Direct synthesis of α-hydroxyketone phosphates from terminal alkynes and H-phosphine oxides in the presence of PhI(OAc)2and H2O

Article abstract of DOI:10.1016/j.cclet.2016.05.029

A simple and highly efficient one-pot method for the construction of α-hydroxyketone phosphates from terminal alkynes and H-phosphine oxides has been developed in the presence of PhI(OAc)₂and H₂O. The present protocol provides an attractive approach to α-hydroxyketone phosphates in good to high yields, with the advantages of operation simplicity, the use of commercially available materials, broad substrate scope, high atom efficiency and good tolerance to scale-up synthesis.

Full text of DOI:10.1016/j.cclet.2016.05.029

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CCLET-3718; No. of Pages 5
Chinese Chemical Letters xxx (2016) xxx–xxx
Contents lists available at ScienceDirect
Chinese Chemical Letters
journal homepage: www.elsevier.com/locate/cclet
Original article
Direct synthesis of
a-hydroxyketone phosphates from terminal
alkynes and H-phosphine oxides in the presence of PhI(OAc)2 and H2O
Dong-Yan Hu a,c, Meng-Shun Li a,c, Wen-Wu Zhong b,c, Jian-Xin Ji b, Jin Zhu a, Wei Wei d,
b,
Qiang Zhang b, , Ming Cheng
*
*
a Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, China
b Chengdu Institute of Biology, Chinese Academy of Sciences, Chengdu 610041, China
c University of the Chinese Academy of Sciences, Beijing 100049, China
d School of Chemistry and Chemical Engineering, Qufu Normal University, Qufu 273165, China
A R T I C L E I N F O
A B S T R A C T
Article history:
A simple and highly efficient one-pot method for the construction of a-hydroxyketone phosphates from
Received 1 April 2016
Received in revised form 4 May 2016
Accepted 10 May 2016
Available online xxx
terminal alkynes and H-phosphine oxides has been developed in the presence of PhI(OAc)2 and H2O. The
present protocol provides an attractive approach to -hydroxyketone phosphates in good to high yields,
a
with the advantages of operation simplicity, the use of commercially available materials, broad substrate
scope, high atom efficiency and good tolerance to scale-up synthesis.
ß 2016 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.
Published by Elsevier B.V. All rights reserved.
Keywords:
a-Hydroxyketone phosphates
Alkynes
H-Phosphine oxides
Water
Phenyliodine diacetate
1. Introduction
iodine compound intermediate, which was preformed from the
reaction of phosphonic acid with iodosobenzene (Scheme 1, Eq. (1))
Organophosphates have attracted increasingly synthetic pur-
suit of chemists because of their widely applications in many major
physiological processes [1], drug discovery [2], organic synthesis
[9]. However, all these methods suffer from limitations such as
unreadily available starting materials, tedious work-up procedures,
relatively harsh reaction conditions, toxic chemical wastes, the poor
substrate scope, or low yields. Therefore, it is still highly desirable to
[3] and agrochemicals [4]. Particularly,
a-hydroxy-ketone phos-
phates can be used as sugar analogues [5] and important
intermediates for the construction of phospholipid and oligonu-
cleotide through the selective hydrolytic removal of the ketoxide
motif [6]. As such, the development of general and efficient methods
develop a simple, convenient and efficient approach to
xyketone phosphates.
a-hydro-
In 2012, Yan [10] and co-workers reported iodobenzene/m-
chloroperbenzoic acid (m-CPBA) mediated the -phosphoryl-
a
to access
Traditionally,
the -phosphoryloxylation of ketones with the [hydroxy(pho-
sphoryloxy)iodo]arenes [7], the reaction of 2,2,2-trialkoxy-1,3,2-
dioxaphospholen with hydrogen chloride [5], and the oxypho-
sphorylation of silyl enol ethers with phosphoric acid and
p-(difluoroiodo) toluene [8]. An alternative method for the
a
-hydroxyketone phosphates is of great interest.
