3-Phosphono-2-(N-cyanoimino)thiazolidine derivatives, new phosphorylating agents for alcohols

Article abstract of DOI:10.1016/S0040-4020(02)00312-5

We have developed new phosphorylating agents, 3-phosphono-2-(N-cyanoimino)-thiazolidine derivatives (3-phosphono-NCTs), which were readily synthesized by phosphorylation of NCT, and transformed primary and secondary alcohols into phosphates in good yield. The transfer of three kinds of dialkylphosphono groups [(PhO)₂P(O)-, (EtO)₂P(O)-, (Cl₃CCH₂O)₂P(O)-] proceeded in excellent yields. Selective phosphorylation of various alcohols was also accomplished.

Full text of DOI:10.1016/S0040-4020(02)00312-5

TETRAHEDRON
Pergamon
Tetrahedron 58 (2002) 3493±3498
3-Phosphono-2-(N-cyanoimino)thiazolidine derivatives,
new phosphorylating agents for alcohols
Naoyoshi Maezaki,a Akemi Furusawa,a Yuki Hirose,a Shuji Uchidab and Tetsuaki Tanakaa,p
aGraduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565-0871, Japan
bFaculty of Pharmaceutical Sciences, Setsunan University, 45-1 Nagaotogecho, Hirakata, Osaka 573-1041, Japan
Received 23 January 2002; accepted 14 March 2002
AbstractÐWe have developed new phosphorylating agents, 3-phosphono-2-(N-cyanoimino)-thiazolidine derivatives (3-phosphono-NCTs),
which were readily synthesized by phosphorylation of NCT, and transformed primary and secondary alcohols into phosphates in good yield.
The transfer of three kinds of dialkylphosphono groups [(PhO)2P(O)±, (EtO)2P(O)±, (Cl3CCH2O)2P(O)±] proceeded in excellent yields.
Selective phosphorylation of various alcohols was also accomplished. q 2002 Elsevier Science Ltd. All rights reserved.
1. Introduction
reagents are stable crystalline compounds and the NCT
produced by the reactions is recovered for reuse. We also
demonstrated that these reagents can be applied to asym-
metric reactions using chiral NCT derivatives.7±9 Next, we
aimed at the development of a novel phosphorylating agent
bearing NCT as a leaving group (Scheme 1).
Trialkyl phosphate is an important synthetic intermediate
employed in various reactions1±3 and also an important
precursor of monoalkyl phosphate, which is found in a
number of biologically important substances such as nucleic
acids, phospholipids, and inositol phosphates. Phosphoro-
chloridates [(RO)2P(O)Cl] are widely used as phosphoryl-
ating agents for the synthesis of trialkyl phosphate.
However, the reagents are moisture-sensitive and decom-
pose to generate harmful hydrochloric acid. Therefore,
they must be stored under nitrogen in a refrigerator.
In this paper, we describe the phosphorylation reaction of
various alcohols using novel 3-phosphono-2-(N-cyano-
imino)thiazolidine derivatives [(RO)2P(O)±NCT].
2. Results and discussion
2-(N-Cyanoimino)thiazolidine (NCT) is a heterocyclic
compound having a unique conjugate system and can be
readily synthesized according to Neidlein's procedure.4
We have reported that its N-substituted derivatives can be
used as reagents for acylation5,6 and sulfenylation.7 These
2.1. Preparation of 3-phosphono-NCT
Phosphorylating agents 1a±c were readily prepared
by phosphorylation of NCT with the corresponding
Scheme 1.
Scheme 2.
Keywords: phosphorylation; phosphoric acid and derivatives; thiazolidines.
Corresponding author. Tel.: 181-6-6879-8210; fax: 181-6-6879-8214; e-mail: t-tanaka@phs.osaka-u.ac.jp
p
0040±4020/02/$ - see front matter q 2002 Elsevier Science Ltd. All rights reserved.
PII: S0040-4020(02)00312-5

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N. Maezaki et al. / Tetrahedron 58 (2002) 3493±3498
Table 3. Phosphorylation of various secondary alcohols
Table 1. Phosphorylation of 3-butyn-1-ol with 3-phosphono±NCT 1a
Entry
Alcohol
B
Condition
A
Time (h)
1
Product
Yield (%)a
Entry
Conditions (epuiv.)
