An effective catalytic α-phosphoryloxylation of ketones with iodobenzene

Article abstract of DOI:10.1055/s-0031-1289630

An effective catalytic method for α-phosphoryloxylation of ketones is reported. When ketones were reacted with phosphates in the presence of iodobenzene as the recyclable catalyst and m-chloroperbenzoic acid as the terminal oxidant in acetonitrile at room temperature, the α- phosphoryloxylation of ketones took place easily and the corresponding keto phosphates were obtained in moderate to good yields. Georg Thieme Verlag Stuttgart. New York.

Full text of DOI:10.1055/s-0031-1289630

PAPER
99
An Effective Catalytic a-Phosphoryloxylation of Ketones with Iodobenzene
Ye Pu,a Liumian Gao,b Huijun Liu,a Jie Yan*a
a
College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310032, P. R. of China
Fax +86(571)88320238; E-mail: jieyan87@zjut.edu.cn
Research Institute of Nanjing Chemical Industrial Group, Nanjing 210048, P. R. of China
b
Received 23 August 2011; revised 18 October 2011
ketones has not been reported before. In order to extend
the scope of catalytic application of hypervalent iodine re-
agents in organic synthesis, we have investigated the a-
phosphoryloxylation of ketones with iodobenzene as cat-
Abstract: An effective catalytic method for a-phosphoryloxylation
of ketones is reported. When ketones were reacted with phosphates
in the presence of iodobenzene as the recyclable catalyst and m-
chloroperbenzoic acid as the terminal oxidant in acetonitrile at room
temperature, the a-phosphoryloxylation of ketones took place easi- alyst. Herein, we would like to report the novel and effec-
ly and the corresponding keto phosphates were obtained in moder-
ate to good yields.
tive catalytic a-phosphoryloxylation of ketones.
The selected model reaction was carried out with ace-
Key words: a-phosphoryloxylation, keto phosphate, hypervalent
tophenone, diphenyl phosphate, m-CPBA, and a catalytic
iodine reagent, catalytic oxidation
amount of iodobenzene in several organic solvents at
room temperature (Table 1). When acetophenone was re-
acted with equimolar amounts of diphenyl phosphate and
m-CPBA in the presence of 0.1 equivalent of iodobenzene
in acetonitrile at room temperature for 72 hours, the de-
Organic hypervalent iodine reagents have found broad ap-
plications in organic chemistry and are frequently used in
organic synthesis due to similar chemical properties and
reactivities to those of mercury(II), thallium(III), and
sired product a-phosphoryloxyacetophenone was isolated
in 60% of yield (Table 1, entry 1). It was found that when
lead(IV), but without the toxic and environmental prob-
more diphenyl phosphate was added to the reaction, the
lems of these heavy metal congeners.1 Among these
yield was increased and the reaction time was shorter; and
when 2 equivalents of diphenyl phosphate and m-CPBA
were used, the reaction gave a higher yield of 70% after
24 hours (entries 2, 3). According to our investigation, the
hypervalent iodine reagents, [hydroxy(tosyloxy)io-
do]benzene (Koser’s reagent) is the most popular and use-
ful reagent for the direct a-tosyloxylation of ketones, and
the prepared a-tosyloxyketones are important strategic
yield depended on the solvent used, and acetonitrile was
precursors for the construction of various heteroaromat-
the best choice; other solvents afforded only trace
ics.2 However, the analogue reaction for preparation of the
amounts of the product, except dichloromethane, which
gave a moderate yield (entries 3–8). Other oxidants such
as Oxone, NaBO3, and Na2S2O8 were not successful in the
reaction (entries 9–11). The reaction time was also
important keto phosphates by the direct a-phosphorylox-
ylation of ketones with stoichiometric hypervalent iodine
reagents has been rather limited.3
Recently, the catalytic utilization of hypervalent iodine re- checked, and 24 hours was quite suitable for the reaction
agents is increasing in importance, with the growing inter- (entries 3, 12–17). The amount of catalyst was influential
est in the development of environmentally benign and 0.1 equivalent was the best choice (entries 3, 18, and
synthetic transformations.4 In these catalytic reactions, a 19).