oxylation of ketones with (RO)2PO2H (Scheme 1, Eq. (2)). Very
recently, Wang et al. [11] reported a new method for the
a-hydroxyketone phosphates are synthesized by
a
construction of
mediated direct
a
-hydroxyketone phosphates through I2O5/DBU
-phosphoryloxylation of ketones with H-
a
phosphonates (Scheme 1, Eq. (3)). Nevertheless, stoichiometric
amount of potentially dangerous peroxide oxidant or base are still
required in the two well developed reactions. Here, we wish to
construction of
a
-hydroxyketone phosphates has also been devel-
report
a
simple, convenient and highly efficient PhI(OAc)2
-hydroxyketone
oped via the addition of terminal alkynes with unstable hypervalent
mediated procedure for the construction of
a
phosphates from alkynes and H-phosphine oxides in the presence
of water under mild conditions (Scheme 1, Eq. (4)). The present
protocol provides an alternative and highly attractive route to
*
Corresponding authors.
various
a-hydroxyketone phosphates from the commercially
E-mail addresses: zhangqiang@cib.ac.cn (Q. Zhang),
available starting materials, and especially it avoids the use of
chengming198101@163.com (M. Cheng).
http://dx.doi.org/10.1016/j.cclet.2016.05.029
1001-8417/ß 2016 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences. Published by Elsevier B.V. All rights reserved.
Please cite this article in press as: D.-Y. Hu, et al., Direct synthesis of
a-hydroxyketone phosphates from terminal alkynes and H-
phosphine oxides in the presence of PhI(OAc)2 and H2O, Chin. Chem. Lett. (2016), http://dx.doi.org/10.1016/j.cclet.2016.05.029

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D.-Y. Hu et al. / Chinese Chemical Letters xxx (2016) xxx–xxx
Scheme 1. Methods for the synthesis of
a-hydroxyketone phosphates.
unstable reagents, and stoichiometric amounts of bases, toxic or
potentially dangerous oxidants.
2.3. The reaction of diphenylphosphine oxide 2a with PhI(OAc)2
To a solution of diphenylphosphine oxide 2a (1.0 mmol) in
acetonitrile (6.0 mL) were added PhI(OAc)2 (1.0 mmol) and H2O
(4.0 mmol). The reaction mixture was then stirred for 24 h at 60 8C
in air. After the reaction, the solvents were removed under vacuum.
The residue was purified by flash chromatography on silica gel
using a mixture of dichloromethane and methanol (5:1) with
addition of AcOH (1%) as eluent to give the desired product 6a
(209.0 mg, 96%).
2. Experimental
All chemicals and solvents were purchased from Aldrich, J&K
and Alfa Aesar Chemical Company as reagent grade and used
without further purification unless otherwise stated. 1H NMR and
13C NMR spectra were collected in CDCl3 on a Bruker Avance 400
spectrometer with TMS as internal standard at room temperature,
31P NMR spectra were recorded at 162 MHz, and chemical shifts (
reported relative to external 85% phosphoric acid ( = 0.0 ppm), the
chemical shifts ( ) were expressed in parts per million (ppm) and
d)
2.4. The reaction of phenylacetylene 1a with diphenylphosphinic acid
6a
d
d
J values were given in hertz (Hz). HRMS were performed on a
Brucker Daltonics Bio-TOF-Q mass spectrometer by the ESI method
and LC–MS were obtained on a on a Waters Xevo TQ (Waters,
Manchester, UK) equipped with an ESI source. The products
were purified by flash column chromatography on silica gel
(200–300 mesh).
To a solution of diphenylphosphinic acid 6a (0.5 mmol) in
acetonitrile (3.0 mL) were added PhI(OAc)2 (1.25 mmol), H2O
(2.0 mmol) and phenylacetylene 1a (0.75 mmol). The reaction
mixture was then stirred for 24 h at 60 8C in air. After the reaction,
the solvents were removed under vacuum. The residue was
purified by flash chromatography on silica gel using a mixture of
petroleum ether and ethyl acetate (1:1) as eluent to give the
desired product 3aa (153.0 mg, 91%).
2.1. General procedure for the synthesis of
a-hydroxyketone
phosphates 3
3. Results and discussion
To a solution of diarylphosphine oxides 2 (0.5 mmol) in
acetonitrile (3.0 mL) were added PhI(OAc)2 (1.25 mmol), H2O
(2.0 mmol) and alkynes 1 (0.75 mmol). The reaction mixture was
then stirred for 24 h at 60 8C in air. After the reaction, the
solvents were removed under vacuum. The residue was purified
by flash chromatography on silica gel using a mixture of
petroleum ether and ethyl acetate (1:1) as eluent to give the
desired product 3.