Temp. (8C)
Time (h)
Yield (%)a
1
2
3
4
7
7
7
8
92
19
85
88
1
2
3
4
5
6
7
8
9
10
n-BuLi (1.2)
NaH (1.2)
t-BuMgCl (1.2)
Et3N (1.2)
Pyridine (1.2)
p-TsOH´H2O (0.05)
PPTS (0.25)
Cu(OTf)2 (0.25)
Zr(acac)4 (0.25)
Zr(acac)4 (1.0)
0
0
0
0.25
0.25
0.25
24
24
24
24
5
13
89
87
98
0
0
0
14
C
A
2
0.25
Rt to re¯ux
Rt to re¯ux
Rt to re¯ux
Rt to re¯ux
Rt
5
6
A
A
0.5
9.5
9
87
23
0
22
35
89
10
Rt
Rt
0.5
Method A: alcohol was activated with t-BuMgCl and reacted with 1a.
Method B: alcohol was reacted with 1a in the presence of Zr(acac)4.
Method C: alcohol was activated with t-BuMgCl and reacted with
(PhO)2P(O)Cl in re¯uxing THF.
a
Isolated yield.
a
Isolated yield.
phosphorochloridates in the presence of Et3N in CH2Cl2 at rt
in good yields (Scheme 2). All the compounds are stable and
odorless crystals, and are far less sensitive to moisture
compared with the corresponding phosphorochloridates.
of the phenol part with the alcohol was detected. It is noted
that the NCT was recovered for reuse in good yield (.80%).
Then, we investigated phosphorylation of various primary
alcohols using the established reaction conditions. The
results are summarized in Table 2. Although satisfactory
results were obtained in all cases except entry 9, the acti-
vation using t-BuMgCl almost exhibited higher yields than
that using Zr(acac)4. (PhO)2P(O)±NCT 1a exhibited better
yield than (PhO)2P(O)Cl (entries 1±3).
2.2. Phosphorylation of alcohols with 3-phosphono-NCT
Using (PhO)2P(O)±NCT 1a, we examined suitable reaction
conditions for phosphorylation of 3-butyn-1-ol under basic
and acidic conditions (Table 1). We found that activation of
the alcohol with a strong base was effective to give the
phosphate in good yields (entries 1±3). However, use of
an amine base such as Et3N or pyridine did not afford the
product (entries 4 and 5). On the other hand, protic acids did
not promote the reaction (entries 6 and 7), but some Lewis
acids were effective (entries 8±10). Especially, the condi-
Next, we examined phosphorylation of secondary alcohols
with (PhO)2P(O)±NCT (Table 3). Magnesium salts of the
secondary alcohols were phosphorylated with 1a at rt in
good yield (entries 1, 4, and 5). We found that
(PhO)2P(O)±NCT can be suf®ciently used in place of
(PhO)2P(O)Cl even for secondary alcohols by using this
method (entry 3). For secondary alcohols, phosphorylation
using Zr(acac)4 was sluggish and the yield was poor (entry
2). The reagent was not effective for phosphorylation of
tert-butanol, and the phosphorylated product was obtained
only in 23% yield (entry 6).
10
tions using one equivalent of Zr(acac)4 gave satisfactory
yield (entry 10). As a result of the preliminary experiments,
we adopted two promising reaction conditions, i.e. the
t-BuMgCl and Zr(acac)4 methods. In these reactions, the
NCT is selectively replaced with alcohol, and no exchange
Table 2. Phosphorylation of various primary alcohols
Phosphates of allylic1 and propargylic alcohols11 are impor-
tant synthetic intermediates for various reactions. The
3-phosphono-NCT converted these alcohols into the corre-
sponding phosphates in excellent yields (Table 4).
Entry
Alcohol
0.5
Condition Time (h) Product Yield (%)a
1
2B
3
A
0.08
2
2
2
3
3
4
4
5
5
6
6
98
89
85
91
73
50
72
88
8
Table 4. Phosphorylaton of allylic and propargylic alcohols
C
A
B
A
B
A
B
A
B
4
0.25
1.0
0.17
1.75
0.33
1.5
0.5
1.0
4
5
6
7
8
9
10
11
Entry
1
Alcohol
Time (h)
0.25
Product
Yield (%)a
85
11
100
59
2
3
0.5
12
13
85
Method A: alcohol was activated with t-BuMgCl and reacted with 1a.
Method B: alcohol was reacted with 1a in the presence of Zr(acac)4.
Method C: alcohol was activated with t-BuMgCl and reacted with
(PhO)2P(O)Cl.
