I2O5/DBU mediated direct α-phosphoryloxylation of ketones with H-phosphonates leading to α-hydroxyketone phosphates

Article abstract of DOI:10.1016/j.tet.2015.07.017

A simple and convenient procedure has been developed for the construction of α-hydroxyketone phosphates via I₂O₅/DBU mediated direct α-phosphoryloxylation of ketones with H-phosphonates. This new reaction proceeds through three steps involving α-iodination of ketones, oxidation of H-phosphonates, and nucleophilic substitution of α-iodo ketones to access a series of α-hydroxyketone phosphates of biological importance.

Full text of DOI:10.1016/j.tet.2015.07.017

Accepted Manuscript
I O /DBU mediated direct α-phosphoryloxylation of ketones with H-phosphonates
2 5
leading to α-hydroxyketone phosphates
Chunli Liu, Wei Wei, Daoshan Yang, Yuanyuan Zheng, Yanshuai Bi, Min Chen, Hua
Wang
PII:
S0040-4020(15)01054-6
10.1016/j.tet.2015.07.017
TET 26962
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 18 May 2015
Revised Date: 2 July 2015
Accepted Date: 5 July 2015
Please cite this article as: Liu C, Wei W, Yang D, Zheng Y, Bi Y, Chen M, Wang H, I O /DBU mediated
2 5
direct α-phosphoryloxylation of ketones with H-phosphonates leading to α-hydroxyketone phosphates,
Tetrahedron (2015), doi: 10.1016/j.tet.2015.07.017.
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I2O5/DBU
mediated
direct
α-
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phosphoryloxylation of ketones with H-
phosphonates leading to α-hydroxyketone
phosphates
Chunli Liu, Wei Wei, Daoshan Yang, Yuanyuan Zheng, Yanshuai Bi, Min Chen, Hua Wang
A simple and convenient procedure has been developed for the construction of α-hydroxyketone phosphates via I2O5/DBU
mediated direct α-phosphoryloxylation of ketones with H-phosphonates.

1
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Tetrahedron
journal homepage: www.elsevier.com
I2O5/DBU mediated direct α-phosphoryloxylation of ketones with H-phosphonates
leading to α-hydroxyketone phosphates
Chunli Liua, Wei Weia,* Daoshan Yanga, Yuanyuan Zhenga, Yanshuai Bia, Min Chena, Hua Wanga,*
a The Key Laboratory of Life-Organic Analysis and Key Laboratory of Pharmaceutical Intermediates and Analysis of Natural Medicine, School
of Chemistry and Chemical Engineering, Qufu Normal University, Qufu 273165, Shandong, China.
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
A simple and convenient procedure has been developed for the construction of α-hydroxyketone
phosphates via I2O5/DBU mediated direct α-phosphoryloxylation of ketones with H-
phosphonates. This new reaction proceeds through three steps involving α-iodination of ketones,
oxidation of H-phosphonates, and nucleophilic substitution of α-iodo ketones to access a series
of α-hydroxyketone phosphates of biological importance.
Available online
Keywords:
α-Phosphoryloxylation
Ketones
2009 Elsevier Ltd. All rights reserved
.
H-Phosphonates
α-hydroxyketone phosphates
Iodine pentoxide
1. Introduction
or low yields. Therefore, the development of simple, convenient
and efficient methods for preparing ketol phosphates is still
highly desirable in synthetic and pharmaceutical chemistry.
Iodine pentoxide (I2O5, IP), which are safe, reliable and
promising single-electron oxidative surrogates for organic
hypervalent iodines, have been recently employed for various
organic transformations due to their particular stability, ready
availability, and cost-effectiveness.13 As part of our continuous
interest in metal-free synthetic transformations,14 here, we wish
to report a new I2O5/DBU-mediated one-pot protocol for the
synthesis of α-hydroxyketone phosphates via direct α-
phosphoryloxylation reaction of ketones with H-phosphonates
(Eq. 1). The present methodology provides a convenient and
highly attractive approach to a variety of α-hydroxyketone
phosphates in moderate to good yields under the metal and
peroxide-free conditions.
Organophosphates are key structural motifs in living organisms
such as DNA, RNA, ATP, and cell membranes.1 They are also
the important elements in drug discovery2 and many
agrochemicals such as insecticides and herbicides.3 Moreover,
some biologically active phosphates analog can be employed as
the extremely useful tools in investigating mechanistic details of
various enzymatic systems.4 In particular, α-hydroxyketone
phosphates have attracted great interest of chemists serving as
sugar analogues5 and the key intermediates in the synthesis of
phospholipid and oligonucleotide6 due to the selective hydrolytic
removal of the ketoxide motif can be achieved under mildly basic
conditions.7 Generally, α-hydroxyketone phosphates are prepared
by the treatment of 2,2,2-trialkoxy-1,3,2-dioxaphospholen with
hydrogen chloride8 or the a-phosphoryloxylation of ketones with
the preformed [hydroxy(phosphoryloxy)iodo]arenes.9 Alternative
procedures have also been developed such as the conversion of
O
O
O
O
I2O5 / DBU
R3
H P R3
R3
O
(1)
terminal
alkynes
to
ketol
phosphates
with
R1
H
+
P
R1
[hydroxy((bis(pheny1oxy)phosphory1)oxy)
idolbenzene,10
R3
R2
CH3CN, 80oC
peroxide free
R2
oxyphosphorylation of silyl enol ethers with phosphoric acid and
p-(dif1uoroiodo)toluene,11 and iodobenzene promoted a-
phosphoryloxylation of ketones with (RO)2PO2H in the presence
of stoichiometric amounts of m-chloroperbenzoic acid (m-
CPBA12. However, most of these methods could suffer from
some limitations such as extra steps for preparation of active
precursors, low atom economy, the poor substrate scope,
potentially dangerous peroxide oxidants, toxic chemical wastes,
1
2
3
2. Results and discussion
Initially, the model reaction of propiophenone 1a with
(EtO)2P(O)H 2a was performed aiming to screen various iodine
reagents
in
the
presence
of
DABCO
(1,4-
___________
Diazabicyclo[2.2.2]octane) in CH3CN at 80oC. Gratifyingly, the
desired ketol phosphate 3aa was obtained in 33% yield when
I2O5 was tested (Table 1, entry 5). Other iodine reagents such as
Corresponding author. Tel.:+86 537 4458317; fax:+86 537 4458317;
E-mail: weiweiqfnu@163.com; huawang_qfnu@126.com

2
Tetrahedron
ACCEPTED MANUSCRIPT
Table 1.
