Copper-catalyzed direct esterification of P(O)-OH compounds with phenols

Article abstract of DOI:10.1016/j.tet.2015.10.028

A novel copper-catalyzed method for the direct esterification of P(O)-OH compounds using phenols as efficient esterification reagents is illustrated. It is a simple way to generate a broad spectrum of functionalized O-aryl phosphinates, phosphonates, and phosphates from basic starting materials with moderate to excellent yields.

Full text of DOI:10.1016/j.tet.2015.10.028

Accepted Manuscript
Copper-Catalyzed Direct Esterification of P(O)-OH Compounds with Phenols
Biquan Xiong, Kui Zeng, Shanshan Zhang, Yongbo Zhou, Chak-Tong Au, Shuang-
Feng Yin
PII:
S0040-4020(15)30128-9
10.1016/j.tet.2015.10.028
TET 27200
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 16 August 2015
Revised Date: 8 October 2015
Accepted Date: 10 October 2015
Please cite this article as: Xiong B, Zeng K, Zhang S, Zhou Y, Au C-T, Yin S-F, Copper-Catalyzed Direct
Esterification of P(O)-OH Compounds with Phenols, Tetrahedron (2015), doi: 10.1016/j.tet.2015.10.028.
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Graphical Abstract
Copper-Catalyzed Direct Esterification of
P(O)-OH Compounds with Phenols
Leave this area blank for abstract info.
Biquan Xiong, Kui Zeng, Shanshan Zhang, Yongbo Zhou, Chak-Tong Au, Shuang-Feng Yin*
State Key Laboratory of Chemo/Biosensing and Chemometrics, Hunan Provincial Key Laboratory for Cost-
effective Utilization of Fossil Fuel Aimed at Reducing Carbon-dioxide Emissions, College of Chemistry and
Chemical Engineering, Hunan University, Changsha, 410082, P.R.China.

1
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Tetrahedron
journal homepage: www.elsevier.com
Copper-Catalyzed Direct Esterification of P(O)-OH Compounds with Phenols
Biquan Xiong, Kui Zeng, Shanshan Zhang, Yongbo Zhou, Chak-Tong Au, Shuang-Feng Yin*
State Key Laboratory of Chemo/Biosensing and Chemometrics, Hunan Provincial Key Laboratory for Cost-effective Utilization of Fossil Fuel Aimed at
Reducing Carbon-dioxide Emissions, College of Chemistry and Chemical Engineering, Hunan University, Changsha, 410082, P.R.China.
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
A novel copper-catalyzed method for the direct esterification of P(O)-OH compounds using
phenols as efficient esterification reagents is illustrated. It is a simple way to generate a broad
spectrum of functionalized O-aryl phosphinates, phosphonates, and phosphates from basic
starting materials with moderate to excellent yields.
Available online
2015 Elsevier Ltd. All rights reserved
.
Keywords:
Copper catalysis
Esterification
P(O)-OH compounds
Phenols
1. Introduction
compounds without the use of diaryliodonium salts. Compared
with P(O)-H or P-Cl compounds, P(O)-OH compounds are more
air- and/or moisture-stable, and the use of them is more cost-
saving and environment-benign. To the best of our knowledge,
the synthesis of O-aryl organophosphorus compounds via the
esterification of P(O)-OH compounds with phenols has not been
realized.[10-12]
Organophosphorus compounds are important intermediates in
organic synthesis for the generation of industrial materials,
medicinal chemicals, lubricants, and phosphine ligands,[1-6]
showing a broad range of biological properties and acting as
bioactive entitles. Certain phosphoryl esters are motifs in natural
products, pharmacological agents, amino acid analogues, and
synthetic precursors. In recent years, there is a growing interest in
these kinds of compounds. For their preparation, orthodox
nucleophlic substitution of toxic phosphorus halides with phenols
are commonly adopted.[7] The reaction of P(O)-H compounds
with phenols (the Atherton-Todd reaction) is also extensively
used for the synthesis of the compounds, but the approach suffers
from the low tolerance of functional groups and substrate
limitations.[8] In 2014, FanÞanaìs-Mastral and Feringa first
disclosed the synthesis of mixed alkyl aryl phosphonates using
easily available phosphonates as starting materials over copper
catalysts, where the P=O bond coordinates with copper
efficiently to activate the phosphonates.[9]
Scheme 1. Methods for the synthesis of O-aryl containing organophosphorus
compounds.
So far, the direct cross-coupling of P(O)-OH compounds with
iodobenzene or phenyl boronic acid has not been disclosed. We
recently reported the reaction of P(O)-OH compounds with diaryl
iodonium triflates for the synthesis of O-aryl organophosphorus
compounds.[12k] As an ongoing effort on the activation of P(O)-
OH compounds, we studied the direct esterification of P(O)-OH
compounds with phenols under mild conditions using copper as
catalyst. Herein we report this efficient and simple protocol that
is more economical and convenient than those reported in the
literature for the synthesis of O-aryl organophosphorus
2. Results and Discussion
The reaction of diphenyl phosphinic acid with phenol at 100
oC with the assistance of CuI, CCl4 and Et3N in the presence of
Na2CO3 under air atmosphere gives O-phenyl diphenyl
phosphinate 3a in 12% yield (Table 1, entry 1). The use of CCl4
and Et3N is crucial for the reaction. Among the copper sources
(CuI, CuBr, CuCl, CuBr2, CuCl2, Cu(OAc)2, CuO, Cu2O, and Cu
powder), Cu powder gives the best result (Table 1, entries 1-9).
We investigated the effect of loading and found that when the

2
Tetrahedron
ACCEPTED MANUSCRIPT
amount of Cu powder is increased from 10 to 20 mol%, the
plausibly due to steric hindrance. For most cases, electron-
product yield increases from 23% to 43%, and a further increase
of Cu powder to 50 mol% causes further increase to 91% (Table
1, entries 1, 9-11). Besides Na2CO3, we tested other bases such as
K2CO3, t-BuONa, K3PO4, KOH, NaHCO3 and AcOK. It is
apparent that Na2CO3 is the best, and 91% yield of 3a is obtained
at a “diphenyl phosphinic acid:Na2CO3 molar ratio” of 1:2 (Table
1, entries 15-20).
donating groups (Table 2, 3b-3d, 3h, 3j, 3o, 3q-3r) or electron-
withdrawing groups (Table 2, 3e-3g, 3i, 3m-3n and 3p) of
phenols do not change the yields significantly.
