99, 132.07
(d, J = 3.5 Hz), 132.62 (d, J = 4.0 Hz), 133.78 (d, J = 2.3 Hz), 135.31
(d, J = 8.0 Hz), 135.84 (d, J = 2.9 Hz), 165.68 (d, J = 8.0 Hz); 31P NMR
(121 MHz, CDCl3, H3PO4): δ 31.31. Anal. calcd for C24H21Cl2O3P: C,
62.76; H, 4.61; P, 6.74; found: C, 62.71; H, 4.63; P, 6.71.
Methyl 2-((Diphenylphosphoryl)(furan-2-yl)methyl)acrylate
(4e)
White solid: mp 82–83◦C, IR (KBr): 3059, 2926, 2854, 1718, 1622,
1
1587, 1500, 1437, 1392, 1271, 1203, 1120 cm−1; H NMR (300 MHz,
CDCl3): δ 3.54 (s, 3H), 5.38 (d, J = 10.5 Hz, 1H), 6.20–6.22 (m, 1H),
6.39–6.41 (m, 1H), 6.53 (dd, J = 10.2 Hz, J = 3.5 Hz, 2H), 7.23 (s,
1H), 7.35–7.48 (m, 6H), 7.65–7.81 (m, 4H); 13C NMR (75 MHz, CDCl3,
TMS): δ 34.81 (d, J = 67.0 Hz), 47.09, 104.67, 105.55, 123.13, 123.28,
126.25, 126.37, 126.50, 126.59, 126.64, 126.68, 126.70, 126.74, 128.14

Efficient Synthesis of 2-Methylene-3-phosphorylalkanoates
2055
(d, J = 4.1 Hz), 136.95 (d, J = 1.7 Hz), 143.24 (d, J = 4.0 Hz), 161.23 (d,
J = 5.8 Hz); 31P NMR (121 MHz, CDCl3, H3PO4): δ 29.59. Anal. calcd
for C21H19O4P: C, 68.85; H, 5.23; P, 8.45; found: C, 68.90; H, 5.26; P,
8.41.
Ethyl 2-((Diphenylphosphoryl)(4-nitrophenyl)methyl)acrylate
(4f)
White solid: mp 155–156◦C, IR (KBr): 3417, 3059, 2980, 1713, 1626,
1516, 1437, 1319, 1244, 1180, 1124 cm−1; 1H NMR (300 MHz, CDCl3):
δ 1.19 (t, J = 6.9 Hz, 3H), 4.06–4.14 (m, 2H), 5.17 (d, J = 8.1 Hz, 1H),
6.51 (d, J = 1.5 Hz, 1H), 6.85 (d, J = 2.1 Hz, 1H), 7.27–7.33 (m, 2H),
7.37 (t, J = 7.2 Hz, 1H), 7.48–7.55 (m, 7H), 7.86–7.91 (m, 2H), 8.02 (d, J
= 8.1 Hz, 2H); 13C NMR (75 MHz, CDCl3, TMS): δ 13.92, 45.49 (d, J =
67.3 Hz), 61.21, 127.08 (d, J = 2.0 Hz), 127.94, 128.10, 128.20, 128.40,
128.55, 129.97, 130.05, 130.87, 130.99, 131.09, 131.21, 131.31 (d, J=2.6
Hz), 131.60 (d, J=2.6 Hz), 132.86 (d, J = 5.2 Hz), 134.85 (d, J = 5.4 Hz),
136.67, 166.21 (d, J = 9.6 Hz); 31P NMR (121 MHz, CDCl3, H3PO4): δ
31.60. Anal. calcd for C24H22NO5P: C, 66.20; H, 5.09; P, 7.11; found: C,
66.23; H, 5.11; P, 7.10.
