A convenient phosphoryloxylactonization of pentenoic acids with (diacetoxyiodo)benzene

Article abstract of DOI:10.1016/j.cclet.2010.04.011

The convenient one-pot method for phosphoryloxylactonization of alkenoic acids was reported: when (diacetoxyiodo)benzene, various 4-pentenoic acids and phosphates were mixed in CH₃CN at room temperature, phosphoryloxylactones were obtained in g

Full text of DOI:10.1016/j.cclet.2010.04.011

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Chinese Chemical Letters 21 (2010) 1041–1044
www.elsevier.com/locate/cclet
A convenient phosphoryloxylactonization of pentenoic
acids with (diacetoxyiodo)benzene
b
Zhong Shi Zhou a, , Xue Han He
*
a College of Biological and Environmental Sciences, Zhejiang Shuren University, Hangzhou 310015, China
b Zhejiang Institute of Geology and Mineral Resource Laboratory, Hangzhou 310007, China
Received 29 December 2009
Abstract
The convenient one-pot method for phosphoryloxylactonization of alkenoic acids was reported: when (diacetoxyiodo)benzene,
various 4-pentenoic acids and phosphates were mixed in CH3CN at room temperature, phosphoryloxylactones were obtained in
good to excellent yields in short times, some had two diastereoisomers.
# 2010 Zhong Shi Zhou. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
Keywords: Phosphoryloxylactonization; (Diacetoxyiodo)benzene; Alkenoic acid; Synthesis
Hypervalent iodine reagents have found broad application in organic chemistry and nowadays frequently used in
synthesis due to they are nonmetallic oxidation reagents and avoid the issues of toxicity of many transition metals
commonly involved in such processes [1–10]. Using hypervalent iodine reagents some special phosphate esters which
are important in organic chemistry as well as biochemistry have been prepared: Stang and his workers reported the first
alkynyl phosphates synthesis in 1987 [11]; Koser et al. also prepared a novel hypervalent iodine reagent,
[hydroxy((bis(phenyloxy)phosphoryl)oxy)iodo]benzene, and found that it can react with 4-pentenoic acids and three
phosphoryloxylactones were obtained [12]. However, the yields of Koser’s reaction were middle or poor and the
reaction needed several hours; moreover, the number of phosphoryloxylactones was only three till now. In order to
improve the yield, short the reaction time and find a convenient method to prepare more and important
phosphoryloxylactones, we have investigated the reaction of alkenoic acids, (diacetoxyiodo)benzene and phosphates.
Here we would like to report a fast and convenient one-pot method for phosphoryloxylactonization of alkenoic acids, a
series of new 5-phosphoryloxy-4-pentanol-actones were synthesized.
We first investigated the ‘‘one-pot’’ procedure to improve Koser’s method due to the preparation of
[Hydroxyl((bis(phenyloxy)phosphoryl)oxy)iodo]benzene and its reaction with 4-pentenoic acids were separated in
two steps. When equal equivalent of (diacetoxyiodo)benzene, diphenyl phosphate and 4-pentenoic acid were mixed in
CH3CN at room temperature and stirred, we found that only after 1 h the reaction was completed, giving the desired 5-
(bis(phenyloxy)phosphoryl)oxy-4-pentanolactone in 85% of yield (Scheme 1). Prompted by the result, a series of
experiments were performed on the reaction of 4-pentenoic acid with (diacetoxyiodo)benzene and diphenyl phosphate
* Corresponding author.
E-mail address: zhoushan@hz.zj.cn (Z.S. Zhou).
1001-8417/$ – see front matter # 2010 Zhong Shi Zhou. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
doi:10.1016/j.cclet.2010.04.011