Table 2
Scope of phenols a
O
P
O
P
Cu powder (50 mol%), CCl4 (4 eq), Et3N (1 eq)
Na2CO3 (2 eq), 100 oC, air
Ph
OH
+
ArOH
Ph
OAr
2
Ph
1a
Ph
3 b
Table 1
O
P
O
Optimization of the esterification of 1a with 2a a
O
O
P
Ph
OPh
Ph
P
O
t-Bu
Ph
)
P
O
Ph
O
OMe
O
O
[Cat.], [Base], [Additive]
100 oC, CH2Cl2, air
Ph
Ph
Ph
3b, 83%
Ph
3a, 87% (91% c
3d, 91%
3c, 81%
+
P OPh
Ph
P OH PhOH
Ph
Ph
3a
O
O
O
P
Ph
1a
2a
O
Br
Ph
Ph
P
O
F
NO2
Ph
P
O
Ph
O
Ph
P
O
Ph
Ph
Ph
Ph
Entry
1
2
3
4
5
6
7
8
Catalyst (10 mol%)
CuI
Base
Yield b
12%
9%
10%
9%
7%
7%
5%
9%
23%
43% c
91% d
27% e
66% f
35% g
87%
64%
73%
27%
89%
trace
29% h
N.D. i
3e, 95%
3f, 92%
3h, 86%
3g, 88%
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
K2CO3
t-BuONa
K3PO4
KOH
NaHCO3
AcOK
Na2CO3
Na2CO3
NO2
OMe
CuBr
CuCl
CuBr2
CuCl2
Cu(OAc)2
CuO
Cu2O
Cu powder
Cu powder
Cu powder
Cu powder
Cu powder
Cu powder
Cu powder
Cu powder
Cu powder
Cu powder
Cu powder
Cu powder
Cu powder
O
O
O
O
P
O
Ph
P
O
Ph
P
O
Ph
P
O
Ph
3i, 79%
Ph
Ph
Ph
3j, 89%
3k, 81%
3l, 84%
OMe
CN
Br
O
O
O
O
Ph
P
O
Cl
Ph
Ph
P
O
Ph
P
O
Ph
P
O
9
Ph
Ph
Ph
Ph
10
11
12
13
14
15
16
17
18
19
20
21
22
3n, 77%
3m, 62%
3o, 81%
t-Bu
3p, 93%
O
P
O
P
O
P
O
Ph
O
t-Bu
Ph
O
Ph
Ph
3r, 57%
Ph
3s, N.D.d
3q, 65%
a
Reaction conditions: diphenyl phosphinic acid (0.5 mmol), phenols (1.0
mmol), Na2CO3 (1.0 mmol), Cu powder (50 mol%), CCl4 (2.0 mmol), Et3N
o
b
c
(0.5 mmol), CH2Cl2 (3 mL), air, 100 C, 12 h. Isolated yields. Yield was
d
determined by GC analysis, and dodecane was used as internal standard.
N.D. = Not detected.
a
Reactions were carried out with diphenyl phosphinic acid (0.5 mmol),
Table 3
phenol (1.0 mmol), Et3N (0.5 mmol), CCl4 (2.0 mmol), and base (1.0 mmol)
in CH2Cl2 (3 mL), under air atmosphere stirred at 100 oC for 12 h. Entries 12-
Scope of P(O)-OH compounds a
b
O
O
P
20, Cu powder (50 mol%). Yield was determined by GC analysis, and
Cu powder (50 mol%), CCl4 (4 eq), Et3N (1 eq)
Na2CO3 (2 eq), 100 oC, air
R1
P
OH + PhOH
R1
OAr
dodecane was used as internal standard. c Cu powder (20 mol%). d Cu powder
R2
1
R2
2a
e
o
f
o
o
h
i
(50 mol%). 60 C. 80 C. g 120 C. No solvent used. Copper powder (0
4 b
mol%), N.D. = Not detected.
O
O
O
O
PhO
P
OPh
n-Bu
P
OPh
n-Bu
4c, 81%
Ph
P
OPh
OEt
4d, 85%
BuO
P
OPh
OBu
4b, 73%
OPh
4a, 79%
It turned out that the copper-catalyzed esterification reaction is
generally applicable for the transformation of P(O)-OH
compounds to O-aryl organophosphorus compounds. As shown
in Table 2, phenols such as p-cresol, 4-tert-butyl phenol, 4-
methoxy phenol, 4-bromo phenol, 4-fluoro phenol, 4-nitro
phenol, m-cresol, and 3-nitro phenol react efficiently with
diphenyl phosphinic acid (1a) under the optimized reaction
conditions to afford the corresponding products of O-aryl
phosphoryl compounds 3 in moderate to excellent yields (Table
2, 3a-3i). In addition, the reaction of 1a with 3-methoxy phenol
affords the desired product in 89% yield. It is observed that 1-
naphthol and 2-naphthol also exhibit high reactivity, generating
the corresponding products in 81% and 84% yields, respectively
(Table 2, 3k-3l). It was observed that substituted naphthols such
as 1-bromo-2-naphthol, 4-chloro-1-naphtol, 6-methoxy-1-
naphthol, and 6-cyano-1-naphtol give 3m-3p in 62-93% yields.
Ortho-substituted phenols such as 2-methyl phenol and 2,4-
dimethyl phenol both react with diphenyl phosphinic acid
efficiently, affording 3q and 3r in 65% and 57% yields. When
2,4-di-tert-butyl phenol was adopted for the reaction, the
esterification product 3s is not detected. And the phenomenon is
O
P
O
P
OPh F3C
OPh
O
P
O
O
O
O
OPh
P
OPh
4h, N.D. c
4e, 93%
4f, 96%
4g, 94%
CF3
a
Reaction conditions: P(O)-OH compounds (0.5 mmol), phenol (1.0 mmol),
Na2CO3 (1.0 mmol), Cu powder (50 mol%), CCl4 (2.0 mmol), Et3N (0.5
mmol), CH2Cl2 (3 mL), air, 100 oC, 12 h. Isolated yields. N.D. = Not
b
c
detected.
As depicted in Table 3, we investigated a variety of substituted
P(O)-OH compounds (1b-1i) with phenol under the optimized
conditions. It is clear that diphenyl hydrogen phosphate, dibutyl
hydrogen phosphate, dibutyl phosphinic acid, and ethyl hydrogen
phenylphosphonate react with phenol (2a) efficiently to give the
corresponding O-aryl phosphoryl products 4a-4d in 73-85%
yields. Aryl substituted diphenyl phosphinic acids such as di-(4-
methyl phenyl) phosphinic acid and di-(4-trifluoromethyl phenyl)

3
phosphinic acid are also good substrates for the reaction, and the
elimination accompanied by the regeneration of Cu or Cu (I) as
a catalytically active species.
ACCEPTED MANUSCRIPT
expected esterification products of 4e and 4f are generated in
93% and 96% yields, respectively. In addition, O-phenyl-
dibenzooxaphosphorine oxide 4g is formed in 94% yield through
the reaction of phenol with 10-hydroxy-9,10-dihydro-9-oxa-10-
3. Conclusion
In summary, we developed an efficient copper-catalyzed
method for O-aryl esterification of P(O)-OH compounds with
phenols through the activation of P=O double bond. The
approach avoids the use of air-sensitive reagents, and the reaction
can be performed under ambient conditions, making the
experimental procedure simple. The synthetic method has high
potential for the synthesis of biologically active molecules,
catalytic ligands, and organophosphorus compounds.
phosphaphenanthren-e-10-oxide. However, when
a
five-
membered cyclic P(O)-OH compound (1i) is adopted, there is no
detection of the corresponding esterification product. It is
deduced that 1h is unstable and plausibly undergoes
decomposition under the adopted reaction conditions.
O
P
O
P
Cu powder (50 mol%), CCl4 (4 eq), Et3N (1 eq)
CH2Cl2 (3 mL), Na2CO3 (2 eq), 100 oC, N2
a)
b)
+
PhOH
Ph
Ph
OH
Ph
OPh
4. Experimental section
2a
Ph
1a
Ph
3a, 76%
4.1 General information and materials.
O
P
O
Cu powder (50 mol%), CCl4 (4 eq), Et3N (1 eq)
The reactions were conducted in a sealed Schlenk tube at 100
oC under N2 or air atmosphere. All solvents used in reactions
were freshly distilled. All other reagents were recrystallized or
distilled as necessary. All reactions were performed under an
atmosphere of dry nitrogen. The copper powder (99.9%, 231 um)
and phenols (AR) adopted in the reaction were purchased from
OH + PhOH
Ph
P
OPh
TEMPO (1.1 eq), Na2CO3 (2 eq), 100 oC, air
CH2Cl2 (3 mL)
2a
Ph
1a
Ph
3a, 71%
Scheme 2. Mechanistic investigation.