Optimization of the reaction conditionsa
Table 2.
Results for I2O5/DBU mediated direct α-phosphoryloxylation of ketones with
H-phosphonatesab,
Iodine
reagent
Base
Solvent
Yield
(%)b
Entry
I2
DABCO
DABCO
DABCO
DABCO
DABCO
DBU
1
2
CH3CN
0
0
O
O
O
KI
O
O
O
O
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
THF(reflux)
1,4-dioxane
DCE
O
O
P
P
P
O
O
O
NaI
TBAI
I2O5
I2O5
I2O5
I2O5
I2O5
I2O5
I2O5
I2O5
I2O5
I2O5
I2O5
I2O5
I2O5
I2O5
I2O5
I2O5
I2O5
--
O
3
O
O
0
MeO
Br
4
3ba
(70%)
O
3aa
(80%)
0
3ca
(68%)
O
5
O
O
33
80
0
O
P
O
O
O
O
P
P
6
O
O
O
O
O
O
F
Cl
Et3N
7
3ea
(65% )
3da
(66%)
3fa
(58%)
KOH
8
trace
0
O
O
O
O
O
O
Na2CO3
Cs2CO3
DBU
O
O
9
O
P
P
O
P
O
O
O
O
O
10
11
12
13
14
15
16
17
18
19
20
21
22
23
S
0
3ga (64%)
3ha
3ia
(68%)
(75%)
51
58
63
68
55
0
DBU
O
O
O
O
O
O
O
O
O
P
DBU
P
P
O
O
O
O
O
O
Ph
DBU
DME
3la
(26%)
3ka
(24%)
DBU
3ja
(76%)
Toluene
EtOH
O
DBU
O
O
O
O
O
O
O
P
O
P
O
DBU
P
DMF
0
O
O
O
O
O
DBU
DMSO
H2O
0
3ad
(76%)
3ac
(67% )
3ab
(70% )
DBU
0
O
O
CH3CN
CH3CN
CH3CN
CH3CN
0c
52d
0
Ph
O
O
DBU
O
O
P
P
O
Ph
O
O
O
O
DBU
P
Ph
O
O
Ph
DBU
3af
(74%)
3jd
3ef
(57%)
3ae
(60%)
I2O5
--
0
O
O
Ph
P
Ph
O
O
Ph
a
O
Ph
Reaction conditions: 1a (0.25 mmol), 2a (0.75 mmol), iodine reagent (1
O
P
Ph
P
O
Ph
equiv), base (1 equiv), solvent (2 mL), 80°C, 48 h. TBAI=(n-Bu)4NI; DME:
1,2-Dimethoxyethane, DCE: 1,2-Dichloroethane.
O
Br
O
Cl
MeO
3ff
(66%)
(72%)
3cf
(67%)
b Isolated yields based on 1a.
c 25oC
d 60oC.
a Reaction conditions: 1a (0.25 mmol), 2a (0.75 mmol), I2O5 (0.25 mmol),
DBU (0.25 mmol), CH3CN (2 mL), 80°C, 48 h.
b Isolated yields based on 1.
I2, KI, NaI, and TBAI did not promote the formation of product
3aa (Table 1, entries 1-4). Further optimization of bases
suggested that DBU (1,8-diazabicycloundec-7-ene) stood out to
be the best choice, while the others such as Et3N, KOH, Na2CO3,
Cs2CO3 and DABCO were less effective (Table 1, entries 6-10).
Also, the effects of various solvents were investigated. Among a
range of solvents examined, CH3CN was found to be the
optimized reaction medium for this transformation, while THF,
DME, 1,4-dioxane, DCE, and toluene performed with moderate
efficiency (Table 1, entries 11-15). The reaction did not occur in
EtOH, DMF, DMSO, and H2O (Table 1, entries 16-19).
Moreover, none of the desired product 3aa was obtained when
the reaction was performed at room temperature (Table 1, entry
20). The reaction efficiency was obviously improved with
increasing of the reaction temperature and the best yield (80%)
was achieved when the reaction proceeded at 80°C (Table 1,
entries 6, 20-21). Additionally, no product was detected when the
reaction was conducted in the absence of I2O5 or DBU (Table 1,
entries 22 and 23).
With the optimized conditions in hand, we next explored the
scope and generality of this α-phosphoryloxylation reaction
(Table 2). In general, propiophenone derivatives with both
electron-donating and electron-withdrawing substituents on the
benzene ring could be smoothly transformed into the desired
products in moderate to good yields (3aa-3fa). Notably, halo
substituents including F, Cl, and Br could be tolerated in this
procedure, thus providing chances for further modification of
these compounds (3da-3fa). Heteroaromatic ketone such as 1-
(thiophen-2-yl)propan-1-one was also suitable for this process,
with the corresponding product in 64% yield (3ga). Moreover,
long chain alkyl substituted aromatic ketone did not hinder the
reaction, affording the desired products in good yields (3ha-3ja).

3
Nevertheless, none of the desired product was obtained when
dialkyl substituted aromatic ketone such as 2-methyl-1-
phenylpropan-1-one was used as the substrate, which might be
caused by the steric effect. Unfortunately, when 1,2-
diphenylethanone and acetophenone were used as the substrates,
the corresponding products were obtained in relatively low yields
(3ka and 3la). With respect to the H-phosphonates, dimethyl,
diisopropyl, dibutyl, and dibenzyl phosphonates were discovered
to be suitable substrates in addition to 2a, which delivered the
desired α-phosphoryloxylation products in moderate to good
yields. In addition, this synthetic methodology was extended to
Ph2P(O)H, showing the corresponding products in good yields
(3af-3ff).
In order to understand the detailed reaction mechanism,
several control experiments were performed as shown in Eq. 2-5.
When propiophenone 1a independently reacted with I2O5, the 2-
iodo-1-phenylpropan-1-one 4a could be obtained in 85% yield
(Eq. 2). On the other hand, the diethyl hydrogen phosphate 5a
was isolated in 82% yield when the reaction of diethyl
phosphonate 2a with I2O5 was performed in CH3CN at 80oC (Eq.