1[(Schme_1)TD$FIG] 042
Z.S. Zhou, X.H. He / Chinese Chemical Letters 21 (2010) 1041–1044
Scheme 1. .
[(Schme_2)TD$FIG]
Scheme 2. .
to determine the suitable reaction conditions, and CH3CN was found to be the most preferred solvent. When
CF3CH2OH was used in place of CH3CN, the reaction gave product in 60% of yield. Other solvents, such as CH2Cl2,
CH3OH and DMF were not effective, the reaction occurred slowly and afforded the product with poor yields.
Under the optimum reaction conditions, the reaction of a series of alkenoic acids (1) with phosphates (2) and
(diacetoxyiodo)benzene in CH3CN at room temperature were investigated, several 5-phosphoryloxy-4-pentanol-
actones (3) were provided, most of them were new compounds (Scheme 2), which were characterized by 1H NMR, 13
C
NMR, IR, MS spectra and melting points, the good results are summarized in Table 1.
It is shown from Table 1 that 4-pentenoic acids easily reacted with phosphates and (diacetoxyiodo)benzene, a
serious of 5-phosphoryloxy-4-pentanolactones with good yields were obtained in 1–2 h. Similar treatment of 5-
hexenoic acid, the desired product of 6-phosphoryloxy-5-hexanolactone was found from the crude product in middle
1
yield by H NMR technique, but it decomposed during purification, which agreed with Koser’s report that it was
unstable [12]. We also checked 3-butenoic acid, trans-3-hexenoic acid and 2-cyclopentene-acetic acid under the
optimum reaction conditions, unfortunately, only the corresponding unsaturated lactones were obtained.
Koser found when 2-methyl-4-pentenoic acid 1b was treated with the hypervalent iodine reagent, a mixture of
diastereomers was obtained, the ratio varied from 1.2 to 1.4:1 [12]. In our reaction protocol, we also found when 1b
was used, the corresponding products were mixture of diastereomers, the ratio was 2.9:1, which was determined by
examination of the 1H NMR spectra of phosphoryloxylactones; while 3-methyl-4-pentenoic acid 1c was treated in the
reaction, the ratio for the obtained mixture of diastereomers was nearly1:1, which meant that 1b had better
stereoselectivity than 1c.
The proposed mechanism for the one-pot phosphorylactonization of alkenoic acids is similar to the literature
procedure (Scheme 3) [13], which included the electrophilic addition of (diacetoxyiodo)benzene on the double bond,
[(Schme_3)TD$FIG]
Scheme 3. .

Z.S. Zhou, X.H. He / Chinese Chemical Letters 21 (2010) 1041–1044
1043
Table 1
The result of the phosphoryloxylactonization of alkenoic acids.
Entry
1
Alkenoic acids (1)
Phosphates (2)
Phosphoryloxylactones (3)
Time (h)
1
Yield (%)a
85
[TD$LINE]
[DT$LINE]
[DT$LINE]
2
2a
1
87
[TD$LINE]
[DT$LINE]
3
4
2a
2a
2
1
80
84
[TD$LINE]
[DT$LINE]
[TD$LINE]
[DT$LINE]
5
6
1a
1d
2
2
85
85
[DT$LINE]
[DT$LINE]
2b
[DT$LINE]
7
8
a
1a
1d
2
2
75b
[DT$LINE]
[DT$LINE]
2c
73b
[DT$LINE]
Isolated yield.
Determined by the 1H NMR.
b
then an intramolecular nucleophilic displacement was happened, followed by another nucleophilic displacement to
give the phosphorylactone.
A typical procedure for the phosphoryloxylactonization of alkenoic acids:4-pentenoic acid 1a (0.3 mmol),
(diacetoxyiodo)benzene (0.3 mmol) and diphenyl phosphate 2a (0.3 mmol) were added in CH3CN (2 mL). The
mixture was stirred at room temperature for 1 h and then separated on a silica gel plate using (3:2 hexane-ethyl acetate)
1
as eluant to give 5-(bis(phenyloxy)phosphoryl)oxy-4-pentanolactone 3a in 85% of yield. Mp 77–78 8C; H NMR
(500 MHz, CDCl3): d 7.37-7.34 (m, 4H), 7.23–7.20 (m, 6H), 4.72–4.70 (m, 1H), 4.47–4.43 (m, 1H), 4.32–4.27 (m,
1H), 2.49–2.45 (m, 2H), 2.33–2.26 (m, 1H), 2.10–2.03 (m, 1H); 13C NMR (125 MHz, CDCl3): d 176.2, 150.3 (dd,
J = 6.3, 2.5 Hz), 129.9, 125.6, 120.0 (d, J = 5.0 Hz), 77.3, 69.2 (d, J = 5.0 Hz), 27.9, 23.2; IR (film): n = 1771, 1593,

1044
Z.S. Zhou, X.H. He / Chinese Chemical Letters 21 (2010) 1041–1044
1489, 1293, 1221, 1189, 1044, 947 cmÀ1; MS (EI, m/z, %): 348 (M+, 62.3), 255 (100); HRMS: C17H17O6P, calcd.
348.0763, found 348.0755.
In summary, we have successfully developed a convenient one-pot phosphoryloxylactonization of pentenoic acids
with (diacetoxyiodo)benzene and phosphates, several 5-phosphoryloxy-4-pentanolactones were prepared in good
yields. This method has some advantages such as mild reaction conditions, 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 (No. Y4080068) is greatly
appreciated.
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