At the outset of our investigation, the reaction of phenylace-
tylene 1a and diphenylphosphine oxide 2a was chosen as the
model reaction to optimize the reaction conditions. Gratifyingly,
the desired product 3aa was obtained in 26% yield when the model
reaction was performed in the presence of PhI(OAc)2 (1.0 equiv.)/
H2O (1.0 equiv.) at 60 8C in air for 24 h (Table 1, entry 1). It was
found that the reaction gave a better yield 40% when the loading of
H2O was increased to 4.0 equiv. (Table 1, entry 4). Further
optimization suggested that the reaction efficiency was obviously
improved with the increasing of PhI(OAc)2 loading, the best yield
was obtained when 2.5 equivalent of PhI(OAc)2 was used (Table 1,
entry 9). The screening of other oxidants, such as K2S2O8, m-CPBA,
TBHP and H2O2 could not improve the reaction efficiency (Table 1,
entries 11–14). Subsequent investigation on the effect of solvents
showed that the reaction performed in MeCN was found to be
superior for the formation of 3aa (Table 1, entries 15–20). In
addition, we found that the reaction temperature also played an
important role in this transformation (Table 1, entries 9, 21–23).
The desired product 3aa was isolated in only 36% yield when the
model reaction was carried out at room temperature (Table 1,
entry 21), and the best yield was obtained when the reaction was
2.2. The procedure of gram-scale reaction for the synthesis of 3aa
To a solution of diphenylphosphine oxide 2a (2.02 g, 10.0 mmol)
in acetonitrile (60.0 mL) were added PhI(OAc)2 (8.05 g, 25.0 mmol),
H2O (720.0
mL, 40.0 mmol) and phenylacetylene 1a (1.53 g,
15.0 mmol). The reaction mixture was then stirred for 24 h at
60 8C in air. After the reaction, the solvents were removed under
vacuum. Water (60.0 mL) was added to the reaction mixture, and
then the mixture was extracted with EtOAc. The combined organic
phase was dried over Na2SO4 and concentrated. The residue was
purified by flash chromatography on silica gel using a mixture of
petroleum ether and ethyl acetate (1:1) as eluent to give the desired
product 3aa (2.99 g, 89%).
Please cite this article in press as: D.-Y. Hu, et al., Direct synthesis of
a-hydroxyketone phosphates from terminal alkynes and H-
phosphine oxides in the presence of PhI(OAc)2 and H2O, Chin. Chem. Lett. (2016), http://dx.doi.org/10.1016/j.cclet.2016.05.029

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D.-Y. Hu et al. / Chinese Chemical Letters xxx (2016) xxx–xxx
3
Table 1
Optimization of reaction conditions.a
Entry
H2O (equiv.)
Oxidant (equiv.)
Solvent
T (8C)
Yield (%)b
Entry
H2O (equiv.)
Oxidant (equiv.)
Solvent
T (8C)
Yield (%)b
1
1.0
2.0
3.0
4.0
5.0
6.0
4.0
4.0
4.0
4.0
4.0
4.0
PhI(OAc)2 (1.0)
PhI(OAc)2 (1.0)
PhI(OAc)2 (1.0)
PhI(OAc)2 (1.0)
PhI(OAc)2 (1.0)
PhI(OAc)2 (1.0)
PhI(OAc)2 (1.5)
PhI(OAc)2 (2.0)
PhI(OAc)2 (2.5)
PhI(OAc)2 (3.0)
K2S2O8 (2.5)
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
60
60
60
60
60
60
60
60
60
60
60
60
26
33
38
40
39
36
61
82
90
88
0
13
14
15
16
17
18
19
20
21
22
23
24
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
0
TBHP (2.5)
MeCN
MeCN
1,4-dioxane
THF
60
60
60
60
60
60
60
60
25
40
70
60
0
0
2
H2O2 (2.5)
3
PhI(OAc)2 (2.5)
PhI(OAc)2 (2.5)
PhI(OAc)2 (2.5)
PhI(OAc)2 (2.5)
PhI(OAc)2 (2.5)
PhI(OAc)2 (2.5)
PhI(OAc)2 (2.5)
PhI(OAc)2 (2.5)
PhI(OAc)2 (2.5)
PhI(OAc)2 (2.5)
0
4
0
5
Toluene
DCE
79
81
12
21
36
55
84
0
6
7
EtOH
8
DMF
9
MeCN
MeCN
MeCN
MeCN
10
11
12
m-CPBA (2.5)
0
a
Reaction conditions: Phenylacetylene 1a (0.75 mmol), diphenylphosphine oxide 2a (0.5 mmol), H2O (0–6 equiv.), oxidant (1–3 equiv.), solvent (3.0 mL), air, 24 h.