Aladdin Industrial Inc. H (400 MHz), 13C (100 MHz), and 31P
1
In order to clarify the reaction mechanism, we tested the effect
(162 MHz) spectra were recorded on a 400MHz spectrometer in
CDCl3. 1H NMR chemical shifts are reported using TMS as
internal standard; 13C NMR chemical shifts are reported relative
to CDCl3 as internal standard. The electron ionization method
was used as the ionization method for the HRMS measurement,
and the mass analyzer type is double-focusing.
of oxygen in this reaction. In a control reaction of diphenyl
phosphinic acid with phenol under the same reaction conditions
but in N2 rather than in air, there is the generation of
esterification product 3a in 76% yield (Scheme 3, path a).13 In
addition, 3a is also obtained in 71% yield with the addition of
TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy) to the reaction.
Thus, it is deduced that the reaction does not involve a step of
radical interaction.
4.2 General procedure.
A mixture of P(O)-OH compounds (0.5 mmol), Na2CO3 (1
mmol), CCl4 (2 mmol), Et3N (0.5 mmol) and Cu powder (0.25
mmol) in CH2Cl2 (3 mL) was stirred at 100 oC under air
atmosphere for 12 h. Removal of the solvent under reduced
pressure gave the crude product; pure product was obtained by
passing the crude product through a short silica gel column using
Hexane/EtOAc (1:1 to 5:1) as eluent
CCl4
Et3N
O
P
[Cu(I)]
Ar-OH
Cu
O
P
R1
OHEt3N
R1
OH
CCl3
CCl4
R2
(B)
R2
(A)
Cl Ar
(I)
4.2.1. O-phenyl phenyl (phenyl) phosphinate (3a).12k Yield: 127.8
Cu
O
[Cu] or [Cu(I)]
Et3NH
H
1
o
O
R1
R2
Et3NH
mg, (87 %). Yellow oil. H NMR (400 MHz, CDCl3, 25 C,
TMS): δ= 7.87-7.92 (m, 4H; Ar), 7.49-7.53 (m, 2H; Ar), 7.42-
7.46 (m, 4H; Ar), 7.19-7.26 (m, 4H; Ar), 7.04-7.07 (m, 1H; Ar);
P
O
Et3N
Cl-CCl3
(C)
o
1
13C NMR (100 MHz, CDCl3, 25 C, TMS): δ= 150.9 (d, J (C,P)
= 8.1 Hz; Ar), 132.5 (d, 1J (C,P) = 2.8 Hz; Ar), 131.8 (d, 1J (C,P)
= 10.4 Hz; Ar), 131.0 (d, 1J (C,P) = 137.4 Hz; Ar-C-P), 129.7 (s;
[Cu(II)]
ArOH
OAr
+
Na2CO3
O
P
Cl Ar
(II)
ArOH
R1
1
1
Cu
O
Ar), 128.6 (d, J (C,P) = 13.4 Hz; Ar), 124.6 (s; Ar), 120.7 (d, J
H
(C,P) = 4.8 Hz; Ar); 31P NMR (160 MHz, CDCl3, 25 C): δ=
o
O
R2
(E)
R1
R2
Na+
CHCl3
+
Cl
NaCl
P
O
30.38.
OAr
(D)
Scheme 3. Proposed mechanism.
4.2.2. 4-Methyl-O-phenyl phenyl (phenyl) phosphinate (3b).12k
Yield: 127.6 mg, (83 %). Yellow oil. 1H NMR (400 MHz,
o
CDCl3, 25 C, TMS): δ= 7.86-7.92 (m, 4H; Ar), 7.47-7.53 (m,
2H; Ar), 7.44-7.47 (m, 4H; Ar), 7.06-7.09 (m, 2H; Ar), 7.00-7.03
(m, 2H; Ar), 2.24 (s, 3H; -CH3); 13C NMR (100 MHz, CDCl3, 25
A plausible mechanism for the copper-catalyzed esterification
of P(O)-OH compounds with phenols is proposed as illustrated in
1
oC, TMS): δ= 148.4 (d, J (C,P) = 8.1 Hz; Ar), 134.0 (s; Ar),
132.3 (s; Ar), 131.7 (d, 1J (C,P) = 10.2 Hz; Ar), 130.9 (d, 1J (C,P)
14]
Scheme 3.[12k,
P(O)-OH compound (A) first combines with
1
= 139.0 Hz; Ar-C-P), 130.0 (s; Ar), 128.4 (d, J (C,P) = 13.4 Hz;
1
Ar), 120.3 (d, J (C,P) = 3.7 Hz; Ar), 20.6 (s; -CH3); 31P NMR
Et3N to form intermediate B. In the presence of CCl4, copper
powder is readily oxidized to the corresponding copper (I) salts.
With the assistance of CCl4, there is simultaneous coordination of
intermediate B with Cu(I) and phenol, forming transition state C
as a result. Then another molecule of phenol attacks C to give the
copper (II) coordinated transition state D together with the
elimination of CHCl3 and Cl-. Finally, the catalytic cycle is
completed via the formation of P=O bond by means of
(160 MHz, CDCl3, 25 oC): δ= 28.06.
4.2.3. 4-tert-Butyl-O-phenyl phenyl (phenyl) phosphinate (3c).12k
Yield: 141.7 mg, (81 %). White solid. 1H NMR (400 MHz,
o
CDCl3, 25 C, TMS): δ= 7.78-7.84 (m, 4H; Ar), 7.36-7.42 (m,
2H; Ar), 7.33-7.36 (m, 4H; Ar), 7.14 (d, J = 8.4 Hz, 2H; Ar), 1.15
o
(s, 9H; -CH3); 13C NMR (100 MHz, CDCl3, 25 C, TMS): δ=
1
1
148.3 (d, J (C,P) = 8.3 Hz; Ar), 147.2 (s; Ar), 132.2 (d, J (C,P)
= 2.3 Hz; Ar), 131.6 (d, 1J (C,P) = 7.8 Hz; Ar), 131.1 (d, 1J (C,P)

4
Tetrahedron
1
1
= 137.3 Hz; Ar-C-P), 128.4 (d, J (C,P) = 13.3 Hz; Ar), 126.4
4.0 Hz; Ar), 119.5 (s; Ar), 116.1 (d, J (C,P) = 5.1 Hz; Ar); 31P
ACCEPTED MANUSCRIPT
(s; Ar), 119.9 (d, 1J (C,P) = 4.6 Hz; Ar), 34.1 (s; -C-(CH3)3), 31.2
NMR (160 MHz, CDCl3, 25 oC): δ= 30.63.
(s; CH3); 31P NMR (160 MHz, CDCl3, 25 oC): δ= 31.27.
