Solvent-controlled direct radical oxyphosphorylation of styrenes mediated by Manganese(III)

Article abstract of DOI:10.1016/j.tet.2016.04.013

Direct radical oxyphosphorylation of styrenes with diarylphosphine oxides and dialkyl phosphites mediated by Mn(OAc)₃ is described. The solvent played a key role in this selective difunctionalization reaction.

Full text of DOI:10.1016/j.tet.2016.04.013

Accepted Manuscript
Solvent-Controlled Direct Radical Oxyphosphorylation of Styrenes Mediated by
Manganese(III)
Guo-Yu Zhang, Cheng-Kun Li, Da-Peng Li, Run-Sheng Zeng, Adedamola Shoberu,
Jian-Ping Zou
PII:
S0040-4020(16)30266-6
10.1016/j.tet.2016.04.013
TET 27656
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 17 January 2016
Revised Date: 3 April 2016
Accepted Date: 6 April 2016
Please cite this article as: Zhang G-Y, Li C-K, Li D-P, Zeng R-S, Shoberu A, Zou J-P, Solvent-Controlled
Direct Radical Oxyphosphorylation of Styrenes Mediated by Manganese(III), Tetrahedron (2016), doi:
10.1016/j.tet.2016.04.013.
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Solvent-Controlled Direct Radical Oxyphosphorylation Leave this area blank for abstract info.
of Styrenes Mediated by Manganese(III)
Guo-Yu Zhang,a Cheng-Kun Li, a Da-Peng Li,a Run-Sheng Zeng,*aAdedamola Shoberu,aJian-Ping Zou*a,b
aKey Laboratory of Organic Synthesis of Jiangsu Province,,College of Chemistry and Chemical Engineering,
Soochow University, 199 Renai Street, Suzhou, Jiangsu 215123, China.
bKey Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry,
Chinese Academy of Sciences, Shanghai 200032, China.

1
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Tetrahedron
journal homepage: www.elsevier.com
Solvent-Controlled Direct Radical Oxyphosphorylation of Styrenes Mediated by
Manganese(III)
Guo-Yu Zhang,a Cheng-Kun Li, a Da-Peng Li,a Run-Sheng Zeng,*aAdedamola Shoberu,aJian-Ping Zou*a,b
a Key Laboratory of Organic Synthesis of Jiangsu Province,,College of Chemistry and Chemical Engineering, Soochow University, 199 Renai Street, Suzhou,
Jiangsu 215123, China.
bKey Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032,
China.
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
Direct radical oxyphosphorylation of styrenes with diarylphosphine oxides and dialkyl
phosphites mediated by Mn(OAc)3 is described. The solvent played a key role in this selective
difunctionalization reaction.
2016 Elsevier Ltd. All rights reserved
.
Available online
Keywords:
Keyword_1oxyphosphorylation
Keyword_2 radical reaction
Keyword_3 styrene
Keyword_4 manganese acetate
1. Introduction
radical and carbocation (II) respectively. We envisioned that if
the oxidizing ability of Mn(OAc)3 can be controlled by changing
some reaction conditions involved in the process described in
Scheme 1, the resultant intermediate carbon-centered radical
obtained from the initial addition of the phosphorus-centered
radical might be prevented from further oxidation. This could
then be subjected to other radical transformations thus achieving
a new type of selective difunctionalization of alkenes. Herein, we
report a new protocol involving oxyphosphorylation of alkenes in
the presence of Mn(OAc)3 and air. In this reaction, both H-
phosphonates and diarylphosphine oxides were tolerated giving
the corresponding products.
Difunctionalization reaction involving alkenes has been of
considerable interest in organic synthesis due to advantages such
as its high efficiency, atom and step economy.1 One of the most
significant among this type of reactions are those involving a
phosphorus-containing functional group since the resultant
product can be easily transformed into other compounds such as
β-keto, β-amino, and β-hydroxyphosphonates.2 Several methods
of C-P bond formation have been described in literature,3,4
however, reports on the difunctionalization of alkenes involving
a phosphorus-containing group are few.5 In 2011, Ji’s group
described the first example involving transition metal-catalyzed
oxyphosphorylation of alkenes with dioxygen and H-
phosphonates5g. More recently, our group reported
a
Manganese(III)-mediated acetoxyphosphorylation of alkenes6
with diphenylphosphine oxide or dimethyl phosphite leading
exclusively to acetoxyphosphorylation products. The method
proceeded via a phosphorus-centred radical addition to the alkene
to form (I), subsequent oxidation and solvent (HOAc) attack
tandem process, followed by deprotonation gave compound (IV)
(Scheme 1). The Mn(OAc)3/HOAc system employed possesses a
high oxidative potential as it oxidized both diphenylphosphine
oxide (or dimethyl phosphite) and the intermediate carbon-
centred radical (I) to the corresponding phosphorus-centered
_______
Scheme 1. Plausible mechanism of acetoxyphosphorylation of styrene
Corresponding author. Tel.: +0-86-512-65880336; fax: +0-86-
512-65880335; e-mail: jpzou@suda.edu.cn

2
Tetrahedron
was observed in MeOH for 1 hour at 70°C. The results showed
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that styrenes bearing either electron-donating or electron-
2. Results and Discussion
withdrawing groups on the phenyl ring all afforded
oxyphosphorylation products in moderate to good yields (up to
69%, Table 3, 5a-i). Interestingly, the reaction of 4-nitrostyrene
in this case yielded only a major product 5j in 50% yield thus
indicating that radical reaction is sensitive to the nature of the
phosphorus radical.