3). Furthermore, treatment of 2-iodo-1-phenylpropan-1-one 4a
with diethyl hydrogen phosphate 5a led to the formation of
desired product 3aa in the presence of DBU (Eq. 4). Nevertheless,
the direct reaction of propiophenone 1a with diethyl hydrogen
phosphate 5a did not give the desired α-phosphoryloxylation
product 3aa (Eq. 5). The above results indicated 4a and 5a might
be two key intermediates in the present reaction system.
hydrogen phosphate 5a. Then, the nucleophilic substitution of
ACCEPTED MANUSCRIPT
α-iodo ketone 4a by 5a in the presence of DBU would produce
the desired α-phosphoryloxylation product 3aa.
3. Conclusions
In conclusion, a novel and convenient synthesis method has
been developed for the one-pot construction of α-hydroxyketone
phosphates via direct α-phosphoryloxylation of ketones with H-
phosphonates simply by using I2O5/DBU system. This reaction
was constituted by three steps involving α-iodination of ketones,
oxidation of H-phosphonates, and nucleophilic substitution of α-
iodo ketones. A series of biologically important ketol phosphates
could be conveniently and efficiently obtained in moderate to
good yields from readily-available starting materials. The present
protocol is expected to expand the potential applications of α-
hydroxyketone phosphatess in the pharmaceutical and synthetic
chemistry.
4. Experimental section
4.1. General remarks
All commercially available reagent grade chemicals were
purchased from Aldrich, Acros, Alfa Aesar and Beijing Ouhe
Chemical Company and used as received without further
purification unless otherwise stated. 1H NMR, 13C NMR and 31P
NMR were recorded in CDCl3 on a Bruker Avance III 400
1
O
O
spectrometer with TMS as internal standard (400 MHz H, 100
MHz 13C, 162 MHz 31P ) at room temperature, the chemical shifts
(δ) were expressed in ppm and J values were given in Hz. The
following abbreviations are used to indicate the multiplicity:
singlet (s), doublet (d), triplet (t), quartet (q), doublet of doublets
(dd), doublet of triplets (dt), and multiplet (m). All first order
splitting patterns were assigned on the basis of the appearance of
the multiplet. Splitting patterns that could not be easily
interpreted were designated as multiplet (m). Mass analyses and
I2O5 (1 equiv)
CH3CN, 80oC
(2)
(3)
(4)
I
4a
(85%)
1a
O
O
I2O5 (1 equiv)
CH3CN, 80oC
O
O
P
P
O
H
HO
O
2a
5a (82%)
O
O
HRMS were obtained on
a
Finnigan-LCQDECA mass
spectrometer and Bruker Daltonics Bio-TOF-Q mass
spectrometer by the ESI method, respectively. Column
chromatography was performed on silica gel (200-300 mesh).
O
O
O
O
DBU (1 equiv)
CH3CN, 80oC
a
P
P
+
HO
O
O
O
I
3aa (83%)
4a
5a
O
O
O
O
4.2. Experimental Procedures:
O
DBU (1 equiv)
CH3CN, 80oC
O
(5)
P
P
+
O
HO
O
O
5a
General procedure for I2O5/DBU mediated direct α-
phosphoryloxylation of ketones with H-phosphonates.
3aa
1a
On the basis of the above results and previous reports,13,15
a
In a sealed tube (25 mL), ketones 1 (0.25 mmol), H-
phosphonates 2 (0.75 mmol), I2O5 (0.25 mmol), DBU (0.25
mmol), and CH3CN (2 mL) were added. The reaction vessel was
allowed to stir at 80 °C for 48 h. After the reaction, the solution
was concentrated in vacuum. The resulting mixture purified by
flash column chromatography using a mixture of petroleum ether
and ethyl acetate as eluent to give the desired product 3.
tentative reaction pathway was proposed in Scheme 1. Initially,
α-iodination of propiophenone 1 with I2O5 formed the key
intermediate α-iodo ketone 4a, and the oxidation of diethyl
phosphonate 2a with I2O5 produced the corresponding diethyl
The reaction of propiophenone 1a with I2O5.
In a sealed tube (25 mL), propiophenone 1a (0.25 mmol), I2O5
(0.25 mmol), and CH3CN (2 mL) were added. The reaction
vessel was allowed to stir at 80 °C for 48 h. After the reaction,
the solution was concentrated in vacuum. The resulting mixture
purified by flash column chromatography using a mixture of
petroleum ether and ethyl acetate as eluent to give the desired 2-
iodo-1-phenylpropan-1-one 4a in 85% yield.
The reaction of diethyl phosphonate 2a with I2O5.
Scheme 1. Tentative reaction pathway

4
Tetrahedron
ACCEPTED MANUSCRIPT
In a sealed tube (25 mL), diethyl phosphonate 2a (0.25 mmol),
131.6 (d, J = 9.4 Hz), 130.6 (d, J = 3.0 Hz), 115.9 (d, J = 21.8
I2O5 (0.25 mmol), and CH3CN (2 mL) were added. The reaction
vessel was allowed to stir at 80 °C for 12 h. After the reaction,
the solution was concentrated in vacuum. The resulting mixture
purified by flash column chromatography using a mixture of
petroleum ether and ethyl acetate as eluent to give the desired
diethyl hydrogen phosphate 5a in 82% yield.
Hz), 74.5 (d, J = 5.4 Hz), 64.1 (q, J = 6.0 Hz), 19.2 (d, J = 5.0
Hz), 16.0 (t, J = 6.7 Hz); 31P NMR (162 MHz, CDCl3): δ -1.88;
HRMS calc. for C13H18FO5PNa (M+Na)+, 327.0774; found,
327.0770.
1-(4-Chlorophenyl)-1-oxopropan-2-yl diethyl phosphate,
compound 3ea was obtained in 65% yield according to the
general procedure (48 h). H NMR (CDCl3, 400 MHz, ppm): δ
1
The reaction of 4a and 5a in the presence of DBU.
7.96 (d, J = 8.6 Hz, 2H), 7.48 (d, J = 8.6 Hz, 2H), 5.72-5.65 (m,
1H), 4.16-4.09 (m, 4H), 1.62 (d, J = 6.8 Hz, 3H), 1.35 (dt, J1 =
7.1 Hz，J2 = 0.7 Hz, 3H), 1.29 (dt, J1 = 7.1 Hz, J2 = 0.7 Hz, 3H);
13C NMR (CDCl3, 100 MHz, ppm): δ 195.2 (d, J = 4.9 Hz), 140.2,
132.5, 130.3, 129.1, 74.6 (d, J = 5.4 Hz), 64.2 (q, J = 6.0 Hz),
19.2 (d, J = 5.1 Hz), 16.0 (t, J = 6.5 Hz); 31P NMR (162 MHz,
CDCl3): δ -1.92; HRMS calc. for C13H19ClO5P (M+H)+, 321.0659;
found, 321.0656.