4.2.10. 3-Methoxy-O-phenyl phenyl (phenyl) phosphinate (3j).15c
Yield: 140.6 mg, (89 %). Colorless oil. H NMR (400 MHz,
CDCl3, 25 C, TMS): δ= 7.87-7.92 (m, 4H; Ar), 7.43-7.54 (m,
4.2.4. 4-Methoxy-O-phenyl phenyl (phenyl) phosphinate (3d). 12k
Yield: 147.1 mg, (91 %). White solid. H NMR (400 MHz,
CDCl3, 25 C, TMS): δ= 7.86-7.91 (m, 4H; Ar), 7.48-7.55 (m,
1
1
o
o
6H; Ar), 7.09-7.13 (m, 1H; Ar), 6.78-6.80 (m, 2H; Ar), 6.61-6.63
2H; Ar), 7.43-7.47 (m, 4H; Ar), 7.10 (d, J = 11.2 Hz, 2H; Ar),
6.74 (d, J = 11.2 Hz, 2H; Ar), 3.71 (s, 3H; OCH3); 13C NMR (100
MHz, CDCl3, 25 oC, TMS): δ= 156.1 (s; Ar), 144.0 (d, 1J (C,P) =
8.2 Hz; Ar), 132.1 (d, 1J (C,P) = 2.4 Hz; Ar), 131.5 (d, 1J (C,P) =
(m, 1H; Ar), 3.70 (s, 3H; OCH3); 13C NMR (100 MHz, CDCl3,
o
1
25 C, TMS): δ= 160.6 (s; Ar), 132.5 (d, J (C,P) = 2.9 Hz; Ar),
1
1
131.8 (d, J (C,P) = 10.3 Hz; Ar), 130.9 (d, J (C,P) = 137.5 Hz;
1
Ar-C-P), 130.0 (s; Ar), 128.7 (s; Ar), 128.6 (s; Ar), 112.9 (d, J
10.5 Hz; Ar),130.7 (d, 1J (C,P) = 137.1 Hz; Ar-C-P), 128.3 (d, J
(C,P) = 4.8 Hz; Ar), 110.7 (s; Ar), 106.7 (d, J (C,P) = 5.2 Hz;
1
1
1
o
(C,P) = 13.3 Hz; Ar), 121.3 (d, J (C,P) = 4.3 Hz; Ar), 114.3 (s;
Ar), 55.3 (s; OCH3); 31P NMR (160 MHz, CDCl3, 25 C): δ=
Ar), 55.1 (d, J (C,P) = 4.2 Hz; OCH3); 31P NMR (160 MHz,
30.42.
1
CDCl3, 25 oC): δ= 28.44.
4.2.11. O-Naphthalen-1-yl phenyl (phenyl) phosphinate (3k).15d
4.2.5. 4-Bromo-O-phenyl phenyl (phenyl) phosphinate (3e).12k
Yield: 177.5 mg mg, (95 %). Colorless oil. H NMR (400 MHz,
CDCl3, 25 C, TMS): δ= 7.85-7.90 (m, 4H; Ar), 7.52-7.54 (m,
Yield: 139.4 mg, (81 %). Yellow oil. 1H NMR (400 MHz,
1
o
CDCl3, 25 C, TMS): δ= 8.20-8.22 (m, 1H; Ar), 7.94-7.99 (m,
o
4H; Ar), 7.78-7.80 (m, 1H; Ar), 7.44-7.54 (m, 10H; Ar), 7.23-
2H; Ar), 7.44-7.48 (m, 4H; Ar), 7.32-7.34 (m, 2H; Ar), 7.09-7.11
7.27 (m, 1H; Ar); 13C NMR (100 MHz, CDCl3, 25 oC, TMS): δ=
(m, 2H; Ar); 13C NMR (100 MHz, CDCl3, 25 oC, TMS): δ= 149.8
171.2 (s; Ar), 147.1 (d, J (C,P) = 8.3 Hz; Ar), 134.8 (s; Ar),
132.6 (d, J (C,P) = 2.7 Hz; Ar), 131.7 (d, J (C,P) = 10.4 Hz;
Ar), 131.0 (d, J (C,P) = 137.8 Hz; Ar-C-P), 128.7 (d, J (C,P) =
3.4 Hz; Ar), 127.9 (s; Ar), 126.6 (s; Ar), 126.5 (s; Ar), 125.6 (s;
Ar), 124.4 (s; Ar), 121.6 (s; Ar), 115.3 (d, 1J (C,P) = 4.4 Hz; Ar);
31P NMR (160 MHz, CDCl3, 25 oC): δ= 30.97.
1
1
1
1
(d, J (C,P) = 7.9 Hz; Ar), 132.6 (s; Ar), 132.5 (s; Ar), 131.6 (d,
1J (C,P) = 10.4 Hz; Ar), 130.3 (d, J (C,P) = 137.1 Hz; Ar-C-P),
1
1
1
1
1
128.6 (d, J (C,P) = 13.4 Hz; Ar), 122.4 (d, J (C,P) = 4.6 Hz;
Ar), 117.5 (s; Ar); 31P NMR (160 MHz, CDCl3, 25 oC): δ= 29.16.
4.2.6. 4-Fluoro-O-phenyl phenyl (phenyl) phosphinate (3f).12k
Yield: 143.8 mg, (92 %). Yellow oil. 1H NMR (400 MHz,
4.2.12. O-Naphthalen-2-yl phenyl (phenyl) phosphinate (3l).
o
CDCl3, 25 C, TMS): δ= 7.85-7.90 (m, 4H; Ar), 7.52-7.54 (m,
Yield: 144.8 mg, (84 %). Yellow oil. 1H NMR (400 MHz,
o
2H; Ar), 7.46-7.49 (m, 4H; Ar), 7.13-7.15 (m, 2H; Ar), 6.69-6.93
CDCl3, 25 C, TMS): δ= 7.93-7.98 (m, 4H; Ar), 7.71-7.76 (m,
(m, 2H ; Ar); 13C NMR (100 MHz, CDCl3, 25 C, TMS): δ=
4H; Ar), 7.38-7.53 (m, 9H; Ar); 13C NMR (100 MHz, CDCl3, 25
o
2
1
1
159.5 (d, J (C,F) = 241.8 Hz; Ar-C-F), 146.7 (d, J (C,P) = 5.6
oC, TMS): δ= 148.5 (d, J (C,P) = 8.2 Hz; Ar), 133.8 (s; Ar),
1
1
1
Hz; Ar), 132.6 (d, J (C,P) = 2.4 Hz; Ar), 131.8 (d, J (C,P) =
10.3 Hz; Ar), 130.7 (d, 1J (C,P) = 137.1 Hz; Ar-C-P), 128.7 (d, 1J
(C,P) = 13.4 Hz; Ar), 122.2 (dd, 1J (C,P) = 3.7 Hz, 2J (C,F) = 12.7
132.4 (s; Ar), 131.8 (s; Ar), 131.7 (s; Ar), 130.7 (d, J (C,P) =
137.6 Hz; Ar-C-P), 130.5 (s; Ar), 129.6 (s; Ar), 128.5 (d, 1J (C,P)
1
= 13.4 Hz; Ar), 127.4 (d, J (C,P) = 10.5 Hz; Ar), 126.4 (s; Ar),
Hz; Ar), 116.2 (d, J (C,P) = 23.2 Hz; Ar); 31P NMR (160 MHz,
125.1 (s; Ar), 120.6 (d, J (C,P) = 4.7 Hz; Ar), 117.1 (d, J (C,P)
1
1
1
CDCl3, 25 oC): δ= 29.05; 19F NMR (377 MHz, CDCl3, 25 oC): δ=
= 4.9 Hz; Ar); 31P NMR (160 MHz, CDCl3, 25 C): δ= 28.63.
o
-118.3.
HRMS calcd. for C22H17O2P: 344.0966, found: 344.0963.
