A convenient phosphoryloxylactonization of pentenoic acids with catalytic hypervalent iodine(III) reagent

Article abstract of DOI:10.1016/j.tetlet.2010.02.153

A novel and convenient catalytic method for phosphoryloxylactonization of pentenoic acids is available: the cyclization of 4-pentenoic acids with phosphates using iodobenzene as a recyclable catalyst in combination with m-chloroperbenzoic acid as the terminal oxidant was easily carried out in CF₃CH₂OH at room temperature, giving phosphoryloxylactons in good yields, some of them had two diastereoisomers.

Full text of DOI:10.1016/j.tetlet.2010.02.153

Tetrahedron Letters 51 (2010) 2480–2482
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A convenient phosphoryloxylactonization of pentenoic acids with catalytic
hypervalent iodine(III) reagent
b
Zhong-Shi Zhou a, , Xue-Han He
*
a College of Biological and Environmental Sciences, Zhejiang Shuren University, Hangzhou 310015, PR China
b Zhejiang Institute of Geology and Mineral Resource Laboratory, Hangzhou 310007, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
A novel and convenient catalytic method for phosphoryloxylactonization of pentenoic acids is available:
the cyclization of 4-pentenoic acids with phosphates using iodobenzene as a recyclable catalyst in com-
bination with m-chloroperbenzoic acid as the terminal oxidant was easily carried out in CF3CH2OH at
room temperature, giving phosphoryloxylactons in good yields, some of them had two diastereoisomers.
Ó 2010 Elsevier Ltd. All rights reserved.
Received 19 January 2010
Revised 21 February 2010
Accepted 26 February 2010
Available online 3 March 2010
Organic hypervalent iodine reagents have been receiving much
attention due to their low toxicity, mild reactivity, ready availabil-
ity, high stability, easy handing, etc. and have found broad applica-
tion in organic chemistry as alternatives replacing the highly toxic
Hg(II), Tl(III), and Pb(IV) heavy-metal oxidants.1 They are usually
used as stoichiometric oxidants in synthesis and after the reac-
tions, the at least equimolar amounts of iodoarenes are produced
as by-products, most of them are disposed of and are not well uti-
lized, which restricts their more applications. In 2005, Ochiai’s
group and Kita’s group independently reported the improvement
of using catalytic hypervalent iodine reagents in synthesis,2 which
was economical, environmentally friendly, and has led to recent
new applications of catalytic hypervalent iodine reagents in organ-
ic chemistry.3 In these catalytic reactions, a catalytic amount of
iodoarene together with a stoichiometric oxidant is used. The oxi-
dant generates the hypervalent iodine reagent in situ, and after the
oxidative transformation, the reduced iodoarene is re-oxidized.
Iodobenzene (PhI) is the most utilized iodoarene, m-chloroperben-
zoic acid (mCPBA) and OxoneÒ are usually used as the terminal
oxidants.
catalytic phosphoryloxylactonization of alkenoic acids, a series of
new 5-phosphoryloxy-4-pentanolactones were synthesized.
We first examined the reaction of equal equivalent of 4-pente-
noic acid, diphenyl phosphate, and mCPBA with 0.1 equiv of iodo-
benzene in CF3CH2OH at room temperature, and found that the
Table 1
Optimization of the hypervalent iodine(III)-catalyzed phosphoryloxylactonization of
4-pentenoic acid
O
O
O
mCPBA
O
PhI
O
HOP (OPh)2
OH
RT
O
P(OPh)2
2a
1a
3a
Entry PhI
mCPBA
Diphenyl
Solvent
Time Yielda
(equiv) (equiv)
phosphate
(equiv)
(h)
(%)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
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
1
1
1
1
1
1
1
1
1
1
1
2
1
1
1
1
1
1
1
1
1
1
1
1
1
2
1
1
1
CF3CH2OH 24
65
40
31
10
18
6
32
48
65
64
64
63
54
0
CH2Cl2
CH3CN
THF
CH3OH
DMF
CF3CH2OH
CF3CH2OH
CF3CH2OH
24
24
24
24
24
2
Koser and co-workers first reported the phosphoryloxylacton-
ization of alkenoic acids with the hypervalent iodine reagent,
[hydroxyl((bis(phenyloxy)phosphoryl)oxy)iodo]benzene,
and
some phosphoryloxylactones were obtained in the preparation.4
However, after the report there is no other Letter about the phos-
phoryloxylactonization been published and the numbers of phos-
phoryloxylactones are only a few. In order to extend the scope of
catalytic use of hypervalent iodine reagents in organic synthesis,
and to find a convenient method to prepare more and important
phosphoryloxylactones, we have investigated the phosphoryloxyl-
actonization of pentenoic acids with catalytic hypervalent iodi-
ne(III) reagent. Here we would like to report the convenient and
4
8
CF3CH2OH 16
CF3CH2OH 48
CF3CH2OH 24
CF3CH2OH
8
CF3CH2OH 24
CF3CH2OH 24
0.1
OxoneÒ
(1)
5
16
17
0.1
0.1
NaBO3
(1)
Na2S2O8
(1)
1
1
CF3CH2OH 24
CF3CH2OH 24
3
6
* Corresponding author. Tel.: +86 571 88297172; fax: +86 571 88297099.
E-mail address: zhoushan@hz.zj.cn (Z.-S. Zhou).
a
Isolated yields.
0040-4039/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetlet.2010.02.153