catalytic amount of an iodine-containing molecule togeth-
er with a stoichiometric oxidant are used. The oxidant
generates the hypervalent iodine reagent in situ, and after
the oxidative transformation, the reduced iodine-contain-
Under the optimum reaction conditions, a variety of ke-
tones 1 were tested to react with 2 equivalents of phos-
phates 2 and m-CPBA in the presence of 0.1 equivalent of
iodobenzene as catalyst in acetonitrile at room tempera-
ture for 24 hours. Thus, a series of keto phosphates 3 were
prepared (Scheme 1) and the results are summarized in
Table 2.
ing molecule is re-oxidized. Ochiai and co-workers re-
ported the a-acetoxylation of ketones with iodobenzene as
catalyst and m-chloroperbenzoic acid (m-CPBA) as oxi-
dant.5 Kita’s group demonstrated the catalytic spirocy-
clization of phenol and amide derivatives using
O
O
O
hypervalent iodine reagents as catalysts.6 The iodoben-
zene-catalyzed a-tosyloxylation of ketones with m-CPBA
in the presence of p-toluenesulfonic acid has also received
considerable attention more recently.7 However, to our
knowledge, the similar catalytic a-phosphoryloxylation of
MeCN
r.t.
R1CCH2R2 + PhI + (R3O)2PO2H + m-CPBA
R1CCH(R2)OP(OR3)2
1
2
3
Scheme 1
It is notable that the a-phosphoryloxylaction of ketones
was easily carried out at room temperature and the corre-
sponding keto phosphates were obtained in moderate to
good yields in 24 hours (Table 2, entries 1–7). Ketones
SYNTHESIS 2012, 44, 99–103
Advanced online publication: 30.11.2011
DOI: 10.1055/s-0031-1289630; Art ID: F83011SS
© Georg Thieme Verlag Stuttgart · New York
x
x.
x
x.
2
0
1
1

100
Y. Pu et al.
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Table 1 Optimization of the Iodobenzene-Catalyzed a-Phosphoryloxylation of Acetophenone
O
HOP(OPh)2
O
OP(OPh)2
O
O
m-CPBA
r.t.
PhI
+
+
Ph
Ph
Entry
PhI (equiv)
m-CPBA (equiv)
Diphenyl phosphate Solvent
Time (h)
Yield (%)a
(equiv)
1
2
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.05
0.02
1
1
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
MeCN
MeCN
MeCN
CH2Cl2
THF
72
24
24
24
24
24
24
24
24
24
24
4
60
1
62
3
2
70
4
2
41
5
2
2
6
2
MeOH
DMF
trace
trace
4
7
2
8
2
CF3CH2OH
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
9
Oxone (2)
trace
trace
5
10
11
12
13
14
15
16
17
18
19
NaBO3 (2)
Na2S2O8 (2)
2
2
2
2
2
2
2
2
32
8
47
12
16
48
72
24
24
55
61
74
77
54
40
a Isolated yield.