To a mixture of 2-iodo-1-phenylpropan-1-one 4a (0.25 mmol),
diethyl hydrogen phosphate 5a (0.75 mmol) and DBU (0.25
mmol) in a 25 mL round-bottomed flack at room temperature,
was added the CH3CN (2 mL). The reaction vessel was allowed
to stir at 80 °C for 12 h. After the reaction, the solution was
concentrated in vacuum, the desired product 3aa was obtained in
83% yield.
The reaction of 1a and 5a in the presence of DBU.
1-(4-Bromophenyl)-1-oxopropan-2-yl diethyl phosphate,
compound 3fa was obtained in 58% yield according to the
general procedure (48 h). H NMR (CDCl3, 400 MHz, ppm): δ
To a mixture of propiophenone 1a (0.25 mmol), diethyl hydrogen
phosphate 5a (0.75 mmol) and DBU (0.25 mmol) in a 25 mL
round-bottomed flack at room temperature, was added the
CH3CN (2 mL). The reaction vessel was allowed to stir at 80oC
for 12 h. After the reaction, the solution was concentrated in
vacuum, none of the desired product 3aa was detected.
1
7.88 (d, J = 8.6 Hz, 2H), 7.65 (d, J = 8.6 Hz, 2H), 5.72-5.65 (m,
1H), 4.16-4.10 (m, 4H), 1.62 (d, J = 6.8 Hz, 3H), 1.35 (dt, J1 =
7.1 Hz，J2 = 1.0 Hz, 3H), 1.30 (dt, J1 = 7.1 Hz, J2 = 1.0 Hz, 3H);
13C NMR (CDCl3, 100 MHz, ppm): δ 195.5 (d, J = 5.0 Hz), 133.0,
132.1, 130.3, 128.9, 74.6 (d, J = 5.5 Hz), 64.2 (q, J = 6.1 Hz),
19.2 (d, J = 4.7 Hz), 16.0 (t, J = 6.5 Hz); 31P NMR (162 MHz,
CDCl3): δ -1.95; HRMS calc. for C13H18BrO5PNa (M+Na)+,
386.9973; found, 386.9974.
Diethyl 1-oxo-1-phenylpropan-2-yl phosphate, compound 3aa
was obtained in 80% yield according to the general procedure (48
h). 1H NMR (CDCl3, 400 MHz, ppm): δ 7.99 (d, J = 7.2 Hz, 2H),
7.61 (t, J = 7.4 Hz, 1H), 7.50 (t, J = 7.9 Hz, 2H), 5.80-5.73 (m,
1H), 4.16-4.09 (m, 4H), 1.63 (d, J = 6.8 Hz, 3H), 1.35 (dt, J1 =
7.1 Hz, J2 = 0.9 Hz, 3H), 1.28 (dt, J1 = 7.1Hz, J2= 0.9Hz, 3H);
13C NMR (CDCl3, 100 MHz, ppm): δ 196.4 (d, J = 4.8 Hz), 134.3,
133.7, 130.9, 128.8, 74.6 (d, J = 5.4 Hz), 64.1 (q, J = 6.0 Hz),
19.4 (d, J = 5.0 Hz), 16.0 (t, J = 6.9 Hz); 31P NMR (162 MHz,
CDCl3): δ -1.88; HRMS calc. for C13H19O5PNa (M+Na)+,
309.0868; found, 309.0871.
Diethyl
1-oxo-1-(thiophen-2-yl)propan-2-yl
phosphate,
compound 3ga was obtained in 64% yield according to the
1
general procedure (48 h). H NMR (CDCl3, 400 MHz, ppm): δ
7.93 (d, J = 3.8 Hz, 1H), 7.73 (d, J = 4.9 Hz, 1H), 7.18 (t, J = 4.2
Hz, 1H), 5.52-5.45 (m, 1H), 4.16-4.09 (m, 4H), 1.66 (d, J = 6.8
Hz, 3H), 1.34 (d, J = 7.0 Hz, 3H), 1.29 (d, J = 7.1 Hz, 3H); 13C
NMR (CDCl3, 100 MHz, ppm): δ 189.5 (d, J = 5.1 Hz), 140.3,
135.0, 133.6, 128.4, 75.7 (d, J = 5.5 Hz), 64.2 (t, J = 6.4 Hz),
19.9 (d, J = 5.1 Hz), 16.1 (d, J = 4.6 Hz), 16.0 (d, J = 4.6 Hz); 31P
Diethyl 1-oxo-1-p-tolylpropan-2-yl phosphate, compound 3ba
was obtained in 70% yield according to the general procedure (48
h). 1H NMR (CDCl3, 400 MHz, ppm): δ 7.88 (d, J = 8.2 Hz, 2H),
7.28 (d, J = 8.0 Hz, 2H), 5.78-5.70 (m, 1H), 4.16-4.07 (m, 4H),
2.42 (s, 3H), 1.61 (d, J = 6.8 Hz, 3H), 1.33 (dt, J1 = 7.1 Hz, J2 =
0.8 Hz, 3H), 1.28 (dt, J1 = 7.1 Hz, J2 = 0.8 Hz, 3H); 13C NMR
(CDCl3, 100 MHz, ppm): δ 195.8 (d, J = 4.8 Hz), 144.6, 131.6,
129.4, 128.9, 74.5 (d, J = 5.4 Hz), 64.1 (q, J = 6.0 Hz), 21.7, 19.5
(d, J = 5.1 Hz), 16.0 (t, J = 6.6 Hz); 31P NMR (162 MHz, CDCl3):
δ -1.91; HRMS calc. for C14H21O5PNa (M+Na)+, 323.1024; found,
323.1028.
NMR (162 MHz, CDCl3):
δ
-2.13; HRMS calc. for
C11H17O5PSNa (M+Na)+, 315.0432; found, 315.0428.