0.25
100
Alcohol was activated with t-BuMgCl and reacted with 1a.
Isolated yield.
a
a
Isolated yield.

N. Maezaki et al. / Tetrahedron 58 (2002) 3493±3498
3495
Table 5. Reactions of various 3-phosphono-NCTs
Entry
Alcohol
Reagent
R0
Time (h)
Product
Yield (%)a
1
2
3
4
5
6
1a
1b
1c
1a
1b
1c
Ph
Et
Cl3CCH2
Ph
Et
Cl3CCH2
0.25
1.5
0.17
0.25
1.5
14
15
16
17
18
19
70
84
76
98
97
78
0.25
a
Isolated yield.
Considerable attention has been paid towards the develop-
ment of diversely protected phosphorylating agents, since
conversion of trialkyl phosphates into the corresponding
monoalkyl phosphates should take place under different
conditions depending on the substrates.12 Therefore, we
examined the ability of 3-phosphono-NCTs 1b, c as
phosphorylating agents and found that these compounds
smoothly converted both the primary and secondary alco-
hols into corresponding phosphates in good yields (Table 5).
Phosphorylation using 3-phosphono-NCTs 1a and c was
completed faster than that using (EtO)2P(O)±NCT 1b
presumably due to a resonance effect of the phenyl groups
and inductive effect of the trichloroethyl groups, respec-
tively.
volatile cyclohexanol could not be recovered, no phos-
phorylated cyclohexanol 7 was detected. Similarly, cyclo-
hexanol was predominantly phosphorylated to give 7 with
1a in the presence of 2-phenyl-2-propanol. Two primary
alcohols with different steric demand were also differen-
tiated clearly. Thus, 3-butyn-1-ol was exclusively phos-
phorylated to give 2 in the presence of neopentyl alcohol
with 1a. Similarly, differentiation of two secondary alcohols
in cyclohexanol and l-menthol was accomplished, giving 7
and 9 in 57 and 8% yields, respectively.
3. Conclusions
3-Phosphono-NCTs 1a±c can be used as a stable alternative
to phosphorchloridates. Phosphorylation of primary and
secondary alcohols proceeds in good yield. In addition,
compound 1a selectively phosphorylates different kinds of
alcohols. As we have demonstrated with three kinds of
phosphorylating agents 1a±c in this paper, NCT would be
a promising leaving group for other phosphorylating agents
Selective phosphorylation of alcohols is required for the
synthesis of the monophosphate from polyol compounds
without protection. We examined competitive phosphoryl-
ation toward two kinds of alkoxides using the 3-phosphono-
NCT 1a (Scheme 3). 3-Butyn-1-ol was selectively phos-
phorylated to 2 in the presence of cyclohexanol. Although
Scheme 3.

3496
N. Maezaki et al. / Tetrahedron 58 (2002) 3493±3498
having a variety of protection. Further studies along these
lines are in progress.
Jˆ7.3 Hz, 2H, CH2S), 4.18 (m, 4H, CH2O), 4.33 (t, Jˆ
7.3 Hz, 2H, CH2N). 13C NMR (methanol-d4) d: 16.4 (d,
J(C,P)ˆ6.7 Hz, 2C), 31.5 (d, J(C,P)ˆ8.4 Hz), 55.1 (d,
J(C,P)ˆ5.0 Hz), 66.7 (d, J(C,P)ˆ6.1 Hz, 2C), 116.0,
181.8 (d, J(C,P)ˆ2.2 Hz). IR 2194 (CN), 1238 (P±O),
1144 (P±O). MS (EI) m/z (%) 263 (M1, 31.9). HRMS
(EI) Calcd C8H14N3O3PS (M1): 263.0493. Found:
263.0492.
4. Experimental
4.1. General
Melting points are uncorrected. Optical rotations were
measured using a JASCO DIP-360 digital polarimeter.
4.1.3.
3-[Bis-(trichloroethyl)phosphono]-2-(N-cyano-
1
Unless otherwise stated, H and 13C NMR spectra were
imino)thiazolidine (1c). (CCl3CH2O)2P(O)Cl (226 mg,
0.60 mmol) was added to a mixture of NCT (64 mg,
0.50 mmol) and i-Pr2NEt (0.26 ml, 1.50 mmol) in CH2Cl2
(2.5 ml) with stirring at rt under N2 and the stirring was
continued at rt for 30 min. The mixture was washed with
10% KOH prior to drying and solvent evaporation. The
crude was washed with n-hexane to give 1c (170 mg,
73%) as a colorless powder. Mp 161.0±162.08C (AcOEt).