4.2.7. 4-Nitro-O-phenyl phenyl (phenyl) phosphinate (3g).15a
4.2.13. O-1-Bromonaphthalen-2-yl phenyl (phenyl) phosphinate
1
Yield: 175.9 mg, (88 %). Yellow oil. 1H NMR (400 MHz,
(3m).15e Yield: 131.1 mg, (62 %). Yellow oil. H NMR (400
o
o
CDCl3, 25 C, TMS): δ= 8.13-8.15 (m, 2H; Ar), 7.86-7.91 (m,
MHz, CDCl3, 25 C, TMS): δ= 8.20-8.22 (m, 1H; Ar), 8.02-8.08
4H; Ar), 7.58-7.59 (m, 2H; Ar), 7.49-7.52 (m, 4H; Ar), 7.37-7.39
(m, 4H; Ar), 7.85-7.87 (m, 1H; Ar), 7.67-7.76 (m, 2H; Ar), 7.42-
7.58 (m, 8H; Ar); 13C NMR (100 MHz, CDCl3, 25 oC, TMS): δ=
146.8 (d, 1J (C,P) = 7.2 Hz; Ar), 132.7 (d, 1J (C,P) = 2.9 Hz; Ar),
(m, 2H; Ar); 13C NMR (100 MHz, CDCl3, 25 oC, TMS): δ= 155.8
1
(d, J (C,P) = 7.5 Hz; Ar), 144.2 (s; Ar), 132.9 (s; Ar), 131.5 (d,
1
1
1J (C,P) = 10.6 Hz; Ar), 129.7 (d, J (C,P) = 137.3 Hz; Ar-C-P),
132.1 (d, 1J (C,P) = 145.6 Hz; Ar-C-P), 132.0 (d, J (C,P) = 10.6
128.7 (d, 1J (C,P) = 13.6 Hz; Ar), 125.5 (s; Ar), 121.1 (d, 1J (C,P)
Hz; Ar), 131.3 (s; Ar), 130.0 (s; Ar), 129.0 (s; Ar), 128.7 (d, J
1
= 5.0 Hz; Ar); 31P NMR (160 MHz, CDCl3, 25 oC): δ= 30.49.
(C,P) = 13.6 Hz; Ar), 128.2 (s; Ar), 127.8 (s; Ar), 126.7 (s; Ar),
1
1
125.8 (s; Ar), 120.5 (d, J (C,P) = 3.5 Hz; Ar), 112.5 (d, J (C,P)
4.2.8. 3-Methyl-O-phenyl phenyl (phenyl) phosphinate (3h).15b
= 7.6 Hz; Ar); 31P NMR (160 MHz, CDCl3, 25 oC): δ= 32.04.
Yield: 132.4 mg, (86 %). Yellow oil. 1H NMR (400 MHz, CDCl3,
o
25 C, TMS): δ= 7.86-7.92 (m, 4H; Ar), 7.49-7.53 (m, 2H; Ar),
4.2.14. O-1-Chloronaphthalen-4-yl phenyl (phenyl) phosphinate
1
7.42-7.47 (m, 4H; Ar), 7.05-7.11 (m, 2H; Ar), 6.96-6.98 (m, 1H;
(3n). Yield: 145.9 mg, (77 %). Yellow oil. H NMR (400 MHz,
Ar), 6.86-6.88 (m, 1H; Ar), 2.25 (s, 3H; CH3); 13C NMR (100
CDCl3, 25 C, TMS): δ= 8.19-8.24 (m, 2H; Ar), 7.92-7.97 (m,
o
o
1
MHz, CDCl3, 25 C, TMS): δ= 150.7 (d, J (C,P) = 8.1 Hz; Ar),
4H; Ar), 7.34-7.63 (m, 10H; Ar); 13C NMR (100 MHz, CDCl3,
1
o
1
1
139.7 (s; Ar), 132.3 (s; Ar), 131.7 (d, J (C,P) = 10.2 Hz; Ar),
25 C, TMS): δ= 146.1 (d, J (C,P) = 8.2 Hz; Ar), 132.7 (d, J
131.1 (d, 1J (C,P) = 174.2 Hz; Ar-C-P), 129.2 (s; Ar), 128.4 (d, 1J
(C,P) = 2.9 Hz; Ar), 131.8 (d, J (C,P) = 10.4 Hz; Ar), 131.7 (s;
Ar), 130.7 (d, J (C,P) = 137.4 Hz; Ar-C-P), 128.9 (s; Ar), 128.7
1
1
1
(C,P) = 13.4 Hz; Ar), 125.3 (s; Ar), 121.2 (d, J (C,P) = 4.6 Hz;
Ar), 117.4 (d, J (C,P) = 4.6 Hz; Ar), 21.2 (s; CH3); 31P NMR
(s; Ar), 127.7 (s; Ar), 127.6 (s; Ar), 127.0 (s; Ar), 125.7 (s; Ar),
1
(160 MHz, CDCl3, 25 oC): δ= 27.97.
124.7 (s; Ar), 122.1 (s; Ar), 115.3 (d, J (C,P) = 4.3 Hz; Ar); 31P
1
o
NMR (160 MHz, CDCl3, 25 C): δ= 31.63. HRMS calcd. for
4.2.9. 3-Nitro-O-phenyl phenyl (phenyl) phosphinate (3i).15a
C22H16ClO2P: 378.0576, found: 378.0574.
Yield: 134.2 mg, (79 %). Yellow oil. 1H NMR (400 MHz,
o
CDCl3, 25 C, TMS): δ= 7.88-8.02 (m, 6H; Ar), 7.63-7.66 (m,
4.2.15.
O-2-Methoxynaphthalen-5-yl
phenyl
(phenyl)
1H; Ar), 7.56-7.61 (m, 2H; Ar), 7.48-7.53 (m, 4H; Ar), 7.41-7.45
phosphinate (3o). Yield: 151.1 mg, (81 %). Yellow oil. 1H NMR
(400 MHz, CDCl3, 25 oC, TMS): δ= 7.90-7.95 (m, 4H; Ar), 7.58-
7.61 (m, 3H; Ar), 7.42-7.52 (m, 6H; Ar), 7.30-7.33 (m, 1H; Ar),
7.03-7.10 (m, 2H; Ar); 13C NMR (100 MHz, CDCl3, 25 oC,
(m, 1H; Ar); 13C NMR (100 MHz, CDCl3, 25 oC, TMS): δ= 151.1
1
(d, J (C,P) = 7.4 Hz; Ar), 148.7 (s; Ar), 132.9 (s; Ar), 131.6 (d,
1
1J (C,P) = 10.6 Hz; Ar), 130.2 (s; Ar), 129.8 (d, J (C,P) = 137.0
1
1
1
Hz; Ar), 128.7 (d, J (C,P) = 13.5 Hz; Ar), 127.0 (d, J (C,P) =
TMS): δ= 157.3 (s; Ar), 146.9 (d, J (C,P) = 8.4 Hz; Ar), 132.5
1
1
(d, J (C,P) = 2.9 Hz; Ar), 131.8 (d, J (C,P) = 10.3 Hz; Ar),

5
1
131.7 (s; Ar), 131.0 (d, J (C,P) = 137.4 Hz; Ar-C-P), 129.2 (s;
4.2.22. Ethyl O-phenyl phenylphosphonate (4d).12k Yield: 111.6
1 o
ACCEPTED MANUSCRIPT
1
Ar), 128.9 (s; Ar), 128.6 (d, J (C,P) = 13.4 Hz; Ar),, 128.4 (s;
mg, (85 %). Yellow oil. H NMR (400 MHz, CDCl3, 25 C,
TMS): δ= 7.85-7.91 (m, 2H; Ar), 7.53-7.57 (m, 1H; Ar), 7.43-
7.48 (m, 2H; Ar), 7.24-7.28 (m, 2H; Ar), 7.15-7.17 (m, 2H; Ar),
7.08-7.12 (m, 1H; Ar), 4.20-4.29 (m, 2H; OCH2), 1.34 (t, J = 7.2
1
1
Ar), 121.1 (d, J (C,P) = 4.8 Hz; Ar), 119.4 (s; Ar), 117.3 (d, J
(C,P) = 5.0 Hz; Ar), 105.7 (s; Ar), 55.3 (s; OCH3); 31P NMR (160
o
MHz, CDCl3, 25 C): δ= 30.70. HRMS calcd. for C23H19O3P:
374.1072, found: 374.1069.