To test our hypothesis, the reaction between styrene (1a) and
diphenylphosphine oxide (2) was carried out in the presence of
Mn(OAc)3 under aerobic conditions. At the outset, polar solvents
such as MeOH, t-BuOH, CH3CN, THF, DMF, and DMSO were
used. To our delight, a new product, 2-(diphenylphosphoryl)-1-
phenylethanone (3a) was observed in all cases (Table 1, entries
1-6). MeOH, t-BuOH and CH3CN were the best solvents among
which MeOH was selected for further optimization. Subsequently,
Table 2. Reactions of styrenes 1and diphenylphosphine oxide 2a, b
the
reaction
temperature,
time
and
ratio
of
styrene/HP(O)Ph2/Mn(OAc)3 were screened. The best result was
obtained when a ratio of styrene/HP(O)Ph2/Mn(OAc)3 (1:2:2)
was reacted in MeOH for 1 h at 30°C (Table 1, entry 7). It was
interesting that the yield of product obtained under air was higher
than in O2 atmosphere (Table 1, entry 10); this implied that the
concentration of oxygen has an important influence on the
outcome of reaction.
Table 1. Optimization of the reaction conditions
a Reaction conditions: styrene (1.0 mmol), HP(O)Ph2 (2.0 mmol),
Mn(OAc)3 (2.0 mmol) in MeOH (10 mL), 30 oC, 60 min;
b Isolated yield.
Table 3. Reactions of styrenes 1and dialkylphosphites 4a, b
Products 5 and Yield
a Isolated yield;
O
PO(OCH3)2
bThe reaction was carried out under O2 atmosphere.
5a, 69%
O
O
O
O
PO(OCH3)2
5c, 56%
PO(OCH3)2
5b, 58%
The optimal reaction conditions obtained above were applied to
different set of styrenes to evaluate the scope of this reaction. In
general, electronic effect had less influence on the yield as both
electron-withdrawing and electron-donating styrene all afforded
the expected 2-(diphenylphosphoryl)-1-arylethanones in yields
ranging from 60−75% (Table 2, 3a-i). However, the reaction of
H3CO
PO(OCH3)2
5d,54%
PO(OCH3)2
5e, 63%
F
Cl
O
O
O
O
4-nitrostyrene with
2
produced
a
mixture of 2-
F3C
PO(OCH3)2
5h, 60%
PO(OCH3)2
5g,58%
(diphenylphosphoryl)-1-(4-nitrophenyl)ethanone (3j) and (2-
hydroxy-2-(4-nitrophenyl)ethyl)diphenylphosphine oxide (3j’) in
55% combined yield. The strong electron-withdrawing group
NO2 could be responsible for the competitive reaction pathways
involved.
Br
PO(OCH3)2
5j, 50%
PO(OCH3)2
5i, 59%
O2N
NC
Considering
the
success
of
the
reaction
with
a Reaction conditions: styrene (1.0 mmol), HPO(OR)2 (2.0 mmol), Mn(OAc)3
(2.0 mmol) in CH3OH (10 mL), 70 oC, 60 min; b Isolated yield.
diphenylphosphine oxide 2, the reaction with dialkylphosphites
was also tested. With, dimethylphosphite (4), the best condition

3
Moving further, the effects of α- or β-substituents on styrene
Table 4. Reactions of α- and β-substituted styrenes 1 with
diphenylphosphine oxide 2 and dimethyl phosphite 4a,b
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were studied. The reactions of both α-methylstyrene (1k) and α-
phenylstyrene (1m) with diphenylphosphine oxide (2) afforded
the hydroxyphosphorylation products 3k and 3m in 73% and 74%
yields respectively (Table 4). Oxyphosphorylation products were
not observed in this case due to the presence of α-substituents.
However, in a situation where the α-substituent could be lost
easily, oxyphosphorylation products were obtained as is the case
with α-bromostyrene (1l); the reaction with 2 and 4 produced 3a
and 5a respectively in moderate yields. Surprisingly, the reaction
of 1m with dimethylphosphite (4) yielded alkenylphosphonate
5m in 75% yield. Product 5m could have been derived from the
dehydration of the corresponding hydroxyphosphonylation
intermediate. Furthermore, the reactions of both β-methylstyrene
(1n) and β-phenylstyrene (1p) with 2 gave the corresponding
hydroxyphosphorylation products 3n (73%) and 3p (65%)
respectively (Table 4). The reaction of 1n with 4 gave benzoic
acid rather than the expected product 5n due to the oxidation of
1n. Also, the reactions of β-bromostyrene (1o) with 2 and 4 both
led to addition-elimination products 3o and 5o via the
phosphorus-centred radical addition to the terminal C=C double
bond, followed by elimination of bromo radical to form
alkenylphosphonylation products. The attack of oxygen on
intermediate carbon radical is not observed in this case. Based on
the results above, the reactions of α- or β-substituted styrenes
with diphenylphosphine oxide (2) and dimethylphosphite (4)
gave diverse products depending on the nature and position of
substituents. Finally, reactions involving several non-conjugated
terminal alkenes were carried out giving exclusively
hydrophosphorylation products 3q-t in good yields (Table 4).
a Reaction conditions: styrene (1.0 mmol), HP(O)Ph2 (2.0 mmol),
Mn(OAc)3 (2.0 mmol) in MeOH (10 mL), 30 oC, 60 min; styrene (1.0
mmol), HP(O)(OCH3)2 (2.0 mmol), Mn(OAc)3 (2.0 mmol) in CH3OH
(10 mL), 70 oC, 60 min;
To confirm the reaction proceeded via radical process, a
control experiment has been done, and the result indicates that
the reaction of styrene with diphenylphosphine oxide can be
inhibited by addition of 1,1-diphenyl styrene (Scheme 2). A
mechanism for the reactions of alkenes with diphenylphosphine
oxide (2) and dialkyl phosphites (4) is proposed in Scheme 2. A
phosphorus-centred radical 6 derived from 2 or 4 selectively adds
to the terminal end of C=C double bond of 1 to form a carbon-
centered intermediate radical 7. When R is an alkyl, 7 becomes
reactive thus abstracting a proton to give hydrophosphorylation
products. On the other hand, if R is an aryl, 7 could be stabilized
making it to interact with O2 to form peroxy radical 8; subsequent
proton abstraction and dehydration leads to products 3 or 5.
bIsolated yield.