Diethyl 1-oxo-1-phenylbutan-2-yl phosphate, compound 3ha
was obtained in 68% yield according to the general procedure (48
h). 1H NMR (CDCl3, 400 MHz, ppm): δ 7.97 (d, J = 7.2 Hz, 2H),
7.61 (t, J = 7.4 Hz, 1H), 7.50 (t, J = 7.8 Hz, 2H), 5.63-5.58 (m,
1H), 4.17-4.09 (m, 4H), 2.06-1.99 (m, 1H), 1.96-1.89 (m, 1H),
1.34 (dt, J1 = 7.0 Hz, J2 = 0.9 Hz, 3H), 1.29 (dt, J1 = 7.1 Hz, J2 =
0.9 Hz, 3H), 1.05 (t, J = 7.4 Hz, 3H); 13C NMR (CDCl3, 100
MHz, ppm): δ 196.4 (d, J = 2.7 Hz), 134.7, 133.6, 128.8, 128.6,
79.5 (d, J = 5.6 Hz), 64.1 (q, J = 6.0 Hz), 26.8 (d, J = 6.3 Hz),
16.0 (t, J = 6.8 Hz), 9.3; 31P NMR (162 MHz, CDCl3): δ -1.64;
HRMS calc. for C14H21O5PNa (M+Na)+, 323.1024; found,
323.1019.
Diethyl 1-(4-methoxyphenyl)-1-oxopropan-2-yl phosphate,
compound 3ca was obtained in 68% yield according to the
1
general procedure (48 h). H NMR (CDCl3, 400 MHz, ppm): δ
7.98 (d, J = 8.9 Hz, 2H), 6.96 (d, J = 8.9 Hz, 2H), 5.75-5.68 (m,
1H), 4.15-4.07 (m, 4H), 3.88 (s, 3H), 1.61 (d, J = 6.8 Hz, 3H),
1.33 (dt, J1 = 7.0 Hz, J2 = 0.8 Hz 3H), 1.27 (dt, J1 = 7.0 Hz, J2 =
0.8 Hz, 3H); 13C NMR (CDCl3, 100 MHz, ppm): δ 194.6 (d, J =
4.8 Hz), 163.9, 131.1, 127.0, 114.0, 74.3 (d, J = 5.4 Hz), 64.0 (q,
J = 6.0 Hz), 55.5, 19.5 (d, J = 5.0 Hz), 16.0 (t, J = 6.5 Hz); 31P
NMR (162 MHz, CDCl3): δ -2.01; HRMS calc. for C14H21O6PNa
(M+Na)+, 339.0973; found, 33.9.0977.
Diethyl 1-oxo-1-phenylpentan-2-yl phosphate, compound 3ia
was obtained in 75% yield according to the general procedure (48
h). 1H NMR (CDCl3, 400 MHz, ppm): δ 7.96 (d, J = 7.2 Hz, 2H),
7.59 (t, J = 7.4 Hz, 1H), 7.48 (t, J = 7.8 Hz, 2H), 5.64 (q, J = 7.1
Hz, 1H), 4.16-4.08 (m, 4H), 1.90-1.85(m, 2H), 1.55-1.49 (m, 2H),
1.32 (dt, J1 = 7.0 Hz, J2 = 0.7 Hz, 3H), 1.28 (dt, J1 = 7.1 Hz, J2 =
0.8 Hz, 3H), 0.96 (t, J = 7.4 Hz, 3H); 13C NMR (CDCl3, 100
MHz, ppm): δ 196.5 (d, J = 2.4 Hz), 134.7, 133.6, 128.8, 128.6,
78.3 (d, J = 5.6 Hz), 64.0 (q, J = 6.0 Hz), 35.5 (d, J = 6.5 Hz),
18.3, 16.0 (t, J = 6.7 Hz), 13.6; 31P NMR (162 MHz, CDCl3): δ -
1.67; HRMS calc. for C15H24O5P (M+H)+, 315.1361; found,
315.1364.
Diethyl
1-(4-fluorophenyl)-1-oxopropan-2-yl
phosphate,
compound 3da was obtained in 66% yield according to the
1
general procedure (48 h). H NMR (CDCl3, 400 MHz, ppm): δ
8.06-8.03 (m, 2H), 7.17 (m, 2H), 5.73-5.66 (m, 1H), 4.16-4.07
(m, 4H), 1.62 (d, J = 6.8 Hz, 3H), 1.34 (dt, J1 = 7.1 Hz, J2 = 1.0
Hz, 3H), 1.28 (dt, J1 = 7.1 Hz, J2 = 1.0 Hz, 3H); 13C NMR (CDCl3,
100 MHz, ppm): δ 194.8 (d, J = 5.0 Hz), 166.0 (d, J = 254.5 Hz),

5
Diethyl 1-oxo-1-phenylhexan-2-yl phosphate, compound 3ja
was obtained in 76% yield according to the general procedure (48
h). 1H NMR (CDCl3, 400 MHz, ppm): δ 7.97 (d, J = 7.4 Hz, 2H),
7.61 (t, J = 7.3 Hz, 1H), 7.49 (t, J = 7.8 Hz, 2H), 5.67-5.62 (m,
1H), 4.19-4.10 (m, 4H), 1.94-1.86 (m, 2H), 1.51-1.46 (m, 2H),
1.38-1.27 (m, 8H), 0.89 (t, J = 7.3 Hz, 3H); 13C NMR (CDCl3,
100 MHz, ppm): δ 196.6 (d, J = 2.4 Hz), 134.6, 133.6, 128.8,
128.6, 78.5 (d, J = 5.6 Hz), 64.1 (q, J = 6.0 Hz), 33.2 (d, J = 6.5
Hz), 27.1, 22.2, 16.0 (t, J = 6.6 Hz), 13.8; 31P NMR (162 MHz,
CDCl3): δ -1.67; HRMS calc. for C16H25O5PNa (M+Na)+,
351.1337; found, 351.1339.
(d, J = 5.8 Hz), 13.6 (d, J = 3.8 Hz); 31P NMR (162 MHz,
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CDCl3): δ -1.74; 1HRMS calc. for C17H27O5PNa (M+Na)+,
365.1494; found, 365.1495.
Dibenzyl 1-oxo-1-phenylpropan-2-yl phosphate, compound
3ae was obtained in 60% yield according to the general
procedure (48 h). 1H NMR (CDCl3, 400 MHz, ppm): δ 7.94 (d, J
= 7.2 Hz, 2H), 7.60 (t, J = 7.4 Hz, 1H), 7.47 (t, J = 7.8 Hz, 2H),
7.36 (s, 5H), 7.32 (s, 5H), 5.78-5.71 (m, 1H), 5.12-5.03 (m, 4H),
1.57 (d, J = 6.9 Hz, 3H); 13C NMR (CDCl3, 100 MHz, ppm): δ
196.2 (d, J = 4.6 Hz), 135.7 (dd, J1 = 1.8 Hz, J2 = 7.3 Hz), 134.1,
133.7, 128.8 (d, J = 1.7 Hz), 128.6 (d, J = 4.6 Hz), 128.6, 128.5,
128.0 (d, J = 3.4 Hz), 74.9 (d, J = 5.4 Hz), 69.5 (q, J = 2.5 Hz),
19.3 (d, J = 5.3 Hz); 31P NMR (162 MHz, CDCl3): δ -1.92;
1HRMS calc. for C23H24O5P (M+H)+, 411.1361; found, 411.1364.