Hz, 3H; CH3); 13C NMR (100 MHz, CDCl3, 25 C, TMS): δ=
o
150.6 (d, 1J (C,P) = 7.1 Hz; Ar), 132.8 (d, 1J (C,P) = 3.1 Hz; Ar),
132.0 (d, 1J (C,P) = 10.1 Hz; Ar), 129.6 (s; Ar), 128.5 (d, 1J (C,P)
= 15.3 Hz; Ar), 127.6 (d, 1J (C,P) = 189.7 Hz; Ar-C-P), 124.8 (d,
1J (C,P) = 1.0 Hz; Ar), 120.5 (d, 1J (C,P) = 4.5 Hz; Ar), 62.9 (d, 1J
4.2.16. O-2-Cyanonaphthalen-5-yl phenyl (phenyl) phosphinate
1
(3p). Yield: 171.8 mg, (93 %). Yellow oil. H NMR (400 MHz,
CDCl3, 25 oC, TMS): δ= 8.12 (s, 1H; Ar), 7.91-7.96 (m, 4H; Ar),
7.76-7.80 (m, 3H; Ar), 7.47-7.58 (m, 8H; Ar); 13C NMR (100
(C,P) = 5.9 Hz; OCH2), 16.3 (d, J (C,P) = 6.4 Hz; CH3); 31P
1
o
1
NMR (160 MHz, CDCl3, 25 oC): δ= 15.48.
MHz, CDCl3, 25 C, TMS): δ= 151.1 (d, J (C,P) = 8.2 Hz; Ar),
135.5 (s; Ar), 133.8 (s; Ar), 132.8 (d, J (C,P) = 2.8 Hz; Ar),
131.7 (d, J (C,P) = 10.4 Hz; Ar), 130.5 (d, J (C,P) = 137.2 Hz;
Ar-C-P), 137.5 (s; Ar), 129.4 (s; Ar), 128.9 (s; Ar), 128.8 (d, J
1
1
1
4.2.23. O-phenyl 4-methylphenyl (4-methylphenyl) phosphinate
1
(4e).12k Yield: 150.1 mg, (93 %). Yellow oil. 1H NMR (400 MHz,
1
o
(C,P) = 13.5 Hz; Ar), 127.1 (s; Ar), 122.6 (d, J (C,P) = 5.1 Hz;
CDCl3, 25 C, TMS): δ= 7.66-7.71 (m, 4H; Ar), 7.10-7.18 (m,
Ar), 119.1 (s; CN), 117.3 (d, 1J (C,P) = 5.1 Hz; Ar), 108.7 (s; Ar);
8H; Ar), 6.95-6.99 (m, 1H; Ar), 2.29 (s, 6H; CH3); 13C NMR
31P NMR (160 MHz, CDCl3, 25 C): δ= 31.84. HRMS calcd. for
o
o
(100 MHz, CDCl3, 25 C, TMS): δ= 150.0 (d, J (C,P) = 8.1 Hz;
C23H16NO2P: 369.0919, found: 369.0917.
Ar), 141.9 (d, J (C,P) = 2.9 Hz; Ar), 130.7 (d, J (C,P) = 10.7 Hz;
Ar), 128.5 (s; Ar), 128.2 (d, J (C,P) = 13.7 Hz; Ar), 127.0 (d, J
(C,P) = 140.0 Hz; Ar-C-P), 123.4 (s; Ar), 119.7 (d, J (C,P) = 4.8
4.2.17. 2-Methyl-O-phenyl phenyl (phenyl) phosphinate (3q).
Yield: 100.4 mg, (65 %). Colorless oil. H NMR (400 MHz,
CDCl3, 25 C, TMS): δ= 7.86-7.91 (m, 4H; Ar), 7.45-7.54 (m,
1
Hz; Ar), 20.6 (s; CH3); 31P NMR (160 MHz, CDCl3, 25 C): δ=
o
o
31.41.
6H; Ar), 7.24-7.26 (m, 1H; Ar), 7.13-7.14 (m, 1H; Ar), 6.96-7.03
(m, 2H; Ar), 2.30 (s, 3H; CH3); 13C NMR (100 MHz, CDCl3, 25
4.2.24. O-phenyl 4-trifluoromethylphenyl (4-trifluoromethyl
oC, TMS): δ= 149.6 (d, 1J (C,P) = 8.3 Hz; Ar), 132.4 (d, J (C,P)
1
phenyl) phosphinate (4f).12k Yield: 206.8 mg, (96 %). Yellow oil.
1
1
1H NMR (400 MHz, CDCl3, 25 C, TMS): δ= 8.01-8.07 (m, 4H;
= 2.8 Hz; Ar), 131.7 (d, J (C,P) = 10.4 Hz; Ar), 131.4 (d, J
(C,P) = 137.5 Hz; Ar-C-P), 131.3 (s; Ar), 129.1 (d, 1J (C,P) = 5.7
Hz; Ar), 128.6 (d, 1J (C,P) = 13.3 Hz; Ar), 126.9 (s; Ar), 124.4 (s;
o
Ar), 7.74-7.76 (m, 4H; Ar), 7.11-7.30 (m, 5H; Ar); 13C NMR
(100 MHz, CDCl3, 25 oC, TMS): δ= 150.3 (d, J (C,P) = 8.2 Hz;
1
Ar), 120.2 (d, J (C,P) = 3.7 Hz; Ar), 16.9 (s; CH3); 31P NMR
1
1
2
Ar), 134.6 (dd, J (C,P) = 3.1 Hz, J (C,F) = 32.8 Hz; Ar), 134.5
(d, J (C,P) = 137.7 Hz; Ar-C-P), 132.3 (d, J (C,P) = 10.6 Hz;
Ar), 130.0 (s; Ar), 125.7 (dd, J (C,P) = 3.7 Hz, J (C,F) = 13.7
(160 MHz, CDCl3, 25 oC): δ= 29.91. HRMS calcd. for
1
1
C19H17O2P: 308.0966, found: 308.0964.
1
2
2
Hz; Ar), 125.3 (s; Ar), 123.4 (d, J (C,F) = 272.0 Hz; -CF3),
4.2.18. 2,4-Di-methyl-O-phenyl phenyl (phenyl) phosphinate (3r).
Yield: 91.8 mg, (57 %). Colorless oil. 1H NMR (400 MHz,
120.5 (d, 1J (C,P) = 4.8 Hz; Ar); 31P NMR (160 MHz, CDCl3, 25
o
oC): δ= 26.21; 19F NMR (377 MHz, CDCl3, 25 oC): δ= -63.4.