3. Conclusion
In conclusion, a new general protocol of Mn(OAc)3-mediated
oxyphosphorylation of styrenes in air has been developed. The
solvent played an important role in this reaction leading
exclusively to oxyphosphorylation products. Advantages of this
methodology include mild reaction conditions, wide scope of
substrates, and the need for no further additives or oxidant. Both
diarylphosphine oxides and dialkyl phosphites were suitable
under this transformation. This protocol provides a new route to
β-ketophosphonates which can be easily transformed into other
compounds such as α,β-unsaturated carbonyl compounds, chiral
β-amino and β-hydroxy phosphonic acids etc.
4. Experimental Section
4.1. General
1H NMR(400 MHz or 300 MHz) and 13C NMR (100 or 75 MHz)
spectra were determined with CDCl3 or DMSO-d6 as solvent and
tetramethylsilane (TMS) as internal standard or 85% H3PO4 as
external standard for 31P NMR (162 MHz). Chemical shifts were
Scheme 2. Possible mechanism of oxyphosphorylation of alkenes

4
Tetrahedron
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reported in ppm from internal TMS(δ), all coupling constants (J
1-(4-Chlorophenyl)-2-(diphenylphosphoryl)ethanone (3e)10
values) were reported in Hertz (Hz). High resolution mass spectra
were recorded on a TOF machine (ESI). Column chromatography
was performed with 300-400 mesh silica gel using flash column
techniques. All of the reagents were used directly as obtained
commercially unless otherwise noted. All alkenes were purified
by flash column chromatography (Al2O3) before use.
White solid, mp 159−160 °C, 70% yield (247.8 mg); 1H NMR
(400 MHz, DMSO-d6): δ8.02−7.97 (m, 2H), 7.86−7.79 (m, 4H),
7.59−7.48 (m, 8H), 4.54 (d, J = 14.6 Hz, 2H);13C NMR (100
MHz, DMSO-d6):δ192.9 (d, J = 6.4 Hz), 139.0, 136.2, 133.7 (d, J
= 101.4 Hz), 132.3 (d, J = 2.6 Hz), 131.4, 131.1 (d, J = 9.7
Hz),129.1 (d, J = 5.1 Hz), 129.0, 41.9 (d, J = 59.8 Hz); 31P NMR
(162 MHz, CDCl3):δ26.67; HRMS (ESI-TOF) m/z: (M+H)+Calcd
for C20H17ClO2P 355.0655, found 355.0664.
4.2. General procedure for the preparation of 2-
(diphenylphosphoryl)-1-arylethanones3
Typical
procedure
for
the
preparation
of
2-
1-(3-Chlorophenyl)-2-(diphenylphosphoryl)ethanone (3f)
(diphenylphosphoryl)-1-phenylethanone (3a).To a solution of
methanol (10 mL), styrene (0.11 g, 1.0 mmol) and
diphenylphosphine oxide (0.40 g, 2.0 mmol) was added
Mn(OAc)3 (0.54 g, 2.0 mmol) over 30 minutes at 30oC, and the
mixture was stirred for another 30 minutes to complete the
reaction. Then, the solvent was removed under vacuum. To the
residue was added water (20 mL) and extracted with ethyl acetate
(10 mL × 3). The combined organic fractions were dried over
anhydrous Na2SO4, and concentrated under vacuum to yield the
crude product, which was purified by column chromatography
(silica gel, petroleum ether/EtOAc/CH2Cl2 (10:1:1)) to give pure
2-(diphenylphosphoryl)-1-phenylethanone (3a).
White solid, mp 158−159 °C, 65% yield (230.1 mg); 1H NMR
(400 MHz, CDCl3): δ7.81 (d, J = 12.0 Hz, 2H), 7.70 (dd, J = 11.2,
8.0 Hz, 4H), 7.43–7.34 (m, 7H), 7.29–7.24 (m, 1H), 4.03 (d, J =
14.9 Hz, 2H);13C NMR (100 MHz, CDCl3):δ191.7 (d, J = 5.6 Hz),
138.5, 134.82, 133.5, 132.34 (d, J = 2.4 Hz), 131.1, 131.0, 129.9,
128.9, 128.7 (d, J = 12.3 Hz), 127.7, 43.4 (d, J = 57.2 Hz); 31P
NMR (162 MHz, CDCl3): δ26.80; HRMS (ESI-TOF) m/z:
(M+H)+Calcd for C20H17ClO2P 355.0655, found 355.0670.
1-(4-Bromophenyl)-2-(diphenylphosphoryl)ethanone (3g)
White solid, mp 144−145 °C,60 % yield (238.8 mg); 1H NMR
(400 MHz, CDCl3): δ7.91−7.84 (m, 2H), 7.83−7.74 (m, 4H),
7.59−7.50 (m, 4H), 7.43−7.49 (m, 4H), 4.10 (d, J = 15.2 Hz,
2H);13C NMR (100 MHz, CDCl3):δ191.9 (d, J = 5.6 Hz), 135.7,
132.3 (d, J = 2.8 Hz), 131.9, 131.1 (d, J = 9.8 Hz), 130.9, 129.1,
128.7 (d, J = 12.3 Hz), 43.6 (d, J = 56.7 Hz); 31P NMR (162
MHz, CDCl3): δ 26.90; HRMS (ESI-TOF) m/z: (M+H)+ Calcd for
C20H17BrO2P 399.0150, found 399.0177.