Isolated yields based on 2a.
b
Table 2
Results for the synthesis of
a
-hydroxyketone phosphates from terminal alkynes and H-phosphine oxides.a
Entry
R1
R2
Product
Yield (%)
Entry
R1
R2
Product
Yield (%)
1
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
3aa
3ba
3ca
3da
3ea
3fa
90
65
83
80
75
69
79
82
80
69
82
81
75
76
15
16
17
18
19
20
21
22
23
24
25
26
27
4-(CH2CN)C6H4
1-naphthyl
3-thienyl
2-phenylethyl
Cyclohexyl
n-Butyl
C6H5
3oa
3pa
3qa
3ra
3sa
3ta
85
64
78
83
73
74
68
70
69
68
65
87
91
2
2-MeC6H4
3-MeC6H4
4-MeC6H4
4-EtC6H4
4-MeOC6H4
4-FC6H4
C6H5
3
C6H5
4
C6H5
5
C6H5
6
C6H5
7
3ga
3ha
3ia
t-Butyl
C6H5
3ua
3va
3wa
3ab
3ac
3ad
3ae
8
4-BrC6H4
4-ClC6H4
2-ClC6H4
3-ClC6H4
4-CF3C6H4
4-NO2C6H4
Cyclopentylmethyl
3-Cyano-n-Propyl
C6H5
C6H5
9
C6H5
10
11
12
13
14
3ja
4-MeOC6H4
4-MeC6H4
4-FC6H4
4-ClC6H4
3ka
3la
C6H5
C6H5
3ma
3na
C6H5
4-(CO2Me)C6H4
a
Reaction conditions: 1 (0.75 mmol), 2 (0.5 mmol), PhI(OAc)2 (1.25 mmol), H2O (2.0 mmol), MeCN (3.0 mL), 60 8C, air, 24 h. Isolated yields based on 2.
conducted at 60 8C. It should be noted that none of desired product
3aa was detected when the reaction performed in the absence of
H2O, suggesting that H2O could play the key role in the synthesis of
bearing both electron-donating and electron-withdrawing groups
were all suitable substrates, leading to the corresponding products
in good to excellent yields (Table 2, 3ab–3ae).
a
-hydroxyketone phosphates (Table 1, entry 24).
With the optimal conditions in hand, we next examined the
Furthermore, the synthetic applicability of this method was
investigated on a gram scale by using the model reaction between
1a and 2a. As shown in Scheme 2, the reaction could afford 2.99 g of
3aa in 89% yield without any significant loss of its efficiency. Thus,
this reaction could serve as a practical and efficient protocol to
substrate scope of this transformation. In general, both electron-
rich and electron-deficient aromatic alkynes were all suitable for
this reaction to afford a-hydroxyketone phosphates in good to high
yields under the standard conditions (Table 2, 3aa–3oa). The
substituent groups on the ortho-position of aromatic ring led to a
negative effect on the reaction efficiency, which might be caused
by the steric hindrance (Table 2, 3ba and 3ja). Also, functional
groups such as halogen, trifluoromethyl, nitro, cyano, and
carboxylic ester were all well tolerated, whose corresponding
products can be applied in further modifications (Table 2, 3ga–
3oa). It was observed that 1-ethynylnaphthalene and heteroaro-
matic alkenes such as 3-ethynylthiophene were also tolerated to
afford the product 3pa and 3qa in 64% and 78% yields, respectively.
Notably, when aliphatic alkynes were used as the substrates, the
corresponding products were also obtained in good yields (Table 2,
3ra–3wa). With respect to the H-phosphine oxides, in addition
to diphenylphosphine oxide 2a, other diarylphosphine oxides
synthesize a-hydroxyketone phosphates.
In order to gain some insights into this reaction mechanism,
two control experiments were conducted (Scheme 3). When
diphenylphosphine oxide 2a was independently treated with
PhI(OAc)2 (1.0 equiv.)/H2O (4.0 equiv.) in the absence of pheny-
lacetylene, the diphenylphosphinic acid 6a was obtained in 96%
Scheme 2. Gram scale reaction.
Please cite this article in press as: D.-Y. Hu, et al., Direct synthesis of
a-hydroxyketone phosphates from terminal alkynes and H-
phosphine oxides in the presence of PhI(OAc)2 and H2O, Chin. Chem. Lett. (2016), http://dx.doi.org/10.1016/j.cclet.2016.05.029

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Scheme 3. Control experiments.