Ethyl 2-((Dibenzylphosphoryl)(4-nitrophenyl)methyl)acrylate
(4g)
White solid: mp 110–111◦C, IR (KBr): 3063, 2982, 2929, 1711, 1622,
1
1599, 1522, 1495, 1454, 1402, 1348, 1311, 1242, 1186, 1128 cm−1; H
NMR (300 MHz, CDCl3): δ 1.26 (t, J = 7.2 Hz, 3H), 2.85–2.90 (m, 2H),
3.17–3.24(m, 2H), 4.12–4.17 (m, 2H), 4.34 (d, J = 6.9 Hz, 1H), 6.49
(s, 1H), 6.80 (s, 1H), 7.00–7.03 (m, 2H), 7.14–7.17 (m, 5H), 7.17–7.29
(m, 3H), 7.61 (d, J = 8.4 Hz, 2H), 8.06 (d, J = 8.7 Hz, 2H); 13C NMR
(75 MHz, CDCl3, TMS): δ 14.02, 34.95 (d, J = 20.6 Hz), 35.77 (d, J =
18.6 Hz), 44.30 (d, J = 59.4 Hz), 61.65, 123.65, 126.90 (d, J = 2.3 Hz),
127.147 (d, J = 2.6 Hz), 128.49 (d, J = 1.4 Hz), 128.79 (d, J = 1.7 Hz),
129.68, 129.74, 130.44, 130.50, 130.61, 130.68, 130.74, 130.83, 131.42
(d, J = 6.6 Hz), 136.01(d, J = 2.6 Hz), 143.62 (d, J = 4.6 Hz), 147.17,
165.72 (d, J = 8.6 Hz); 31P NMR (121 MHz, CDCl3, H3PO4): δ 43.77.
Anal. calcd for C26H26NO5P: C, 67.38; H, 5.65; P, 6.68; found: C, 67.37;
H, 5.67; P, 6.67.
Ethyl 2-((Diethoxyphosphoryl)(4-nitrophenyl)methyl)acrylate
(4h)
Pale yellow oil, IR (KBr): 3059, 2983, 2906, 1714, 1651, 1622, 1493,
1439, 1392, 1319, 1240, 1205, 1132,1053, 1026, 966, 700 cm−1; 1H NMR
(300 MHz, CDCl3): δ 1.07 (t, J = 7.2 Hz, 3H), 1.17–1.30 (m, 6H),

2056
L. Yang et al.
3.68–3.74 (m, 1H), 3.86–3.91 (m, 1H), 4.04–4.19 (m, 4H), 4.60 (d,
J = 24.3 Hz, 1H), 6.54–6.56 (m, 2H), 7.16–7.28 (m, 2H), 7.44–7.49 (m,
2H); 13C NMR (75 MHz, CDCl3, TMS): δ 13.94, 16.03 (d, J = 5.7 Hz),
16.22 (d, J = 6.0 Hz), 44.2 (d, J = 140.8 Hz), 61.16, 62.32 (d, J = 7.1
Hz), 62.80 (d, J = 6.9 Hz), 127.28 (d, J = 2.6 Hz), 128.33 (d, J = 1.73
Hz), 128.43, 128.52, 129.50, 129.59, 134.81 (d, J = 6.1 Hz), 136.21 (d, J
= 1.7 Hz), 165.99 (d, J = 14.0 Hz); 31P NMR (121 MHz, CDCl3, H3PO4):
δ 24.62. Anal. calcd for C16H22NO7P: C, 51.75; H, 5.97; P, 8.34; found:
C, 51.73; H, 5.99; P, 8.30.
Ethyl 2-((Diethoxyphosphoryl)(phenyl)methyl)acrylate (4i)
Colorless oil, IR (KBr): 3063, 2983, 2933, 1716, 1651, 1622, 1493,
1454,1392, 1296, 1242, 1132, 1055, 1026, 964 cm−1; 1H NMR (300 MHz,
CDCl3): δ 1.07 (t, J = 7.1 Hz, 3H), 1.22–1.31 (m, 6H), 3.68–3.74 (m, 1H),
3.86–3.91 (m, 1H), 4.04–4.20 (m, 4H), 4.59 (d, J = 24.0 Hz, 1H), 6.53–
6.55 (m, 2H), 7.25–7.34 (m, 3H), 7.44–7.47 (m, 2H); 13C NMR (75 MHz,
CDCl3, TMS): δ 13.97, 16.06 (d, J = 5.8 Hz), 16.25 (d, J = 5.7 Hz), 43.94
(d, J = 140.8 Hz), 61.18, 62.36 (d, J = 7.4 Hz), 62.83 (d, J = 6.9 Hz),
127.30 (d, J = 2.9 Hz), 128.36 (d, J = 1.65 Hz), 128.45, 128.53, 129.54,
129.64, 134.89 (d, J = 6.3 Hz), 136.29 (d, J = 2.3 Hz), 166.04 (d, J =
14.3 Hz); 31P NMR (121 MHz, CDCl3, H3PO4): δ 24.60. Anal. calcd for
C16H23O5P: C, 58.89; H, 7.10; P, 9.49; found: C, 58.90; H, 7.13; P, 9.46.
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