1H NMR d: 3.36 (t, Jˆ7.3 Hz, 2H, CH2S), 4.36 (t, Jˆ
7.3 Hz, 2H, CH2N), 4.79 (d, Jˆ7.3 Hz, 4H, CH2O). 13C
NMR d: 30.8 (d, J(C,P)ˆ9.3 Hz), 53.2(d, J(C,P)ˆ
5.6 Hz), 78.0 (d, J(C,P)ˆ5.0 Hz, 2C), 94.1 (d, J(C,P)ˆ
9.3 Hz, 2C), 114.0, 180.0. IR 2199 (CN), 1236 (P±O),
1176 (PvO), 1107 (P±O). MS (FAB) m/z: 468 (MH1).
HRMS (FAB) Calcd C8H9Cl6N3O3PS (MH1): 467.8262.
Found: 467.8291.
recorded in CDCl3 solution. 1H NMR spectra were recorded
at 500 MHz with a JEOL JNM-GX500 spectrometer. 13C
NMR spectra were recorded at 68 or 75 MHz with a
JEOL JNM-EX270 spectrometer or a JEOL JMN-AL-300,
respectively. All signals are expressed as ppm down®eld
from tetramethylsilane used as an internal standard (d
value). IR spectra were measured with a Horiba FT-210
IR spectrometer. Mass spectra were taken with a Shimadzu
QP-1000 mass spectrometer or a JMS-600 mass spectro-
meter. High-resolution mass spectra were measured by a
JEOL JMS-600H. Merck Kieselgel 60 or Kanto silica gel
60 was used as an adsorbent for column chromatography.
All air- or moisture-sensitive reactions were carried out in
¯ame-dried glassware under N2 atmosphere. All organic
extracts were dried over anhydrous MgSO4, ®ltered, and
concentrated with a rotary evaporator under reduced
pressure unless otherwise stated.
4.1.4. General procedure for phosphorylation of alcohols
(t-BuMgCl method). t-BuMgCl (0.97 M, THF solution)
(0.25 ml, 0.24 mmol) was added to a solution of 3-butyn-
1-ol (0.01 ml, 0.20 mmol) in THF (2 ml) with stirring at rt
under N2 and the stirring was continued at rt for 30 min.
Then, (PhO)2P(O)±NCT (86 mg, 0.24 mmol) was added to
the mixture and the whole was stirred at rt for 15 min. The
reaction was quenched with pH 7.0 sodium phosphate buffer
and extracted with AcOEt. The extract was dried and the
solvent was evaporated to give 2 (59 mg, 98%) as a color-
less oil along with NCT (26 mg, 85%). 1H NMR d: 2.00 (t,
Jˆ2.7 Hz, 1H, CuCH), 2.59 (td, Jˆ6.7, 2.7 Hz, 2H,
CuCCH2), 4.31 (dt, Jˆ6.7, 6.7 Hz, 2H, CH2O), 7.19±
7.36 (m, 10H, Ar-H). 13C NMR d: 20.5 (d, J(C,P)ˆ
7.5 Hz), 66.4 (d, J(C,P)ˆ5.6 Hz), 70.6, 77.8, 120.0 (d,
J(C,P)ˆ5.0 Hz, 4C), 125.4 (d, J(C,P)ˆ1.3 Hz, 2C), 129.8
(4C), 150.3 (d, J(C,P)ˆ7.5 Hz, 2C). IR 3295 (CuCH),
2123 (CuCH), 1589 (Ph), 1217 (P±O), 1190 (PvO),
1163 (P±O). MS (FAB) m/z: 303 (MH1). HRMS (FAB)
Calcd C16H16O4P (MH1): 303.0810. Found: 303.0798.