4.3 Characterization
2-(Diphenylphosphoryl)-1-phenylethanone (3a)7
White solid, mp 160−161 °C, 75% yield (240.1 mg); 1H NMR
(400 MHz, CDCl3): δ7.98 (d, J = 7.4 Hz, 2H), 7.84−7.78 (m, 4H),
7.54−7.40 (m, 9H), 4.15 (d, J = 15.3 Hz, 2H);13C NMR (75 MHz,
CDCl3):δ192.8 (d, J = 5.2 Hz), 136.9, 133.6, 132.6, 132.2, 131.1
(d, J = 9.8 Hz), 129.2, 128.7, 128.5, 43.2 (d, J = 57.8 Hz); 31P
NMR (162 MHz, CDCl3):δ26.91; HRMS (ESI-TOF) m/z:
(M+H)+Calcd for C20H18O2P 321.1044, found 321.1047.
2-(Diphenylphosphoryl)-1-(3-(trifluoromethyl)phenyl)ethanone
(3h)
1
White solid, mp 173−174°C, 60% yield (232.8 mg); H NMR
(400 MHz, CDCl3):δ 8.26 (d, J = 7.8 Hz, 1H), 8.18−8.14 (m, 1H),
7.84−7.75 (m, 5H), 7.58−7.46 (m, 7H), 4.17 (d, J = 15.3 Hz,
2H);13C NMR (100 MHz, CDCl3):δ191.3 (d, J = 5.5 Hz), 136.9,
132.3, 131.9 (d, J = 2.6 Hz), 130.6, 130.5, 129.4 (q, J =3.5 Hz),
128.8, 128.3, 128.2, 125.3 (q, J = 3.8 Hz), 43.2 (d, J = 56.3 Hz);
31P NMR (162 MHz, CDCl3): δ26.51; HRMS (ESI-TOF) m/z:
(M+H)+Calcd for C21H17F3O2P 389.0918, found 389.0941.
2-(Diphenylphosphoryl)-1-(p-tolyl)ethanone (3b)8
1
White solid, mp 152−153°C, 65% yield (217.1 mg); H NMR
(400 MHz, CDCl3): δ7.89 (d, J = 7.2 Hz, 2H), 7.76−7.85 (m, 4H),
7.43−7.54 (m, 6H), 7.21 (d, J = 7.2 Hz, 2H), 4.12 (d, J =15.2 Hz,
2H), 2.38 (s, 3H); 13C NMR (100 MHz, CDCl3): δ192.3, 144.6,
134.4, 132.4, 132.1, 131.4, 131.1 (d, J = 9.7Hz), 129.3 (d, J =
17.6 Hz), 128.5 (d, J = 12.3 Hz), 43.1 (d, J = 58.4 Hz), 21.6; MS
(ESI-TOF) m/z: (M+H)+Calcd for C21H20O2P 335.1, found 335.1.
1-(4-Cyanophenyl)-2-(diphenylphosphoryl)ethanone(3i)
White solid, mp 169−170 °C, 60% yield (207.0 mg); 1H NMR
(400 MHz, CDCl3): δ8.13 (d, J = 8.2 Hz, 2H), 7.79 (dd, J = 12.0,
7.5 Hz, 4H), 7.72 (d, J = 8.2 Hz, 2H), 7.57−7.53 (m, 2H),
7.51−7.46 (m, 4H), 4.15 (d, J = 15.0 Hz, 2H);13C NMR (100
MHz, CDCl3):δ191.8 (d, J = 5.8 Hz), 139.8, 132.5 (d, J = 2.7 Hz),
132.4, 131.0 (d, J = 9.8 Hz), 129.8, 128.8 (d, J = 12.4 Hz), 117.9,
116.7, 44.1 (d, J = 55.4 Hz). 31P NMR (162 MHz, CDCl3): δ
2-(Diphenylphosphoryl)-1-(4-methoxyphenyl)ethanone (3c) 9
White solid, mp 147−148 °C, 62% yield (217.1 mg); 1H NMR
(400 MHz, CDCl3):δ7.99 (d, J = 8.8 Hz, 2H), 7.87−7.76 (m, 4
H),7.55–7.43 (m, 6 H),6.89(d, J = 8.7 Hz, 2H), 4.09 (d, J = 15.3
Hz, 2H), 3.85 (s, 3 H);13C NMR (100 MHz, CDCl3): δ191.0 (d, J
= 5.3 Hz), 164.0, 132.6, 132.1 (d, J = 2.3 Hz), 131.8, 131.2 (d, J
= 9.7 Hz), 130.2, 128.6 (d, J = 12.2 Hz), 113.7, 55.5, 43.3 (d, J
=58.3 Hz); 31P NMR (162 MHz, CDCl3):δ27.13; MS (ESI-TOF)
m/z: (M+H)+Calcd for C21H20O3P 351.1, found 351.1.
26.50;
HRMS
(ESI-TOF)
m/z:
(M+H)+Calcd
forC21H17NO2P346.0997, found 346.0990.
2-(Diphenylphosphoryl)-1-(4-nitrophenyl)ethanone (3j)11
2-(Diphenylphosphoryl)-1-(4-fluorophenyl)ethanone (3d)
Yellow solid, mp 163−164 °C,30% yield (109.0 mg); 1H NMR
(400 MHz, CDCl3): δ8.26 (d, J = 8.9 Hz, 2H), 8.20 (d, J = 8.9
Hz, 2H), 7.83–7.76 (m, 4H), 7.56 (td, J = 7.2, 1.3 Hz, 2H), 7.52–
7.47 (m, 4H), 4.17 (d, J = 15.1 Hz, 2H); 13C NMR (100 MHz,
CDCl3):δ191.6 (d, J = 5.8 Hz), 150.5, 141.2, 132.5 (d, J = 2.9
Hz), 131.9, 131.0 (d, J = 9.9 Hz), 130.5, 128.9 (d, J = 12.4 Hz),
1
White solid, mp 156−157 °C, 61% yield (206.2 mg); H NMR
(400 MHz, CDCl3): δ8.02 (dd, J = 8.4, 5.5 Hz, 2H), 7.80 (dd, J =
11.8, 7.5 Hz, 4H), 7.55−7.41 (m, 6H), 7.07 (t, J = 8.5 Hz, 2H),
4.11(d, J = 15.2 Hz, 2H); 13C NMR (100 MHz, CDCl3):δ191.2 (d,
J = 5.6 Hz), 166.0 (d, J = 256.0 Hz), 133.4 (d, J = 2.8 Hz), 132.3,
132.2 (d, J = 2.8 Hz), 132.1 (d, J = 9.6 Hz), 131.3, 131.1 (d, J =
9.8 Hz), 128.7 (d, J = 12.4 Hz), 115.6 (d, J = 22.0 Hz), 43.5 (d, J
= 56.9 Hz);31P NMR (162 MHz, CDCl3): δ26.81; HRMS (ESI-
TOF) m/z: (M+H)+Calcd forC20H17FO2P 339.0950, found
339.0944.