with electron-withdrawing substituent groups in phenyl only in 25% of yield (entry 10). Other phosphates 2b and
usually led to products in good yields (entries 4–7); while 2c were as effective as 2a in the reaction and provided the
ketones with electron-donating groups in phenyl gave corresponding keto phosphates in moderate yields (entries
lower yields compared with the above substrates (entries 11–13). Cyclic ketones such as cyclohexanone and cyclo-
8, 9). For the same reason, the electron-rich 2-acetyl- pentanone were also examined; however, the correspond-
thiophene afforded the corresponding keto phosphate ing keto phosphates were not obtained. Cyclohexanone
O
R2
O
R1
OH
+ H2O
R2
R2
O
I
R1
R1
OPO(OR3)2
OPO(OR3)2
Ph
R1
R2
OH
Ph
I
PhI
OPO(OR3)2
HOPO(OR3)2
m-CPBA
m-CBA
Scheme 2
Synthesis 2012, 44, 99–103
© Thieme Stuttgart · New York

PAPER
Catalytic a-Phosphoryloxylation of Ketones
101
Table 2 Keto Phosphates 3
Entry
1
Ketone 1
Phosphate 2
Keto phosphate 3
Yield (%)a
PhCOMe
1a
HOPO(OPh)2
2a
PhCOCH2OPO(OPh)2
3a
70
58
62
70
71
65
62
41
18b
MeCOMe
1b
MeCOCH2OPO(OPh)2
3b
2
3
4
5
6
7
8
9
2a
2a
2a
2a
2a
2a
2a
2a
EtCOEt
1c
EtCOCHMeOPO(OPh)2
3c
4-O2NC6H4COMe
1d
4-O2NC6H4COCH2OPO(OPh)2
3d
4-BrC6H4COMe
1e
4-BrC6H4COCH2OPO(OPh)2
3e
4-ClC6H4COMe
1f
4-ClC6H4COCH2OPO(OPh)2
3f
3-O2NC6H4COMe
1g
3-O2NC6H4COCH2OPO(OPh)2
3g
4-MeC6H4COMe
1h
4-MeC6H4COCH2OPO(OPh)2
3h
4-MeOC6H4COMe
1i
4-MeOC6H4COCH2OPO(OPh)2
3i
10
2a
OPO(OPh)2
S
25
S
O
O
1j
3j
HOPO(OBn)2
2b
PhCOCH2OPO(OBn)2
3k
11
12
13
1a
58
59
47
MeCOCH2OPO(OBn)2
3l
1b
2b
HOPO(OC6H4-4-NO2)2
2c
PhCOCH2OPO(OC6H4-4-NO2)2
3m
1a
O
O
14
2a
2a
OPO(OPh)2
trace
70c
1k
3n
O
O
O
15
1l
3o
a Isolated yields.
b Yield based on the crude residue. The product decomposed during purification.
c The product was the lactone and not the keto phosphate.
was not active in the reaction and the recovery of it was is generated into hypervalent iodine reagent by the oxida-
near quantitative after 24 hours (entry 14); while cyclo- tion of m-CPBA and used in the cycle.
pentanone gave only the six-membered lactone as product
in a yield of 70% (entry 15).
In summary, we have successfully developed an effective
catalytic a-phosphoryloxylation of ketones providing sev-
The proposed mechanism for the catalytic cycle of a- eral keto phosphates in moderate to good yields. This
phosphoryloxylation of ketones is shown in Scheme 2, method has some advantages such as mild reaction condi-
which includes the electrophilic addition of hypervalent tions and simplicity of the procedure. Furthermore, the
iodine reagent on the double bond, and then a reductive scope of hypervalent iodine reagents in organic synthesis
elimination resulting in the keto phosphates. Iodobenzene is extended.
© Thieme Stuttgart · New York
Synthesis 2012, 44, 99–103

102
Y. Pu et al.
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HRMS: m/z calcd for C20H16NO7P: 413.0664; found: 413.0632.
IR spectra were recorded on a Thermo-Nicolet 6700 instrument. 1H
NMR and 13C NMR spectra were measured on a Bruker Avance
(500M) spectrometer. Mass spectra were determined on Thermo-
ITQ 1100 mass spectrometer. Wakogel B-5F was selected for pre-
parative TLC. Iodobenzene, m-CPBA, ketones, and phosphates
were commercially available.
a-(Diphenylphosphoryloxy)-4-bromoacetophenone (3e)
Oil. Yield: 159 mg (71%).
IR (film): 1707, 1267 cm–1.
1H NMR (500 MHz, CDCl3): d = 7.75 (d, J = 7.0 Hz, 2 H), 7.62 (d,
J = 8.5 Hz, 2 H), 7.37 (t, J = 8.0 Hz, 4 H), 7.30–7.28 (m, 4 H), 7.23
(t, J = 7.5 Hz, 2 H), 5.40 (d, J = 10.0 Hz, 2 H).
a-Phosphoryloxylation of Ketones; a-(Diphenylphosphoryl-
oxy)acetophenone (3a);3a Typical Procedure
13C NMR (125 MHz, CDCl3): d = 190.55 (d, J = 6.3 Hz), 150.38 (d,
J = 7.5 Hz), 137.42, 132.28, 131.89, 129.83, 129.34, 125.60,
120.19 (d, J = 5.0 Hz), 69.77 (d, J = 5.0 Hz).