Diethyl 2-oxo-1,2-diphenylethyl phosphate, compound 3ka
was obtained in 24% yield according to the general procedure (48
h). 1H NMR (CDCl3, 400 MHz, ppm): δ 7.95 (d, J = 7.2 Hz, 2H),
7.54-7.50 (m, 3H), 7.43-7.34 (m, 5H), 6.67 (d, J = 8.0 Hz, 1H),
4.24-4.18(m, 2H), 3.96-3.89 (m, 2H), 1.34 (dt, J1 = 7.1 Hz, J2 =
0.9 Hz, 3H), 1.15 (dt, J1 = 7.1 Hz, J2 = 0.9 Hz, 3H); 13C NMR
(CDCl3, 100 MHz, ppm): δ 193.6 (d, J = 4.6 Hz), 134.9 (d, J =
5.3 Hz), 134.3, 133.6, 129.3, 129.1, 129.0, 128.6, 128.1, 80.1 (d,
J = 4.8 Hz), 64.4 (d, J = 5.9 Hz), 64.0 (d, J = 6.1 Hz), 16.0 (d, J =
7.0 Hz), 15.8 (d, J = 7.1 Hz); 31P NMR (162 MHz, CDCl3): δ -
1.92; HRMS calc. for C18H22O5P (M+H)+, 349.1205; found,
349.1204.
Dibutyl 1-oxo-1-phenylhexan-2-yl phosphate, compound 3jd
was obtained in 57% yield according to the general procedure (48
h). 1H NMR (CDCl3, 400 MHz, ppm): δ 7.98 (d, J = 7.1 Hz, 2H),
7.61 (t, J = 7.4 Hz, 1H), 7.50 (t, J = 7.9 Hz, 2H), 5.67-5.62 (m,
1H), 4.09-4.04 (m, 4H), 1.93-1.87 (m, 2H), 1.67-1.57 (m, 4H),
1.50-1.30 (m, 8H), 0.95-0.87 (m, 9H); 13C NMR (CDCl3, 100
MHz, ppm): δ 196.2 (d, J = 2.5 Hz), 134.6, 133.6, 128.8, 128.7,
78.6 (d, J = 5.7 Hz), 67.8 (t, J = 6.1 Hz), 33.2 (d, J = 6.4 Hz),
32.2 (d, J = 5.1 Hz), 32.1 (d, J = 5.1 Hz), 27.1, 22.2, 18.6 (d, J =
3.8 Hz), 13.8, 13.6 (d, J = 1.9 Hz); 31P NMR (162 MHz, CDCl3):
δ -1.55; HRMS calc. for C20H33O5PNa (M+Na)+, 407.1963; found,
407.1966.
Diethyl 2-oxo-2-phenylethyl phosphate
Compound 3la was obtained in 26% yield according to the
general procedure (48 h). 1H NMR (CDCl3, 400 MHz, ppm): δ
7.91 (d, J = 7.3 Hz, 2H), 7.63 (t, J = 7.4 Hz, 1H), 7.50 (t, J = 7.8
Hz, 2H), 5.34 (d, J = 9.9Hz, 2H), 4.28-4.20 (m, 4H), 1.38 (dt,
6H); 13C NMR (CDCl3, 100 MHz, ppm): δ 192.3 (d, J = 5.2 Hz),
134.0, 133.9, 128.9, 127.8, 68.7 (d, J = 5.2 Hz), 64.4 (d, J = 6.0
Hz), 16.1 (d, J = 6.9 Hz); 31P NMR (162 MHz, CDCl3): δ -0.91;
HRMS calc. for C12H17O5PNa (M+Na)+, 295.0711; found,
295.0775.
1-Oxo-1-phenylpropan-2-yl diphenylphosphinate, compound
3af was obtained in 74% yield according to the general procedure
(48 h). H NMR (CDCl3, 400 MHz, ppm): δ 7.95-7.87 (m, 4H),
1
7.79-7.74 (m, 2H), 7.59-7.54 (m, 2H), 7.52-7.47 (m, 2H), 7.45-
7.41 (m, 3H), 7.39-7.35 (m, 2H), 5.92-5.84 (m, 1H), 1.63 (d, J =
6.8 Hz, 3H); 13C NMR (CDCl3, 100 MHz, ppm): δ 196.7 (d, J =
4.8 Hz), 134.3, 133.5, 132.3 (d, J = 2.8 Hz), 132.2 (d, J = 2.9 Hz),
132.1 (d, J = 65.1 Hz), 131.8 (d, J = 7.9 Hz), 131.6 (d, J = 7.6
Hz), 130.8 (d, J = 62.9 Hz), 128.7 (d, J = 1.8 Hz), 128.6, 128.5 (d,
J = 3.3 Hz), 128.4, 72.0 (d, J = 5.7 Hz), 20.2 (d, J = 3.2 Hz);
31P NMR (162 MHz, CDCl3): δ 33.12; HRMS calc. for
C21H19O3PNa (M+Na)+, 373.0970; found,373.0971.
Dimethyl 1-oxo-1-phenylpropan-2-yl phosphate, compound
3ab was obtained in 70% yield according to the general
procedure (48 h). 1H NMR (CDCl3, 400 MHz, ppm): δ 7.99 (d, J
= 7.2 Hz, 2H), 7.63 (t, J = 7.4 Hz, 1H), 7.51 (t, J = 7.9 Hz, 2H),
5.84-5.77 (m, 1H), 3.79 (t, J = 11.3 Hz, 6H), 1.64 (d, J = 6.9 Hz,
3H); 13C NMR (CDCl3, 100 MHz, ppm): δ 196.2 (d, J = 4.7 Hz),
134.1, 133.8, 128.8, 128.7, 74.8 (d, J = 5.3 Hz), 54.5 (q, J = 6.1
Hz), 19.4 (d, J = 5.2 Hz); 31P NMR (162 MHz, CDCl3): δ 0.33;
HRMS calc. for C11H15O5PNa (M+Na)+, 281.0555; found,
281.0556.