123.7, 44.3 (d,
J =
55.1 Hz); 31P NMR (162 MHz,
CDCl3):δ26.55; MS (ESI-TOF) m/z: (M+H)+Calcd for
C20H19NO4P 366.1, found 366.1.
2-(Diphenylphosphoryl)-1-(4-nitrophenyl)ethanol(3j’)
Yellow solid, mp 170−171 °C, 25% yield (92.1 mg); 1H NMR

5
(400 MHz, CDCl3): δ8.11 (d, J = 8.7 Hz, 2H), 7.75 (dd, J = 11.0,
7.7 Hz, 2H), 7.67 (dd, J = 11.8, 7.5 Hz, 2H), 7.60–7.55 (m, 1H),
7.54–7.46 (m, 5H), 7.43 (dt, J = 7.2, 3.7 Hz, 2H), 5.72 (s, 1H),
5.29 (t, J = 9.5 Hz, 1H), 2.81–2.67 (m, 1H), 2.65–2.55 (m, 1H);
13C NMR (100 MHz, CDCl3):δ151.4 (d, J = 12.5 Hz), 147.2,
132.4 (d, J = 2.4 Hz), 132.3 (d, J = 2.5 Hz), 130.8 (d, J = 9.5 Hz),
130.5 (d, J = 9.8 Hz), 129.0 (d, J = 4.1 Hz, 128.8 (d, J = 12 Hz),
126.5, 123.7, 68.4, 39.0 (d, J = 68.6 Hz); 31P NMR (162 MHz,
CDCl3): δ33.80; HRMS (ESI-TOF) m/z: (M+H)+Calcd for
C20H19NO4P 368.1052, found 368.1061.
J = 2.9 Hz), 131.6 (d, J = 2.5 Hz), 131.3 (d, J = 6.9 Hz), 131.0
ACCEPTED MANUSCRIPT
(d, J = 8.7 Hz), 130.7 (d, J = 9.1 Hz), 129.1 (d, J = 11.4 Hz),
128.3 (d, J = 12.0 Hz), 127.7, 127.2, 127.1, 125.9, 72.6, 53.2 (d,
J = 66.6 Hz);31P NMR (162 MHz, CDCl3):δ36.70; MS (ESI-
TOF) m/z: (M+H)+Calcd for C26H24O2P 399.1, found 399.1.
Diphenyl(3-phenylpropyl)phosphine oxide (3q)16
1
White solid, mp 116.5−117.0 °C, 80% yield (256.1 mg); H
NMR (400 MHz, CDCl3): δ7.72–7.63 (m, 4H), 7.56–7.38 (m,
7H), 7.25–7.22 (m, 1H), 7.20–7.16 (m, 1H), 7.11 (d, J = 6.9 Hz,
2H), 2.76–2.68 (m, 2H), 2.39–2.15 (m, 2H), 1.97–1.94 (m,
2H);13C NMR (75 MHz, CDCl3):δ140.8, 131.7, 130.7 (d, J = 9.0
Hz), 128.7, 128.6, 128.5, 128.4, 126.1, 36.6 (d, J = 14.8 Hz), 28.9
(d, J = 71.9 Hz), 23.0;31P NMR (162 MHz, CDCl3):δ32.46;
HRMS (ESI-TOF) m/z: (M+H)+Calcd for C21H22OP 321.1408,
found 321.1416.
2-(Diphenylphosphoryl)-1-methyl-1-phenyl)ethanol(3k)12
1
White solid, mp 178−179°C, 73% yield (245.4 mg); H NMR
(400 MHz, CDCl3): δ7.74 (dd, J = 11.1, 7.4 Hz, 2H), 7.54–7.46
(m, 3H), 7.37–7.30 (m, 5H), 7.24–7.19 (m, 2H), 7.07 (t, J = 7.3
Hz, 2H), 7.01 (t, J = 7.1 Hz, 1H), 5.05 (s, 1H), 2.92 (d, J = 9.3
Hz, 2H), 1.60 (s, 3H);13C NMR (100 MHz, CDCl3):δ146.7 (d, J =
5.9 Hz), 132.0 (d, J = 2.6 Hz), 131.2 (d, J = 2.7 Hz), 130.3 (d, J =
9.6 Hz), 128.8 (d, J = 11.7 Hz), 128.2 (d, J = 12.1 Hz), 127.8,
126.6, 124.8, 74.2 (d, J = 5.3 Hz), 42.3 (d, J = 69.1 Hz), 32.9 (d,
J = 9.5 Hz);31P NMR (162 MHz, CDCl3):δ32.74; MS (ESI-TOF)
m/z: (M+H)+Calcd for C21H22O2P 337.1, found 337.1.