4.1.1. 3-(Diphenylphosphono)-2-(N-cyanoimino)thiazo-
lidine (1a). (PhO)2P(O)Cl (8.67 g, 60.0 mmol) was added
to a mixture of NCT (3.82g, 30.0 mmol) and Et 3N (20.9 ml,
150 mmol) in CH2Cl2 (150 ml) with stirring at rt under N2
and the stirring was continued at rt for 15 min. The mixture
was partitioned between CH2Cl2 and water. The aqueous
layer was extracted with CH2Cl2. The combined organic
layers were washed with brine prior to drying and solvent
evaporation. The crude was chromatographed on silica gel
with n-hexane±AcOEt (1:1) to give 1b (8.09 g, 75%) as a
colorless powder. Mp 102.0±103.08C (AcOEt). 1H NMRd:
3.33 (t, Jˆ7.0 Hz, 2H, CH2S), 4.19 (t, Jˆ7.0 Hz, 2H,
CH2N), 7.24±7.40 (m, 10H, Ar-H). 13C NMR d: 30.2(d,
J(C,P)ˆ8.1 Hz), 53.7 (d, J(C,P)ˆ5.6 Hz), 114.3, 119.9 (d,
J(C,P)ˆ5.0 Hz, 4C), 126.0 (d, J(C,P)ˆ1.2 Hz, 2C), 129.9
(4C), 149.1 (d, J(C,P)ˆ6.9 Hz, 2C), 178.5. IR 2197 (CN),
1566 (Ph), 1234 (P±O±Ph), 1182 (PvO), 1138 (P±O).
MS (FAB) m/z: 360 (MH1). HRMS (FAB) Calcd
C16H15N3O3PS (MH1): 360.0602. Found: 360.0587. Anal.
calcd for C16H14N3O3PS: C, 53.48; H, 3.93; N, 11.69; S,
8.92. Found: C, 53.56; H, 3.95; N, 11.83, S, 8.83.
4.2. General procedure for phosphorylation of alcohols
[Zr(Ot-Bu)4 method]
4.1.2.
3-(Diethylphosphono)-2-(N-cyanoimino)thiazo-
(PhO)2P(O)±NCT (86 mg, 0.24 mmol) was added to a
mixture of 3-butyn-1-ol (0.01 ml, 0.20 mmol) and Zr(acac)4
(98 mg, 0.20 mmol) in THF (2 ml) with stirring at rt under
N2 and the stirring was continued at rt for 30 min. The
reaction was quenched with pH 7.0 sodium phosphate buffer
and extracted with AcOEt. The extract was dried and the
solvent was evaporated. The crude was chromatographed on
silica gel with n-hexane±AcOEt (1:1) to give 2 (54 mg,
89%) as a colorless oil along with NCT (25 mg, 82%).
lidine (1b). (EtO)2P(O)Cl (3.40 g, 23.6 mmol) was added
to a mixture of NCT (1.50 g, 11.8 mmol) and Et3N (8.20 ml,
59.0 mmol) in CH2Cl2 (30 ml) with stirring at rt under N2
and the stirring was continued at rt for 30 min. The mixture
was partitioned between CH2Cl2 and water. The aqueous
layer was extracted with CH2Cl2. The combined organic
layers were washed with brine prior to drying and solvent
evaporation. The crude was chromatographed on silica gel
with n-hexane±AcOEt (1:1) to give 1b (2.28 g, 74%) as
1
a colorless powder. Mp 81.0±82.08C (AcOEt). H NMR
(acetone-d6) d: 1.32(t, Jˆ7.3 Hz, 6H, CH3), 3.67 (t,
The phosphates 3±8, 10, 12, 13, and 15 are known

N. Maezaki et al. / Tetrahedron 58 (2002) 3493±3498
3497
compounds, which were reported in Refs. 13, 14, 14, 15±18,
2b, 19, and 20, respectively.
369 (MH1). HRMS (FAB) Calcd C21H22O4P (MH1):
369.1280. Found: 369.1268.
4.2.6. Diethyl 1-phenylprop-2-yl phosphate (18). Color-
4.2.1. l-Menthyl diphenyl phosphate (9). Colorless oil
1
25
(87%). [a]D ˆ237.4 (c 0.86, CHCl3).1H NMR d: 0.72
less oil (97%). H NMR d: 1.21 (t, Jˆ7.3 Hz, 3H, CH3),
1.27 (t, Jˆ7.3 Hz, 3H, CH3), 1.33 (d, Jˆ6.1 Hz, 3H, CH3),
2.81 (ddd, Jˆ14.0, 6.1, 1.8 Hz, 1H, PhCH2), 2.97 (dd,
Jˆ14.0, 6.7 Hz, 1H, PhCH2), 3.82(m, 4H, C H2CH3), 4.67
(m, 1H, CHO), 7.21±7.31 (m, 5H, Ar-H). 13C NMR d: 15.9
(d, J(C,P)ˆ1.9 Hz), 16.0 (d, J(C,P)ˆ1.9 Hz), 21.1 (d,
J(C,P)ˆ3.1 Hz), 43.7 (d, J(C,P)ˆ6.9 Hz), 63.2(d,
J(C,P)ˆ5.0 Hz, 2C), 76.1 (d, J(C,P)ˆ6.2Hz), 126.4,
128.2 (2C), 129.4 (2C), 137.2. IR 1497 (Ph), 1273 (P±O),
1263 (P±O), 1167 (PvO), 1034 (P±O). MS (FAB) m/z: 2 73
(MH1). HRMS (FAB) Calcd C13H22O4P (MH1): 273.1296.