1-(4-Methoxyphenyl)-1-oxopropan-2-yl diphenylphosphinate,
compound 3cf was obtained in 67% yield according to the
general procedure (48 h). H NMR (CDCl3, 400 MHz, ppm): δ
1
7.96-7.89 (m, 4H), 7.80-7.74 (m, 2H), 7.59-7.55 (m, 1H), 7.52-
7.43 (m, 3H), 7.39-7.36 (m, 2H), 6.90 (d, J = 9.0 Hz, 2H), 5.89-
5.81 (m, 1H), 3.87 (s, 3H), 1.62 (d, J = 6.8 Hz, 3H); 13C NMR
(CDCl3, 100 MHz, ppm): δ 195.0 (d, J = 4.8 Hz), 163.9, 132.3 (d,
J = 2.8 Hz), 132.2 (d, J = 68.3 Hz), 132.2 (d, J = 2.8 Hz), 131.8
(d, J = 10.4 Hz), 131.7 (d, J = 10.4 Hz), 131.1, 130.8 (d, J = 64.7
Hz), 128.6 (d, J = 8.5 Hz), 128.4 (d, J = 9.5 Hz), 127.0, 113.9,
71.8 (d, J = 5.7 Hz), 55.5, 20.4 (d, J = 3.1 Hz); 31P NMR (162
MHz, CDCl3): δ 33.01; HRMS calc. for C22H21O4PNa (M+Na)+,
403.1075; found, 403.1077.
Diisopropyl 1-oxo-1-phenylpropan-2-yl phosphate, compound
3ac was obtained in 67% yield according to the general
procedure (48 h). 1H NMR (CDCl3, 400 MHz, ppm): δ 8.00 (d, J
= 7.2 Hz, 2H), 7.60 (t, J = 7.4 Hz, 1H), 7.49 (t, J = 7.8 Hz, 2H),
5.75-5.68 (m, 1H), 4.69-4.60 (m, 2H), 1.62 (d, J = 6.8 Hz,
3H), 1.33 (q, J = 6.2 Hz, 6H), 1.27 (t, J = 6.0 Hz, 6H); 13C NMR
(CDCl3, 100 MHz, ppm): δ 196.6 (d, J = 5.1 Hz), 134.3, 133.6,
128.8, 128.7, 74.5 (d, J = 5.5 Hz), 72.9 (q, J = 3.0 Hz), 23.6 (d, J
= 4.8 Hz), 23.4 (d, J = 5.1 Hz), 19.4 (d, J = 4.8 Hz); 31P NMR
(162 MHz, CDCl3): δ -3.48; HRMS calc. for C15H23O5PNa
(M+Na)+, 337.1181; found, 337.1176.
1-(4-Chlorophenyl)-1-oxopropan-2-yl diphenylphosphinate,
compound 3ef was obtained in 72% yield according to the
general procedure (48 h). H NMR (CDCl3, 400 MHz, ppm): δ
1
7.93-7.88 (m, 2H), 7.87-7.84 (m, 2H), 7.77-7.71 (m, 2H), 7.59-
7.55 (m, 1H), 7.51-7.45 (m, 3H), 7.40-7.35 (m, 4H), 5.87-5.80
(m, 1H), 1.60 (d, J = 6.8 Hz, 3H); 13C NMR (CDCl3, 100 MHz,
ppm): δ 195.6 (d, J = 4.7 Hz), 140.1, 132.6, 132.5 (d, J = 2.8 Hz),
132.4 (d, J = 2.8 Hz), 131.9 (d, J = 55.1 Hz), 131.7 (d, J = 1.6
Hz), 131.6 (d, J = 1.4 Hz), 130.5(d, J = 52.6 Hz), 130.2, 129.0,
128.7 (d, J = 11.6 Hz), 128.6 (d, J = 11.6 Hz), 72.0 (d, J = 5.7
Hz), 20.0 (d, J = 3.2 Hz); 31P NMR (162 MHz, CDCl3): δ 33.54;
Dibutyl 1-oxo-1-phenylpropan-2-yl phosphate, compound 3ad
was obtained in 76% yield according to the general procedure (48
h). 1H NMR (CDCl3, 400 MHz, ppm): δ 8.00 (d, J = 7.2 Hz, 2H),
7.61 (t, J = 7.4 Hz, 1H), 7.50 (t, J = 7.8 Hz, 2H), 5.80-5.73 (m,
1H), 4.08-4.01 (m, 4H), 1.69-1.58 (m, 7H), 1.44-1.39 (m, 2H),
1.37-1.31 (m, 2H), 0.94 (t, J = 7.4 Hz, 3H), 0.88 (t, J = 7.4 Hz,
3H); 13C NMR (CDCl3, 100 MHz, ppm): δ 196.4 (d, J = 5.1 Hz),
134.2, 133.6, 128.8 128.7, 74.6 (d, J = 5.4 Hz), 67.8 (t, J = 6.3
Hz), 32.2 (dd, J1 = 5.5 Hz, J2 = 7.0 Hz), 19.3 (d, J = 4.9 Hz), 18.6

6
Tetrahedron
HRMS calc. for C21H18O3ClPNa (M+Na)+, 407.0580; found,
1960, 82, 2652; (b) Ramirez, F.; Glaser, S. L.; Bigler, A. J.; Pilot, J.
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F. J. Am. Chem. Soc. 1969, 91, 496; (c)Ramirez, F.; Bhatia, S. B.;
407.0584.
Bigler, A. J.; Smith, C. P. J. Org. Chem. 1968, 33, 1192; (d)
Ramirez, F.; Bauer, J.; Telefus, C. D. J. Am. Chem. Soc. 1970, 92,
6935; (e) Koser, G. F.; Lodaya, J. S.; Ray, D. G.; Kokil, P. B. J. Am.
Chem. Soc. 1988, 110, 2987; (f) Nabana, T.; Togo, H. J. Org. Chem.
2002, 67, 4362.
1-(4-Bromophenyl)-1-oxopropan-2-yl diphenylphosphinate,
compound 3ff was obtained in 66% yield according to the
general procedure (48 h). H NMR (CDCl3, 400 MHz, ppm): δ
1
7.93-7.87 (m, 2H), 7.78-7.71 (m, 4H), 7.60-7.55 (m, 3H), 7.52-
7.45 (m, 3H), 7.40-7.35 (m, 2H), 5.87-5.79 (m, 1H), 1.60 (d, J =
6.8 Hz, 3H); 13C NMR (CDCl3, 100 MHz, ppm): δ 195.8 (d, J =
4.8 Hz), 133.0, 132.5 (d, J = 2.8 Hz), 132.4 (d, J= 2.8 Hz), 132.0,
131.9 (d, J = 55.6 Hz), 131.7 (d, J = 1.9 Hz), 131.6 (d, J = 1.7
Hz), 130.5 (d, J = 53.2 Hz), 130.2, 128.8, 128.7 (d, J = 11.2 Hz),
128.5 (d, J = 11.2 Hz), 72.0 (d, J = 5.7 Hz), 20.0 (d, J = 3.3 Hz);
31P NMR (162 MHz, CDCl3): δ 33.55; HRMS calc. for
C21H19O3BrP (M+H)+, 429.0255; found, 429.0257.