Diphenyl(4-phenylbutyl)phosphine oxide (3r)17
1
White solid, mp 92−93°C, 86% yield (287.4 mg); H NMR
(400 MHz, CDCl3): δ7.75–7.69 (m, 4H), 7.54–7.43 (m, 6H),
7.26–7.09 (m, 5H), 2.61–2.56 (m, 2H), 2.32–2.24 (m, 2H),1.75–
1.67 (m, 4H);13C NMR (75 MHz, CDCl3):δ141.9, 133.7, 132.4,
131.7, 130.8 (d, J = 8.9 Hz), 128.6 (d, J = 11.3 Hz), 128.3, 125.8,
35.4, 32.7 (d, J = 14.2 Hz), 29.6 (d, J = 71.7 Hz), 21.2;31P NMR
(162 MHz, CDCl3):δ32.38; MS (ESI-TOF) m/z: (M+H)+ Calcd
for C22H24OP 335.1, found 335.1.
2-(Diphenylphosphoryl)-1,1-diphenyl)ethanol(3m)12
White solid, mp 183−184 °C, 74% yield (294.6 mg); 1H NMR
(400 MHz, CDCl3): δ8.05–7.97 (m, 2H), 7.60 (s, 3H), 7.51 (dd, J
= 11.3, 7.4 Hz, 2H), 7.29 (t, J = 7.0 Hz, 1H), 7.24–7.14 (m, 4H),
7.10–7.01 (m, 6H), 6.89–6.84 (m, 2H), 5.51 (d, J = 7.2 Hz, 1H),
5.17 (s, 1H), 3.64 (d, J = 8.0 Hz, 1H);13C NMR (100 MHz,
CDCl3):δ141.2 (d, J = 12.2 Hz), 132.2 (d, J = 2.4 Hz), 131.9 (d,
J= 2.9 Hz), 131.6 (d, J = 2.5 Hz), 131.3 (d, J = 6.9 Hz), 131.1 (d,
J = 8.7 Hz), 130.8 (d, J = 9.1 Hz), 129.1 (d, J = 11.4 Hz), 128.3
(d, J = 12.0 Hz), 127.7, 127.2, 127.1, 125.9, 72.6, 53.2(d, J =
66.6 Hz);31P NMR (162 MHz, CDCl3):δ33.24; MS (ESI-TOF)
m/z: (M+H)+Calcd for C26H24O2P 399.1, found 399.1.
Diphenyl 3-(p-tolyloxy)propyl)phosphine oxide (3s)17
1
White solid, mp 113−114°C, 79% yield (276.6 mg); H NMR
(400 MHz, CDCl3): δ7.82–7.67 (m, 4H), 7.55–7.43 (m, 6H), 7.05
(d, J = 8.1 Hz, 2H), 6.74 (d, J = 8.4 Hz, 2H), 4.00–3.92 (m, 2H),
2.54–2.42 (m, 2H), 2.27 (s, 3H), 2.16–2.02 (m, 2H);13C NMR (75
MHz, CDCl3):δ156.5, 132.8 (d, J = 98.9 Hz), 131.8, 130.8 (d, J =
9.1 Hz), 130.0, 129.9, 128.7 (d, J = 11.5 Hz), 114.3, 67.6 (d, J =
14.3 Hz), 26.4 (d, J = 72.8 Hz), 21.2 (d, J = 102.8 Hz);31P NMR
(162 MHz, CDCl3):δ32.55; HRMS (ESI-TOF) m/z: (M+H)+Calcd
for C22H24O2P 351.1514, found 351.1513.
2-(Diphenylphosphoryl)-2-methyl-1-phenyl)ethanol(3n)13
1
White solid, mp 189−190°C, 70% yield (235.3 mg); H NMR
Diphenyloctylphosphine oxide (3t)17
(400 MHz, CDCl3): δ7.75 (d, J = 6.5 Hz, 2H), 7.38–7.27 (m, 4H),
7.21–7.13 (m, 4H), 7.12–7.02(m, 5H), 4.62 (d, J = 30.7 Hz, 1H),
3.03–2.91 (m, 1H), 1.05 (dd, J = 16.6, 7.5 Hz, 3H);13C NMR
(100 MHz, CDCl3):δ139.3 (d, J = 4.0 Hz), 135.4 (d, J = 95.4 Hz),
132.2 (d, J = 8.4 Hz), 130.9 (d, J = 2.4 Hz), 130.7 (d, J = 4.2 Hz),
130.6, 128.1 (d, J = 11.1 Hz), 127.9, 127.5 (d, J = 11.3 Hz),
126.7, 53.7 (d, J = 3.0 Hz), 37.2 (d, J = 70.3 Hz), 16.7;31P NMR
(162 MHz, CDCl3):δ37.54; MS (ESI-TOF) m/z: (M+H)+Calcd for
C21H22O2P 337.1, found 337.1.
1
White solid, mp57−58°C, 61% yield (191.6 mg); H NMR
(400 MHz, CDCl3): δ7.78–7.70 (m, 4H), 7.53–7.44 (m, 6H),
2.34–2.18 (m, 2H), 1.70–1.54 (m, 2H), 1.43–1.33 (m, 2H),1.28–
1.17 (m, 8H), 0.85 (t, J = 6.7 Hz, 3H);13C NMR (75 MHz,
CDCl3):δ132.8 (d, J = 97.9 Hz), 131.6 , 130.6 (d, J = 9.0 Hz),
128.5 (d, J = 11.3 Hz), 31.6, 30.8 (d, J = 14.2 Hz), 29.5 (d, J =
72.1 Hz), 28.9, 22.4, 21.2 (d, J = 2.7 Hz), 21.1, 13.9;31P NMR
(162 MHz, CDCl3):δ32.96; MS (ESI-TOF) m/z: (M+H)+Calcd for
C20H27OP 315.2, found 315.2.