Found: 273.1274.
(d, Jˆ7.3 Hz, 3H, CH3), 0.84 (d, Jˆ7.3 Hz, 3H, CH3),
0.89 (d, Jˆ6.1 Hz, 3H, CH3), 0.82±1.02 (m, 2H), 1.14 (m,
1H), 1.37±1.46 (m, 2H), 1.65 (d, Jˆ12.2 Hz, 2H),
1.99±2.03 (m, 1H, CH(CH3)2), 2.21 (br d, 1H), 4.39 (ddt,
Jˆ11.0, 6.7, 4.3 Hz, 1H, CHO), 7.16±7.35 (m, 10H, Ar-H).
13C NMR d: 15.5, 20.7, 21.8, 22.7 (d, J(C,P)ˆ1.2Hz), 25.3,
31.4, 33.8, 42.3, 48.2 (d, J(C,P)ˆ7.5 Hz), 81.4 (d, J(C,P)ˆ
6.9 Hz), 120.0 (d, J(C,P)ˆ5.0 Hz, 4C), 125.0 (d, J(C,P)ˆ
1.2 Hz, 2C), 129.5 (4C), 150.6 (d, J(C,P)ˆ1.9 Hz, 2C). IR
1591 (Ph), 1191 (PvO), 1163 (P±O). MS (FAB) m/z: 411
(MNa1). HRMS (FAB) Calcd C22H29NaO4P (MNa1):
411.1712. Found: 411.1723.
4.2.7. Bis-(2,2,2-trichloroethyl) 1-phenylprop-2-yl phos-
phate (19). Colorless oil (78%). 1H NMR d: 1.47 (d,
Jˆ6.1 Hz, 3H, CH3), 2.90 (ddd, Jˆ14.0, 6.1, 3.1 Hz, 1H,
PhCH2), 2.98 (dd, Jˆ14.0, 6.1 Hz, 1H, PhCH2), 4.17 (dd,
Jˆ11.6, 6.1 Hz, 1H, CH2CCl3), 4.29 (dd, Jˆ11.6, 6.1 Hz,
1H, CH2CCl3), 4.33 (dd, Jˆ11.6, 6.1 Hz, 1H, CH2CCl3),
4.43 (dd, Jˆ11.6, 6.1 Hz, 1H, CH2CCl3), 4.84 (m, 1H,
CHO), 7.23±7.34 (m, 5H, Ar-H). 13C NMR d: 21.4 (d,
J(C,P)ˆ3.1 Hz), 43.6 (d, J(C,P)ˆ6.9 Hz), 76.6 (d,
J(C,P)ˆ3.1 Hz, 2C), 78.9 (d, J(C,P)ˆ6.9 Hz), 94.7 (d,
J(C,P)ˆ10.0 Hz, 2C), 127.0, 128.6 (2C), 129.5 (2C),
136.8. IR 1591 (Ph), 1190 (PvO), 1163 (P±O). MS
(FAB) m/z: 477 (MH1). HRMS (FAB) Calcd
C13H16Cl6O4P (MH1): 476.8899. Found: 476.8908.