10 Koser, G. F.; Chen, X.; Chen, K.; Sun, G. Tetrahedron Lett, 1993,
34, 779.
11 Koser, G. F.; Chen, K.; Huang, Y.; Summers, C. A. J. Chem.
Soc.,Perkin Trans.1 1994, 1375.
12 Pu, Y.; Gao, L. M.; Liu, H. J.; Yan, J. Synthesis, 2012, 44, 99.
13 (a) Nicolaou, K. C.; Montagnon, T.; Baran, P. S. Angew. Chem.,
Int. Ed. 2002, 41, 1386; (b) Chai, L.; Zhao, Y.; Sheng, Q.; Liu, Z.-
Q. Tetrahedron Lett. 2006, 47, 9283; (c) Liu, Z.-Q.; Zhao, Y.; Luo,
H.; Chai, L.; Sheng, Q. Tetrahedron Lett. 2007, 48, 3017; (d) Hang,
Z.; Li, Z.; Liu, Z-Q. Org. Lett. 2014, 16, 3648; (e) Zhang, L.; Li, Z.;
Liu, Z-Q. Org. Lett. 2014, 16, 3688.
14 (a) Wei, W.; Wen, J.; Yang, D.; Du, J.; You, J.; Wang, H. Green
Chem., 2014, 16, 2988; (b) Wei, W.; Wen, J.; Yang, D.; Guo, M.;
Wang, Y.;You, J.; Wang, H. Chem. Commun., 2015, 51, 768; (c)
Wei, W.; Wen, J.; Yang, D.; Liu, X.; Guo, M.; Dong, R.; Wang, H.
J. Org. Chem. 2014, 79, 4225; (d) Wei, W.; Wen, J.; Yang, D.; Jing,
H.; You, J.; Wang, H. RSC Adv., 2015, 5, 4416; (e) Wei, W.; Liu,
X.; Yang, D.; Dong, R.; Cui, Y.; Yuan, F.; Wang, H. Tetrahedron
Lett 2015, 56, 1808.
2-Iodo-1-phenylpropan-1-one, compound 4a was obtained in
85% yield from the reaction of propiophenone 1a with I2O5 (48
1
h). H NMR (CDCl3, 400 MHz, ppm): δ 8.04-8.02 (m, 2H), 7.60
(t, J = 7.4 Hz, 1H), 7.50 (t, J = 7.9 Hz, 2H), 5.52 (q, J = 6.7 Hz,
1H), 2.10 (d, J = 6.7 Hz, 3H); 13C NMR (CDCl3, 100 MHz, ppm):
δ 194.8, 133.7, 133.5, 128.7, 128.7, 22.0, 18.1; HRMS calc. for
C9H10OI (M+H)+, 260.9776; found, 260.9771.
15 (a) Guha, S.; Rajeshkumar, V.; Kotha, S. S.; Sekar, G. Org. Lett.
2015, 17, 406; (b) Liang, Y.-F.; Wu, K.; Song, S.; Li, X.; Huang, X.;
Jiao, N.Org. Lett. 2015, 17, 876.
Acknowledgments
This work was supported by the National Natural Science
Foundation of China (No. 21302109, 21302110, and 21375075),
the Taishan Scholar Foundation of Shandong Province, the
Excellent Middle-Aged and Young Scientist Award Foundation
of Shandong Province (BS2013YY019), and the Scientific
Research Foundation of Qufu Normal University (BSQD
2012020).
References and notes
1
2
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Hecker, S. J.; Erion, M. D. J. Med. Chem. 2008, 51, 2328; (e)
Pradere, U.; Garnier-Amblard, E. C.; Coats, S. J.; Amblard,
F.; Schinazi, R. F. Chem. Rev., 2014, 114, 9154.
3
(a) Neumann, R.; Peter, H. H. Experientia 1987, 43, 1235; (b) He,
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55, 472; (d) Vìrtesy, L.; Beck, B.; Bro¨nstrup, M.; Ehrlich, K.; Kurz,
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480; (e) Kiely, T.; Donaldson, D.; Grube, A. EPA-733-R-04-001;
Washington, DC: Office of Pesticide Programs, U.S. Environmental
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4
5
(a) Bandyopadhyay, S.; Dutta, S.; Spilling, C. D.;Dupureur, C. M.;
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K.; Bandyopadhyay, S.; Spilling, C. D.; Dupureur, C. M. Bioorg.
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S.; Martin, B. P.; Delorme, V.; Carriere, F.; Canaan, S.; Rath, N. P.;
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Ramirez, F.; Bauer, J.; Telefus, C. D. J. Am. Chem. Soc. 1970, 92,
6935; see p. 6937 and references cited therein.
6
7
Ramirez, F.; Narecek, J. F. synthesis 1985, 449.
(a) Ramirez, F.; Hansen, B.; Desai, N. B. J. Am. Chem. Soc. 1962,
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113, 996.
8
9
Ramirez, F.; Bauer, J.; Telefus, C. D. J. Am. Chem. Soc. 1970, 92,
6935.
(a) Ramires, F.; Mitra, R. B.; Desai, N. B. J. Am. Chem. Soc.

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Supplementary Information
I2O5/DBU mediated direct α-phosphoryloxylation of ketones
with H-phosphonates leading to α-hydroxyketone
phosphates
Chunli Liua, Wei Wei*a, Daoshan Yanga, Yuanyuan Zhenga, Yanshuai Bia, Min Chena,
Hua Wang*a
The Key Laboratory of Life-Organic Analysis and Key Laboratory of Pharmaceutical
Intermediates and Analysis of Natural Medicine, School of Chemistry and Chemical
Engineering, Qufu Normal University, Qufu 273165, Shandong, China
*Phone:+86 537 4458317; Fax:+86 537 4458317.
. E-mail: weiweiqfnu@163.com; huawang_qfnu@126.com
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