Z.-S. Zhou, X.-H. He / Tetrahedron Letters 51 (2010) 2480–2482
R1
2481
Under the optimum reaction conditions, we investigated the
catalytic phosphoryloxylactonization of equal equivalent of alke-
noic acids (1), phosphate (2), and mCPBA with 0.1 equiv of PhI in
CF3CH2OH at room temperature in 8 h (Scheme 1), the results are
summarized in Table 2.
R3
O
O
O
PhI, mCPBA
R2
R1
R2
HOP(OR4)2
OH
O
CF3CH OH
RT2
O
R3
1
2
OP(OR4)2
3
It is notable that the good yields of 5-phosphoryloxy-4-pent-
anolactones (3) were obtained for a series of 4-pentenoic acids
(1) (entries 1–7). When dibenzyl phosphate (2b) was used, the
yields of the corresponding 5-phosphoryloxy-4-pentanolactones
were higher than that of diphenyl phosphate (2a). It was found
that bis(4-nitrophenyl)phosphate (2c) also reacted with 4-pente-
noic acid, but the product (3h) was unstable and decomposed dur-
ing purification (entry 8). Similar treatment of 3-butenoic acid and
2-cyclopentene-1-acetic acid with 2a did not provide the desired
phosphoryloxylactones, only the unsaturated lactone 2(5H)-fura-
none from 3-butenoic acid and tetrahydro-cyclopenta[b]furan-2-
one from 2-cyclopentene-1-acetic acid was obtained in moderate
yields. In order to prepare six-membered phosphoryloxylactone,
we also checked the reaction of 5-hexenoic acid with 2a and found
that the desired product was first formed, but decomposed during
Scheme 1.
reaction was carried out easily and the desired product of 5-
(bis(phenyloxy)phosphory)oxy-4-pentanolactone was obtained
(3a) in 65% yield in 24 h. Then, the reaction conditions were opti-
mized, and the results are summarized in Table 1. As a suitable sol-
vent, CF3CH2OH was the most preferred (entries 1–6). The reaction
time was influential, the yield of 3a was increased from 2 to 8 h
and 8 h was the best suitable reaction time (entries 1, 7–11). When
2 equiv of diphenyl phosphate and mCPBA was used, the yield of 3a
was not changed (entries 1 and 12). The amount of catalyst of PhI
was influential (entries 9, 13 and 14), and 0.1 equiv was the best
choice. Other oxidants such as OxoneÒ, NaBO3, and Na2S2O8 were
also not successful (entries 15–17).
Table 2
The result of the phosphoryloxylactonization of alkenoic acids
Entry
Alkenoic acids (1)
Phosphates (2)
O
Phosphoryloxylactones (3)
Yielda (%)
O
HOP(OPh)2
CH2@CH(CH2)2CO2H
1a
O
O
1
65
2a
OP(OPh)2
3a
Me
Me
O
CH2=CHCH2CHCO2H
2
3
4
5
6
2a
63
64
66
70
71
O
O
1b
OP(OPh)2
3b
Me
O
CH2=CHCHCH2CO2H
Me
Me
O
2a
2a
O
1c
OP(OPh)2
3c
Me
Me
O
CH2=CHCH2CCO2H
Me
O
O
OP(OPh)2
1d
3d
O
O
O
HOP(OBn)2
1a
O
2b
OP(OBn)2
3e
Me
O
1b
2b
O
O
OP(OBn)
23f
Me
O
Me
7
8
1d
1a
2b
73
O
O
OP(OBn)
23g
O
O
O
HOP(OC6H4NO2-p)2
58b
O
2c
OP(OC6H4NO2-p)
23h
a
Isolated yields.
b
1H NMR analysis.

2482
Z.-S. Zhou, X.-H. He / Tetrahedron Letters 51 (2010) 2480–2482
ganic layer was washed with brine, dried over anhydrous MgSO4,
filtered, and concentrated under reduced pressure. The residue
was purified on a silica gel plate using (3:2 hexane–ethyl acetate)
as an eluant to give 5-(bis(phenyloxy)phosphory)oxy-4-pentano-
lactone (3a) in 65% of yield.
In summary, we have successfully developed a convenient cat-
alytic phosphoryloxylactonization of pentenoic acids, several 5-
phosphoryloxy-4-pentanolactones in good yields were prepared.
This method has some advantages such as mild reaction condi-
tions, simple procedure, and good yields. Furthermore, the scope
of hypervalent iodine reagents in organic synthesis could be
extended.
Acknowledgment
Financial support from the Zhejiang Province Natural Science
Foundation of China (Project Y4080068) is greatly appreciated.
Scheme 2.
References and notes
workup procedure by 1H NMR technique, which agreed with Koser’
report that the six-membered phosphoryloxylacton was unstable.4
Phosphoryloxylactones 3b, 3c, and 3f were mixtures of diastereo-
mers; the ratios were 3.0:1 for 3b, 1.1:1 for 3c, and 2.7:1 for 3f,
respectively, which were determined by examination of the 1H
NMR spectra of phosphoryloxylactons.
The proposed mechanism for the catalytic cycle of phosphoryl-
oxylactonization is shown in Scheme 2,5 which included the elec-
trophilic addition of hypervalent iodine reagent on the double
bond, and then an intramolecular nucleophilic cyclization hap-
pened, followed by another nucleophilic substitution. PhI was gen-
erated into hypervalent iodine reagent by the oxidation of mCPBA
and was used in the cycle.
A typical procedure for the catalytic phosphoryloxylactoniza-
tion of alkenoic acids: alkenoic acid 1a (0.3 mmol), diphenyl phos-
phate 2a (0.3 mmol), mCPBA (75%, 0.3 mmol), and iodobenzene
(0.03 mmol) were added in CF3CH2OH (2 mL). The mixture was
stirred at room temperature for 8 h and then water (5 mL), satd
aq Na2S2O3 (2 mL), and satd aq Na2CO3 (2 mL) were added. The
mixture was extracted with CH2Cl2 (2 Â 5 mL), the combined or-
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