4.2.2. (E)-2-Butenyl diphenyl phosphate (11). Colorless
1
oil (85%). H NMR d: 1.70 (br d, Jˆ6.7 Hz, 3H, CH3),
4.65 (dd, Jˆ8.5, 6.7 Hz, 2H, CH2O), 5.58 (dt, Jˆ15.3,
6.7 Hz, 1H, CH3CHvCH), 5.79 (dq, Jˆ15.3, 6.7 Hz, 1H,
CH3CHvCH), 7.17±7.35 (m, 10H, Ar-H). 13C NMR d:
17.6, 69.7 (d, J(C,P)ˆ6.2Hz), 120.0 (d, J(C,P)ˆ5.0 Hz,
4C), 124.8 (d, J(C,P)ˆ6.3 Hz), 125.2 (d, J(C,P)ˆ1.2Hz),
129.6 (4C), 132.5, 150.4 (d, J(C,P)ˆ6.9 Hz, 2C). IR 1591
(Ph), 1190 (PvO), 1163 (P±O). MS (FAB) m/z: 305
(MH1). HRMS (FAB) Calcd C16H18O4P (MH1):
305.0954. Found: 305.0966.
4.2.3. Diphenyl 2-phenylethyl phosphate (14). Colorless
oil (70%). 1H NMR d: 3.00 (t, Jˆ7.3 Hz, 2H, PhCH2), 4.42
(dt, Jˆ7.3, 7.3 Hz, 2H, CH2O), 7.14±7.37 (m, 10H, Ar-H).
13C NMR d: 36.6 (d, J(C,P)ˆ6.7 Hz), 69.4 (d, J(C,P)ˆ
6.7 Hz), 119.9 (d, J(C,P)ˆ5.0 Hz, 4C), 125.2 (d, J(C,P)ˆ
1.7 Hz, 2C), 126.7 (2C), 128.4 (2C), 129.6 (d, J(C,P)ˆ
1.1 Hz, 4C), 129.7, 136.5, 150.2 (d, J(C,P)ˆ7.3 Hz, 2C).
IR 1591 (Ph), 1190 (PvO), 1163 (P±O). MS (FAB) m/z:
355 (MH1). HRMS (FAB) Calcd C20H20O4P (MH1):
355.1109. Found: 355.1104.
References
1. As a precursor of organometallic reagents, see: Kang, S.-K.;
Kim, D.-Y.; Hong, R.-K.; Ho, P.-S. Synth. Commun. 1996, 26,
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Yanagisawa, A.; Nomura, N.; Yamamoto, H. Tetrahedron
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4.2.4. Bis-(2,2,2-trichloroethyl) 2-phenylethyl phosphate
(16). Colorless oil (76%). H NMR (500 MHz, CDCl3) d:
1
3.05 (t, Jˆ7.0 Hz, 2H, PhCH2), 4.42(dt, Jˆ7.0, 7.0 Hz, 2H,
CH2CH2O), 4.44 (dd, Jˆ11.0, 6.7 Hz, 2H, CH2CCl3), 4.48
(dd, Jˆ11.0, 6.7 Hz, 2H, CH2CCl3), 7.24±7.34 (m, 5H,
Ar-H). 13C NMR (75 MHz, CDCl3) d: 36.5 (d, J(C,P)ˆ
6.9 Hz), 69.5 (d, J(C,P)ˆ6.9 Hz), 76.9 (d, J(C,P)ˆ9.9 Hz,
2C), 94.5 (d, J(C,P)ˆ11.2 Hz, 2C), 127.0, 128.7 (2C), 129.0
(2C), 136.5. IR 1497 (Ph), 1298 (PvO), 1103 (P±O). MS
(FAB) m/z: 463 (MH1). HRMS (FAB) Calcd C12H14Cl6O4P
(MH1): 426.8747. Found: 426.8754.
4.2.5. Diphenyl 1-phenylprop-2-yl phosphate (17). Color-
1
less oil (98%). H NMR d: 1.34 (d, Jˆ6.1 Hz, 3H, CH3),
2.83 (dd, Jˆ15.0, 6.7 Hz, 1H, PhCH2), 3.00 (dd, Jˆ15.0,
6.7 Hz, 1H, PhCH2), 4.91 (m, 1H, CHO), 7.09±7.35 (m,
15H, Ar-H). 13C NMR d: 20.9 (d, J(C,P)ˆ3.7 Hz), 43.5
(d, J(C,P)ˆ6.2Hz), 78.4 (d, J(C,P)ˆ6.9 Hz), 119.9 (d,
J(C,P)ˆ5.0 Hz, 2C), 120.0 (d, J(C,P)ˆ5.0 Hz, 4C), 125.1
(d, J(C,P)ˆ1.2 Hz, 2C), 128.4 (2C), 129.3, 129.5 (d,
J(C,P)ˆ6.9 Hz, 4C), 136.5, 150.5 (d, J(C,P)ˆ2.5 Hz, 2C).
IR 1591 (Ph), 1192(P vO), 1163 (P±O). MS (FAB) m/z:
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