A mixture of acetophenone (1a; 60 mg, 0.5 mmol), iodobenzene (10
mg, 0.05 mmol), diphenyl phosphate (2a; 250 mg, 1.0 mmol), and
m-CPBA (75%, 230 mg, 1.0 mmol) in MeCN (2 mL) was stirred at
r.t. for 24 h, and then the solvent was evaporated under reduced
pressure. H2O (5 mL), sat. aq Na2S2O3 (1 mL), and sat. aq Na2CO3
(1 mL) were added. The mixture was extracted with CH2Cl2 (2 × 5
mL) and the combined organic layers were washed with brine (5
mL), dried (MgSO4), filtered, and concentrated under reduced pres-
sure. The residue was purified on a silica gel plate using (4:1 hex-
ane–EtOAc) as eluent to give 3a; yield: 129 mg (70%); oil.
MS (EI): m/z (%) = 447 (M+, 1.3), 353 (100).
HRMS: m/z calcd for C20H16BrO5P: 445.9919; found: 445.9882.
a-(Diphenylphosphoryloxy)-4-chloroacetophenone (3f)
Oil. Yield: 131 mg (65%).
IR (film): 1710, 1282 cm–1.
1H NMR (500 MHz, CDCl3): d = 7.84–7.82 (m, 2 H), 7.47–7.44 (m,
2 H), 7.38–7.35 (m, 4 H), 7.30–7.28 (m, 4 H), 7.24–7.21 (m, 2 H),
5.41 (d, J = 10.0 Hz, 2 H).
13C NMR (125 MHz, CDCl3): d = 190.29, 150.38 (d, J = 6.3 Hz),
140.63, 137.48, 132.09, 129.80, 129.29, 125.59, 120.19 (d, J = 5.0
Hz), 69.79 (d, J = 6.3 Hz).
IR (film): 1709, 1291 cm–1.
1H NMR (500 MHz, CDCl3): d = 7.89–7.87 (m, 2 H), 7.62–7.59 (m,
1 H), 7.49–7.46 (m, 2 H), 7.37–7.34 (m, 4 H), 7.30–7.26 (m, 4 H),
7.22–7.19 (m, 2 H), 5.46 (d, J = 10.0 Hz, 2 H).
13C NMR (125 MHz, CDCl3): d = 191.20 (d, J = 5.0 Hz), 150.40 (d,
J = 7.5 Hz), 134.04, 133.72, 129.78, 128.88, 127.78, 125.51,
120.18 (d, J = 5.0 Hz), 69.90 (d, J = 5.0 Hz).
MS (EI): m/z (%) = 403 (M+, 2.2), 309 (100).
MS (EI): m/z (%) = 369 (M + 1, 3.5), 275 (100).
HRMS: m/z calcd for C20H16ClO5P: 402.0424; found: 402.0411.
a-(Diphenylphosphoryloxy)acetone (3b)3a
a-(Diphenylphosphoryloxy)-3-nitroacetophenone (3g)
Oil. Yield: 89 mg (58%).
Oil. Yield: 128 mg (62%).
IR (film): 1739, 1290, 1194 cm–1.
1H NMR (500 MHz, CDCl3): d = 7.38–7.34 (m, 4 H), 7.28–7.26 (m,
2 H), 7.23–7.22 (m, 4 H), 4.72 (d, J = 9.5 Hz, 2 H), 2.16 (s, 3 H).
13C NMR (125 MHz, CDCl3): d = 201.39 (d, J = 6.3 Hz), 150.17 (d,
J = 6.3 Hz), 129.72, 125.50, 119.94 (d, J = 5.0 Hz), 71.54 (d,
J = 6.3 Hz), 25.78.
IR (film): 1717, 1534, 1353, 1255 cm–1.