(E)-2-(Diphenylphosphoryl)-1-phenyl)ethylene (3o)14
Preparation of dimethyl (2-oxo-2-arylethyl)phosphonates
5. Typical procedure for the preparation of dimethyl (2-oxo-2-
phenylethyl)phosphonate (5a). To a solution of methanol (10
mL), styrene (0.11 g, 1.0 mmol) and dimethylphosphite (0.22 g,
2.0 mmol) was added Mn(OAc)3 (0.54 g, 2.0 mmol) over 30
minutes at 70oC, and the mixture was stirred for another 30
minutes to complete the reaction. Then, the solvent was removed
under vacuum. To the residue was added water (20 mL) and
extracted with ethyl acetate (10 mL× 3). The combined organic
fractions were dried over anhydrous Na2SO4, and concentrated
under vacuum to yield the crude product, which was purified by
White solid, mp 169−170 °C, 68% yield (206.7 mg); 1H NMR
(400 MHz, CDCl3): δ7.76 (dd, J = 11.9, 7.4 Hz, 4H), 7.58–7.43
(m, 9H), 7.41–7.32 (m, 3H), 6.84 (dd, J = 22.3, 17.4 Hz, 1H);13C
NMR (100 MHz, CDCl3):δ147.6 (d, J = 3.6 Hz), 135.1 (d, J =
17.9 Hz), 133.5, 132.5, 131.9 (d, J = 2.7 Hz), 131.4 (d, J = 10.0
Hz), 130.1, 128.9, 128.6 (d, J = 12.2 Hz), 127.8, 119.8, 118.7;31P
NMR (162 MHz, CDCl3):δ24.48; MS (ESI-TOF) m/z:
(M+H)+Calcd for C20H18OP 305.1, found 305.1.
2-(Diphenylphosphoryl)-1,2-diphenyl)ethanol (3p)15
1
White solid, mp248−249°C, 65% yield (258.8 mg); H NMR
column
chromatography
(silica
gel,
petroleum
(400 MHz, CDCl3): δ8.06–7.96 (m, 2H), 7.63–7.56 (m, 3H), 7.51
(dd, J = 11.3, 7.4 Hz, 2H), 7.29 (t, J = 7.0 Hz, 1H), 7.24–7.14 (m,
4H), 7.11–7.01 (m, 6H), 6.90–6.84 (m, 2H), 5.51 (d, J = 7.2 Hz,
1H), 5.17 (s, 1H), 3.65 (d, J = 8.0 Hz, 1H);13C NMR (100 MHz,
CDCl3): δ141.2 (d, J = 12.2 Hz), 132.2 (d, J = 2.4 Hz), 131.9 (d,
ether/EtOAc/CH2Cl2(10:1:1) ) to give pure dimethyl (2-oxo-2-
phenylethyl)phosphonate (5a).
Dimethyl (2-oxo-2-phenylethyl)phosphonate (5a)18
1
Colorless liquid; 69% yield (157.4 mg); H NMR (400 MHz,

6
Tetrahedron
1
CDCl3): δ8.04–7.97 (m, 2H), 7.61 (t, J = 7.4 Hz, 1H), 7.49 (t,
Colorless liquid, 59% yield (149.0 mg); H NMR (400 MHz,
CDCl3): δ 8.12 (d, J = 8.6 Hz, 2H), 7.80 (d, J = 8.6 Hz, 2H), 3.78
(d, J = 13.5 Hz, 6H), 3.66 (d, J = 22.9 Hz, 2H); 13C NMR (100
MHz, CDCl3):δ190.1 (d, J = 6.7 Hz), 138.7 (d, J = 1.9 Hz),
132.1, 128.9, 117.3, 116.5, 52.9 (d, J = 6.6 Hz), 37.5 (d, J =
130.2 Hz); 31P NMR (162 MHz, CDCl3): δ 21.41; HRMS (ESI-
TOF) m/z: (M+H)+Calcd for C11H13NO4P 254.0582, found
254.0583.
ACCEPTED MANUSCRIPT
J= 7.7 Hz, 2H), 3.79 (d, J = 11.2 Hz, 6H), 3.65 (d, J = 22.6 Hz,
2H);13C NMR (75 MHz, CDCl3):δ191.7 (d, J = 6.6 Hz),136.3 (d,
J = 2.5 Hz), 133.8, 128.9,128.7, 53.2 (d, J = 6.5 Hz), 37.4 (d, J =
131.0 Hz); 31P NMR (162 MHz, CDCl3):δ22.80; HRMS (ESI-
TOF) m/z: (M+H)+Calcd for C10H14O4P 229.0630, found
229.0635.
Dimethyl (2-oxo-2-(p-tolyl)ethyl)phosphonate (5b)18
Dimethyl (2-(4-nitrophenyl)-2-oxoethyl)phosphonate (5j)
1H NMR (400 MHz, CDCl3):δ7.98 (d, J = 8.3 Hz, 2H), 7.36
(d, J = 7.5 Hz, 2H), 3.86 (d, J = 11.2 Hz, 6H), 3.70 (d, J = 22.6
Hz, 2H), 2.50 (s, 3H); 13C NMR (100 MHz, CDCl3):δ190.8 (d, J
= 6.6 Hz), 144.4, 133.5 (d, J = 2.5 Hz), 128.9, 128.7, 52.7 (d, J =
6.5 Hz), 36.9 (d, J = 131.4 Hz), 21.2;31P NMR (162 MHz,
CDCl3):δ23.08; MS (ESI-TOF) m/z: (M+H)+Calcd for C11H16O4P
243.1, found 243.0.
1
Yellow liquid, 50 % yield (136.1 mg); H NMR (400 MHz,
CDCl3): δ 8.34 (d, J = 8.7 Hz, 2H), 8.20 (d, J = 8.8 Hz, 2H), 3.81
(d, J = 11.3 Hz, 6H), 3.71 (d, J = 22.9 Hz, 2H); 13C NMR (100
MHz, CDCl3):δ 190.4 (d, J = 6.8 Hz), 150.6, 140.6 (d, J = 2.0
Hz), 130.1, 123.9, 53.4 (d, J = 6.6 Hz), 38.1 (d, J = 129.5 Hz);
31P NMR (162 MHz, CDCl3): δ 21.30; HRMS (ESI-TOF) m/z:
(M+Na)+Calcd for C10H12NNaO6P 296.0300, found 296.0318.