CDCl3, 25 C, TMS): δ= 7.86-7.91 (m, 4H; Ar), 7.39-7.50 (m,
6H; Ar), 7.12-7.14 (m, 1H; Ar), 6.92 (s, 1H; Ar), 6.77-6.79 (m,
4.2.25. O-phenyl-dibenzooxaphosphorine oxides (4g).12k Yield:
1H; Ar), 2.26 (s, 3H; CH3), 2.17 (s, 3H; CH3); 13C NMR (100
1
o
1
144.5 mg, (94 %). Colorless oil. H NMR (400 MHz, CDCl3, 25
MHz, CDCl3, 25 C, TMS): δ= 147.4 (d, J (C,P) = 8.3 Hz; Ar),
133.8 (d, 1J (C,P) = 0.8 Hz; Ar), 132.4 (d, 1J (C,P) = 2.8 Hz; Ar),
131.9 (s; Ar), 131.7 (d, 1J (C,P) = 10.3 Hz; Ar), 131.4 (d, 1J (C,P)
oC, TMS): δ= 7.93-8.03 (m, 3H; Ar), 7.70-7.74 (m, 1H; Ar),
7.47-7.52 (m, 1H; Ar), 7.36-7.40 (m, 1H; Ar), 7.20-7.29 (m, 4H;
Ar), 7.09-7.13 (m, 1H; Ar), 7.03-7.05 (m, 2H; Ar); 13C NMR
1
= 137.3 Hz; Ar-C-P), 128.7 (d, J (C,P) = 5.6 Hz; Ar), 128.5 (d,
1
(100 MHz, CDCl3, 25 oC, TMS): δ= 149.9 (d, J (C,P) = 8.2 Hz;
1J (C,P) = 13.3 Hz; Ar), 127.3 (s; Ar), 119.9 (d, 1J (C,P) = 3.5 Hz;
Ar), 20.6 (s; Ar), 16.8 (s; CH3); 31P NMR (160 MHz, CDCl3, 25
oC): δ= 29.72. HRMS calcd. for C20H19O2P: 322.1123, found:
322.1120.
Ar), 149.8 (d, 1J (C,P) = 8.5 Hz; Ar), 137.1 (d, 1J (C,P) = 7.0 Hz;
1
1
Ar), 133.9 (d, J (C,P) = 2.4 Hz; Ar), 130.7 (s; Ar), 129.7 (d, J
1
(C,P) = 0.9 Hz; Ar), 129.6 (d, J (C,P) = 234.3 Hz; Ar-C-P),
128.3 (s; Ar), 125.3 (d, J (C,P) = 1.5 Hz; Ar), 125.0 (s; Ar),
1
4.2.19. Triphenyl phosphate (4a).12k Yield: 171.8 mg, (93 %).
Colorless oil. 1H NMR (400 MHz, CDCl3, 25 oC, TMS): δ= 7.44-
7.37 (m, 6H; Ar), 7.19-7.25 (m, 9H; Ar); 13C NMR (100 MHz,
1
124.1 (d, J (C,P) = 12.3 Hz; Ar), 122.6 (s; Ar), 122.5 (s; Ar),
120.7 (s; Ar), 120.6 (s; Ar), 120.3 (d, J (C,P) = 6.9 Hz; Ar); 31P
1
NMR (160 MHz, CDCl3, 25 oC): δ= 6.48.
o
1
CDCl3, 25 C, TMS): δ= 150.5 (d, J (C,P) = 7.4 Hz; Ar), 129.9
(s; Ar), 125.7 (s; Ar), 120.1 (d, J (C,P) = 4.9 Hz; Ar); 31P NMR
1
4.2.26. 1,2-Bis(4-tert-butylphenyl)disulfane (5).15g Yield: 145.3
(160 MHz, CDCl3, 25 oC): δ= -17.66.
1
o
mg, (88 %). Colorless oil. H NMR (400 MHz, CDCl3, 25 C,
TMS): δ= 7.31-7.45 (m, 8H; Ar), 1.29 (s, 18H; CH3); 13C NMR
(100 MHz, CDCl3, 25 oC, TMS): δ= 150.5 (s; Ar), 134.1 (s; Ar),
127.8 (s; Ar), 126.1 (s; Ar), 34.6 (s; -C(CH3)3), 31.3 (s; CH3).
4.2.20. Dibutyl phenyl phosphate (4b).12k Yield: 104.6 mg,
1
(73 %). Colorless oil. H NMR (400 MHz, CDCl3, 25 oC, TMS):
δ= 7.14-7.45 (m, 5H; Ar), 4.12-4.17 (m, 4H; OCH2), 1.65-1.69
(m, 4H; CH2), 1.37-1.42 (m, 4H; CH2), 0.92 (t, J = 7.2 Hz, 6H;
CH3); 13C NMR (100 MHz, CDCl3, 25 oC, TMS): δ= 150.8 (d, 1J
Acknowledgments
1
(C,P) = 6.9 Hz; Ar), 129.6 (s; Ar), 124.9 (s; Ar), 119.9 (d, J
(C,P) = 4.8 Hz; Ar), 68.2 (d, 1J (C,P) = 6.3 Hz; OCH2), 32.2 (d, 1J
(C,P) = 6.8 Hz; CH2), 18.6 (s; CH2), 13.5 (s; CH3); 31P NMR (160
MHz, CDCl3, 25 oC): δ = -6.11.
We thank NSFC (21273067), Program for Changjiang
Scholars and Innovative Research Team in University
(IRT1238), and the Fundamental Research Funds for the Central
Universities (Hunan University) for financial support. CTA
thanks HNU (Hunan University) for an adjunct professorship.
4.2.21. Dibutyl O-phenyl phosphinate (4c).15f Yield: 102.7 mg,
(81 %). Yellow oil. 1H NMR (400 MHz, CDCl3, 25 oC, TMS): δ=
7.22-7.26 (m, 2H; Ar), 7.12-7.14 (m, 2H; Ar), 7.04-7.08 (m, 1H;
Ar), 1.73-1.81 (m, 4H; CH2), 1.52-1.58 (m, 4H; CH2), 1.31-1.37
(m, 4H; CH2), 0.84 (t, J = 7.2 Hz, 6H; CH3); 31P NMR (160 MHz,
CDCl3, 25 oC): δ= 58.35.
Supplementary Material
Supplementary data associated with this article can be found in
the online version.

6
Tetrahedron
Obshchei Khimii, 1988, 58, 777; (d) Dhawan, B.; Redmore, D. Journal of
References and notes
ACCEPTED MANUSCRIPT
Organic Chemistry, 1991, 56, 833; (e) Xu, G.; Fu, W.; Liu, G.;
Senanayake, C. H.; Tang, W. Journal of the American Chemical Society,
2014, 136, 570; (f) Yuan, C.-Y.; Yuan, Q. Huaxue Xuebao, 1980, 38, 339;
(g) Feng, J.; Lu, G.; Lv, M.; Cai, C. Synlett, 2015, 26, 915.
1. (a) Imamoto, T. In Handbook of Organophosphorus Chemistry, Engel, R.
Eds.; Marcel Dekker: New York, 1992; (b) Quin, L. D. In A Guide to
Organophosphorus Chemistry, Wiley-Interscience: New York, 2000.
2. (a) Bock, T.; Möhwald, H.; Mülhaupt, R. Macromol. Chem. Phys. 2007,
208, 1324; (b) Kirumakki, S.; Huang, J.; Subbiah, A.; Yao, J.; Rowland,
A.; Smith, B.; Mukherjee, A.; Samarajeewa, S.; Clearfield, A. J. Mater.