1H NMR (500 MHz, CDCl3): d = 8.71 (s, 1 H), 8.47–8.43 (m, 1 H),
8.22 (d, J = 9.0 Hz, 1 H), 7.72–7.67 (m, 1 H), 7.39–7.35 (m, 4 H),
7.32–7.28 (m, 4 H), 7.25–7.21 (m, 2 H), 5.47 (d, J = 10.0 Hz, 2 H).
13C NMR (125 MHz, CDCl3): d = 189.90 (d, J = 6.3 Hz), 150.33 (d,
J = 7.5 Hz), 148.51, 133.50, 130.26 (d, J = 2.5 Hz), 129.86 (d,
J = 10.0 Hz), 128.22, 125.73, 123.27, 122.92, 120.17 (d, J = 5.0
Hz), 69.95 (d, J = 5.0 Hz).
MS (EI): m/z (%) = 307 (M + 1, 2.0), 250 (100).
a-(Diphenylphosphoryloxy)pentan-3-one (3c)
MS (EI): m/z (%) = 414 (M + 1, 2.3), 94 (100).
Oil. Yield: 104 mg (62%).
HRMS: m/z calcd for C20H16NO7P: 413.0664; found: 413.0611.
IR (film): 1721, 1196 cm–1.
1H NMR (500 MHz, CDCl3): d = 7.38–7.35 (m, 4 H), 7.28–7.21 (m,
6 H), 5.03–4.97 (m, 1 H), 2.59–2.48 (m, 2 H), 1.49 (d, J = 7.0 Hz, 3
H), 1.02 (t, J = 7.0 Hz, 3 H).
13C NMR (125 MHz, CDCl3): d = 214.0, 150.51 (d, J = 7.5 Hz),
129.75, 125.38, 120.20 (d, J = 5.0 Hz), 79.25, 30.94, 18.39, 7.05.
a-(Diphenylphosphoryloxy)-4-methylacetophenone (3h)
Oil. Yield: 78 mg (41%).
IR (film): 1700, 1288 cm–1.
1H NMR (500 MHz, CDCl3): d = 7.79 (d, J = 8.0 Hz, 2 H), 7.38–
7.35 (m, 4 H), 7.32–7.27 (m, 6 H), 7.23–7.18 (m, 2 H), 5.45 (d,
J = 10.0 Hz, 2 H).
MS (EI): m/z (%) = 335 (M + 1, 0.3), 170 (100).
13C NMR (125 MHz, CDCl3): d = 190.79, 150.49 (d, J = 7.5 Hz),
145.12, 131.31, 129.81, 129.61, 128.46, 125.52, 120.20 (d, J = 7.5
Hz), 69.88 (d, J = 6.3 Hz), 21.76.
HRMS: m/z calcd for C17H19O5P: 334.0970; found: 334.0944.
a-(Diphenylphosphoryloxy)-4-nitroacetophenone (3d)3d
Oil. Yield: 145 mg (70%).
IR (film): 1693, 1527, 1346, 1261 cm–1.
1H NMR (500 MHz, CDCl3): d = 8.31 (d, J = 9.0 Hz, 2 H), 8.04 (d,
J = 9.0 Hz, 2 H), 7.36 (d, J = 7.5 Hz, 4 H), 7.29–7.23 (m, 6 H), 5.45
(d, J = 10.5 Hz, 2 H).
MS (EI): m/z (%) = 383 (M + 1, 2.9), 289 (100).
HRMS: m/z calcd for C21H19O5P: 382.0970; found: 382.0953.
a-(Diphenylphosphoryloxy)-2-acetylthiophene (3j)3b
Oil. Yield: 47 mg (25%).
IR (film): 1688, 1291 cm–1.
13C NMR (125 MHz, CDCl3): d = 190.53 (d, J = 5.0 Hz), 150.78,
150.28 (d, J = 7.5 Hz), 138.19, 129.88, 129.10, 125.74, 124.05,
120.14 (d, J = 5.0 Hz), 70.02 (d, J = 5.0 Hz).