Dimethyl (2-(4-methoxyphenyl)-2-oxoethyl)phosphonate (5c)19
Dimethyl (2,2-diphenylvinyl)phosphonate (5m)20
1H NMR (400 MHz, CDCl3): δ7.99 (d, J = 8.9 Hz, 2H), 6.95
(d, J = 8.9 Hz, 2H), 3.88 (s, 3H), 3.78 (d, J = 11.2 Hz, 6H), 3.60
(d, J = 22.6 Hz, 2H); 13C NMR (100 MHz, CDCl3):δ189.6 (d, J =
6.5 Hz), 163.6, 130.9, 129.0 (d, J = 2.4 Hz), 113.4, 55.0, 52.6 (d,
J = 6.5 Hz), 36.7 (d, J = 131.0 Hz);31P NMR (162 MHz,
CDCl3):δ23.24; HRMS (ESI-TOF) m/z: (M+H)+Calcd for
C11H16O5P 259.0735, found 259.0725.
1
Colorless liquid; 75% yield (216.1 mg); H NMR (400 MHz,
CDCl3): δ7.42–7.27 (m, 10H), 6.18 (d, J = 15.6 Hz, 1H), 3.50 (d,
J = 11.1 Hz, 6H);13C NMR (75 MHz, CDCl3): δ160.8 (d, J = 6.4
Hz), 141.1 (d, J = 29.7 Hz), 138.7 (d, J = 7.6 Hz), 129.5, 128.7,
128.3,128.1, 127.9, 127.0, 125.7, 114.8, 112.2, 52.1 (d, J = 6.0
Hz); 31P NMR (162 MHz, CDCl3):δ19.47; HRMS (ESI-TOF)
m/z: (M+H)+Calcd for C16H18O3P 289.0994, found 289.1003.
Dimethyl (2-(4-fluorophenyl)-2-oxoethyl)phosphonate (5d)19
(E)-Dimethyl styrylphosphonate (5o)21
1H NMR (400 MHz, CDCl3):δ8.11–7.99 (m, 2H), 7.20–7.12
(m, 2H), 3.79 (d, J = 11.2 Hz, 6H), 3.62 (d, J = 22.8 Hz, 2H); 13C
NMR (100 MHz, CDCl3):δ189.7 (d, J = 6.5 Hz), 165.7 (d, J =
255 Hz), 132.3 (dd, J = 2.0, 3.0 Hz),131.3 (d, J = 9.6 Hz), 115.4
(d, J = 22.0 Hz), 52.7 (d, J = 6.6 Hz), 37.1 (d, J = 130.9 Hz);31P
NMR (162 MHz, CDCl3):δ22.45; HRMS (ESI-TOF) m/z:
(M+H)+Calcd for C10H13FO4P 247.0535, found 247.0530.
1
Colorless liquid, 64% yield (135.7 mg); H NMR (400 MHz,
CDCl3): δ7.54–7.62 (m, 1H), 7.49–7.53 (m, 2H), 7.38–7.43 (m,
3H), 6.19–6.29 (m, 1H), 3.79 (d, J = 11.1 Hz, 6H); 13C NMR
(100 MHz, CDCl3):δ149.7 (d, J = 6.7 Hz), 134.6 (d, J = 23.3 Hz),
130.4, 128.9, 127.8, 112.3 (d, J = 191.3 Hz), 52.5 (d, J = 5.6 Hz).
31P NMR (162 MHz, CDCl3):δ22.35; MS (ESI-TOF) m/z:
(M+H)+Calcd for C10H14O3P 213.0, found 213.0.
Dimethyl (2-(4-chlorophenyl)-2-oxoethyl)phosphonate (5e)19
1
Colorless liquid, 63% yield (165.1 mg); H NMR (400 MHz,
CDCl3): δ7.96 (d, J = 8.6 Hz, 2H), 7.46 (d, J = 8.6 Hz, 2H), 3.79
(d, J = 11.2 Hz, 6H), 3.61 (d, J = 22.8 Hz, 2H);13C NMR (100
MHz, CDCl3):δ190.6 (d, J = 6.6 Hz), 140.4, 134.7 (d, J = 2.2
Hz), 130.4, 129.0, 53.2 (d, J = 6.5 Hz), 37.6 (d, J = 130.7 Hz);31P
NMR (162 MHz, CDCl3):δ22.42; HRMS (ESI-TOF) m/z:
(M+H)+Calcd for C10H13ClO4P 263.0240, found 263.0238.
Supplementary data
1
Copies of the H, 13C and 31P NMR spectra for compounds 3
and 5 are available.
Acknowledgements
J.-P.Z. expresses gratitude to the National Natural Science
Foundation of China (Nos. 20772088, 21172163, 21472133), the
Priority Academic Program Development of Jiangsu Higher
Education Institutions & State and Local Joint Engineering
Laboratory for Novel Functional Polymeric Materials for their
financial support.
Dimethyl (2-(4-bromophenyl)-2-oxoethyl)phosphonate (5g)19
1
Colorless liquid, 58% yield (117.5 mg); H NMR (400 MHz,
CDCl3): δ7.88 (d, J = 8.6 Hz, 2H), 7.63 (d, J = 8.6 Hz, 2H), 3.79
(d, J = 11.2 Hz, 6H), 3.61(d, J = 22.8 Hz, 2H); 13C NMR (100
MHz, CDCl3):δ190.8 (d, J = 6.0 Hz), 135.1 (d, J = 2.2 Hz),
132.1, 130.5, 129.3, 53.3 (d, J = 6.5 Hz), 37.6 (d, J = 130.0 Hz);
31P NMR (162 MHz, CDCl3): δ 22.30; MS (ESI-TOF) m/z:
(M+Na)+Calcd for C10H12BrO4PNa 328.9, found 328.9.
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