Fig. 2. 31P NMR spectral changes during the reaction process.
iodine intermediate 7a [13]. Next, the selective addition of
hypervalent iodine reagent 7a to phenylacetylene 1a would lead
to the formation of 8a, which underwent isomerization to give
hypervalent iodine intermediate 9a [9,14]. Finally, the reductive
elimination of hypervalent iodine intermediate 9a produced
the desired product 3aa with the release of indobenzene [9]. To
our delight, the proposed intermediate 4a, 5a, 6a, and 7a were all
detected by LC–MS analysis when the model reaction was
performed at 1.5 h (Fig. 1 and Supporting information for detailed
description of LC–MS analysis experiment).
To gain further understanding of the detailed reaction process,
the model reaction was monitored by 31P NMR spectroscopy
(Fig. 2). In a round-bottom flask, a mixture of diphenylphosphine
oxide 2a, PhI(OAc)2, phenylacetylene 1a and H2O was added into
CD3CN. The sample was immediately drawn off and tested by 31P
NMR spectrum. The spectrum showed a signal at 19.06 ppm, which
was assigned as the starting material diphenylphosphine oxide 2a
[15]. After being heated at 60 8C for 10 min, the signal of 2a
disappeared, while two new signals at 29.02 and 25.20 ppm
appeared, which were assigned to be diphenylphosphinic acid 6a
[16] and intermediate 7a [9,13], respectively. Then, after being
heated for 20 min, the signal of diphenylphosphinic acid 6a
slumped while the signal of intermediate 7a increased dramati-
Fig. 1. LC–MS spectrum of 4a, 5a, 6a, 7a and 3aa.
yield (Scheme 3, Eq. (1)). Furthermore, the desired product 3aa
could be isolated in 91% yield when the reaction of diphenylpho-
sphinic acid 6a and phenylacetylene 1a was performed under
standard conditions (Scheme 3, Eq. (2)). The above results
indicated that diphenylphosphinic acid 6a might be
intermediate in the present reaction system.
On the basis of the above results and previous reports [9,12–
14], a tentative reaction pathway was proposed in Scheme 4.
Initially, diphenylphosphine oxide 2a was oxidized by phenylio-
dine diacetate to give diphenylphosphinic acid 6a through the
consecutive transformation of the intermediate 4a and 5a [12].
Subsequently, the resulting diphenylphosphinic acid 6a reacted
with phenyliodine diacetate to form the unstable hypervalent
a key
cally. Moreover,
a signal at 34.09 ppm was simultaneously
observed, corresponding to signals of the final product 3aa [9].
With the progress of the reaction, the 31P NMR signal of
intermediate 7a disappeared gradually and the signal of 3aa
Scheme 4. Possible reaction pathway.
Please cite this article in press as: D.-Y. Hu, et al., Direct synthesis of
a-hydroxyketone phosphates from terminal alkynes and H-
phosphine oxides in the presence of PhI(OAc)2 and H2O, Chin. Chem. Lett. (2016), http://dx.doi.org/10.1016/j.cclet.2016.05.029

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5
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increased. Thus, these data support the mechanistic hypothesis
described in Scheme 4.
4. Conclusion
In conclusion, a new and simple method has been developed for
the one-pot construction of
a-hydroxyketone phosphates from
terminal alkynes and H-phosphine oxides in the presence of
PhI(OAc)2/H2O. This protocol provides a convenient and efficient
approach to various a-hydroxyketone phosphates in good to high
yields from commercially available starting materials with high
regioselectivity and excellent functional group tolerance. Such an
attractive synthesis methodology for
a-hydroxyketone phos-
phates would find the potential applications in the fields of
synthetic and pharmaceutical chemistry. The detailed scope,
mechanism, and synthetic application of this reaction are currently
underway in our laboratory.
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Acknowledgments
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We gratefully acknowledge financial support from the National
Natural Science Foundation of China (Nos. 21172213, 21302109,
21402184, and 21572217).
Appendix A. Supplementary data
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the online version, at http://dx.doi.org/10.1016/j.cclet.2016.05.029.
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Please cite this article in press as: D.-Y. Hu, et al., Direct synthesis of
a-hydroxyketone phosphates from terminal alkynes and H-
phosphine oxides in the presence of PhI(OAc)2 and H2O, Chin. Chem. Lett. (2016), http://dx.doi.org/10.1016/j.cclet.2016.05.029