1H NMR (500 MHz, CDCl3): d = 7.74 (dd, J = 4.0, 1.0 Hz, 1 H),
7.70 (dd, J = 5.0, 1.5 Hz, 1 H), 7.41–7.35 (m, 4 H), 7.34–7.30 (m,
4 H), 7.25–7.21 (m, 2 H), 7.10 (dd, J = 6.0, 4.0 Hz, 1 H), 5.33 (d,
J = 9.5 Hz, 2 H).
MS (EI): m/z (%) = 413 (M+, 1.9), 94 (100).
Synthesis 2012, 44, 99–103
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Catalytic a-Phosphoryloxylation of Ketones
103
13C NMR (125 MHz, CDCl3): d = 184.1, 150.3 (q, J = 7.6 Hz),
139.8, 134.7, 132.3, 129.7, 128.3, 125.4, 120.2 (t, J = 5.0 Hz),
69.70 (d, J = 6.3 Hz).
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IR (film): 1708, 1279 cm–1.
1H NMR (500 MHz, CDCl3): d = 7.84 (d, J = 8.0 Hz, 2 H), 7.58–
7.52 (m, 1 H), 7.47 (d, J = 8.0 Hz, 2 H), 7.34–7.30 (m, 10 H), 5.22
(d, J = 10.0 Hz, 2 H), 5.18 (dd, J = 8.0, 6.0 Hz, 4 H).
13C NMR (125 MHz, CDCl3): d = 191.99 (d, J = 5.0 Hz), 135.67 (d,
J = 6.3 Hz), 133.89, 128.80, 128.51, 128.02, 127.68, 69.70 (d,
J = 5.0 Hz), 68.67 (d, J = 5.0 Hz).
MS (EI): m/z (%) = 397 (M+, 1.8), 199 (100).
HRMS: m/z calcd for C22H21O5P: 396.1127; found: 396.1121.
a-(Dibenzylphosphoryloxy)acetone (3l)3d
Oil. Yield: 99 mg (59%).
IR (film): 1740, 1280 cm–1.
1H NMR (500 MHz, CDCl3): d = 7.38–7.36 (m, 10 H), 5.12 (dd,
J = 18.0, 9.0 Hz, 4 H), 4.45 (d, J = 9.5 Hz, 2 H), 2.12 (s, 3 H).
13C NMR (125 MHz, CDCl3): d = 202.29 (d, J = 6.3 Hz), 135.51 (d,
J = 7.5 Hz), 134.44, 128.62 (d, J = 7.5 Hz), 128.03, 70.66 (d,
J = 6.3 Hz), 69.75 (d, J = 6.3 Hz), 25.85.
MS (EI): m/z (%) = 335 (M + 1, 6.0), 137 (100).
HRMS: m/z calcd for C17H19O5P: 334.0970; found: 334.0934.
a-[Bis(4-nitrophenyloxy)phosphoryloxy]acetophenone (3m)3d
Oil. Yield: 108 mg (47%).
IR (film): 1713, 1518, 1344, 1290 cm–1.
1H NMR (500 MHz, CDCl3): d = 8.30 (d, J = 9.0 Hz, 4 H), 7.87 (d,
J = 7.5 Hz, 2 H), 7.67–7.64 (m, 1 H), 7.53–7.49 (m, 6 H), 5.56 (d,
J = 12.5 Hz, 2 H).
13C NMR (125 MHz, CDCl3): d = 190.58 (d, J = 3.8 Hz), 154.63 (d,
J = 7.5 Hz), 145.39, 134.57, 133.32, 129.12, 127.72, 125.85,
120.96 (d, J = 6.3 Hz), 70.83 (d, J = 5.0 Hz).
MS (EI): m/z (%) = 458 (M+, 1.2), 105 (100).
HRMS: m/z calcd for C20H15N2O9P: 458.0515; found: 458.0488.
Acknowledgment
Financial supports from the Natural Science Foundation of China
(Project 21072176) and the Zhejiang Province Natural Science
Foundation of China (Project Y4100231) are greatly appreciated.
© Thieme Stuttgart · New York
Synthesis 2012, 44, 99–103