Chem. 2009, 19, 2593; (c) Kim, D.; Salman, S.; Coropceanu, V.;
Padmaperuma, A. B.; Sapochak, L. S.; Kahn, A.; Bredas, J. L. Chem.
Mater. 2010, 22, 247.
3. (a) Pollack, S. J.; Jacobs, J. W.; Schultz, P. G. Science. 1986, 234, 1570;
(b) Janda, K. D.; Schloeder, D.; Benkovic, S. J.; Lerner, R. A. Science.
1988, 241, 1188.
4. (a) Baumgartner, T.; Réau, R. Chem. Rev. 2006, 106, 4681; (b) Engel, R.
Chem. Rev. 1977, 77, 349.
5. (a) Williams, N. H.; Harrison, J. M.; Read, R. W.; Black, R. M. Arch.
Toxicol. 2007, 81, 627; (b) Nomura, D. K.; Hudak, C. S.; Ward, A. M.;
Burston, J. J.; Issa, R. S.; Fisher, K. J.; Abood, M. E.; Wiley, J. L.;
Lichtman, A. H.; Casida, J. E. Bioorg. Med. Chem. Lett. 2008, 18, 5875;
(c) Ashani, Y.; Gupta, R. D.; Goldsmith, M.; Silman, I.; Sussman, J. L.;
Tawfik, D. S.; Leader, H. Chem. Biol. Interact. 2010, 187, 362.
6. (a) Spangler, L. A.; Mikolajczyl, M.; Burdge, E. L.; Kielbasinski, P.;
Smith, H. C.; Lyzwa, P.; Fisher, J. D.; Omelańczuk, J. J. Agric. Food
Chem. 1999, 47, 318; (b) Kukhar, V. P.; Hudson, H. R. In
Aminophosphonic and Aminopho-sphinic Acids: Chemistry and
Biological Activity; Wiley & Sons: Chichester, U.K., 2000.
7. (a) Fukuto, T. R.; Metcalf, R. L. J. Am. Chem. Soc. 1959, 81, 372; (b)
Nowlan, C.; Li, Y.; Hermann, J. C.; Evans, T.; Carpenter, J.; Ghanem, E.;
Shoichet, B. K.; Raushel, F. M. J. Am. Chem. Soc. 2006, 128, 15892.
8. (a) Atherton, F. R.; Openshaw, H. T.; Todd, A. R. J. Chem. Soc. 1945,
660; (b) Atherton, F. R.; Todd, A. R. J. Chem. Soc. 1947, 674; (c) Wang,
G.; Shen, R. W.; Xu, Q.; Goto, M.; Zhao, Y.-F.; Han, L.-B. J. Org. Chem.
2010, 75, 3890.
9. Copper-catalyzed O-arylation of the dialkyl phosphonates with
diaryliodonium salts, see: FanÞanaìs-Mastral, M.; Feringa, B. L. J. Am.
Chem. Soc. 2014, 136, 9894.
10. For the activation of P(O)-OH compounds via the P(O)-Cl intermediate,
see: (a) Pollart, K. A.; Harwood, H. J. J. Org. Chem. 1962, 27, 4444; (b)
Kasemsuknimit, A.; Satyender, A.; Chavasiri, W.; Jang, D. O. Bull.
Korean Chem. Soc. 2011, 32, 3486; (c) Swamy, K. C. K.; Kumar, N. S.
Acc. Chem. Res. 2006, 39, 324.
11. For reviews of the synthesis of phosphoric acid esters, see: (a) Hayakawa,
Y. In Comprehensive Organic Synthesis, Trost, B. M.; Fleming, I.;
Winterfeldt, E. Eds.; Pergamon, Oxford, 1991, Vol. 6; (b) Reese, C. B.
Org. Biomol. Chem. 2005, 3, 3851; (c) Keglevich, G.; Kiss, N. Z.; Mucsi,
Z.; Körtvélyesi, T. Org. Biomol. Chem. 2012, 10, 2011; (d) Dumond, Y.
R.; Baker, R. L.; Montchamp, J.-L. Org. Lett. 2000, 2, 3341; (e) Kiss, N.
Z.; Ludányi, K.; Drahos, L.; Keglevich, G. Synth. Commun. 2009, 39,
2392
12. For selected examples for the activation of P(O)-OH compounds, see: (a)
Park, Y.; Seo, J.; Park, S.; Yoo, E. J.; Lee, P. H. Chem. Eur. J. 2013, 19,
16461; (b) Unoh, Y.; Hashimoto, Y.; Takeda, D.; Hirano, K.; Satoh, T.;
Miura, M. Org. Lett. 2013, 15, 3258; (c) Park, Y.; Jeon, I.; Shin, S.; Min,
J.; Lee, P. H. J. Org. Chem. 2013, 78, 10209; (d) Peng, A.-Y.; Ding, Y.-
X. J. Am. Chem. Soc. 2003, 125, 15006; (e) Ryu, T.; Kim, J.; Park, Y.;
Kim, S.; Lee, P. H. Org. Lett. 2013, 15, 3986; (f) Sakakura, A.;
Katsukawa, M.; Ishihara, K. Angew. Chem. Int. Ed. 2007, 46, 1423; (g)
Sakakura, A.; Katsukawa, M.; Ishihara, K. Org. Lett. 2005, 7, 1999; (h)
Sakakura, A.; Katsukawa, M.; Hayashi, T.; Ishihara, K. Green Chem.
2007, 9, 1166; (i) Park, C.-H.; Givens, R. S. J. Am. Chem. Soc. 1997, 119,
2453; (j) Xiong, B.; Ye, Q.; Feng, X.; Zhu, L.; Chen, T.; Zhou, Y.; Au,
C.-T.; Yin, S.-F. Tetrahedron. 2014, 70, 9057; (k) Xiong, B.; Feng, X.;
Zhu, L.; Chen, T.; Zhou, Y.; Au, C.-T.; Yin, S.-F. ACS Catal. 2015, 5,
537.
13. Under the optimized reaction conditions, 4-tert-butylbenzenethiol does
not react with 1a to afford the esterification product, but rather giving 1,2-
bis(4-tert-butylphenyl)disulfane (5) in 88% yield.
14. Selected examples for Cu-catalyzed arylations: (a) Phipps, R. J.;
Grimster, N. P.; Gaunt, M. J. J. Am. Chem. Soc. 2008, 130, 8172; (b)
Phipps, R. J.; Gaunt, M. J. Science. 2009, 323, 1593; (c) Wang, Y.; Chen,
C.; Peng, J.; Li, M. Angew. Chem., Int. Ed. 2013, 52, 5323; (d) Collins, B.
S. L.; Suero, M. G.; Gaunt, M. J. Angew. Chem., Int. Ed. 2013, 52, 5799.
15. (a) Hoz, S.; Dunn, E. J.; Buncel, E.; Bannard, R. A. B.; Purdon, J. G.
Phosphorus, Sulfur and Silicon and the Related Elements, 1985, 24, 321;
(b) Haake, P.; McCoy, D. R..; Okamura, W.; Alpha, S. R.; Wong, S. Y.;
Tyssee, D. A.; McNeal, J. P.; Cook, R. D. Tetrahedron Letters, 1968, 50,
5243; (c) Baranskii, V. A.; Eliseeva, G. D.; Sukhorukova, N. A. Zhurnal