Rapid sulfonyloxylactonization of alkenoic acids under microwave and ultrasound irradiation

Article abstract of DOI:10.1080/15533174.2011.591326

Fast and convenient reactions were investigated under microwave and ultrasound irradiation, providing simple methods for sulfonyloxylactonization of alkenoic acids in good yields in a short time. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/15533174.2011.591326

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Rapid Sulfonyloxylactonization of Alkenoic Acids
Under Microwave and Ultrasound Irradiation
Liumian Gao a , Li Li b & Min Zhu b
a Research Institute of Nanjing Chemical Industrial Group, Nanjing, P. R. China
b College of Biological and Environmental Sciences, Zhejiang Shuren University,
Hangzhou, P. R. China
Version of record first published: 04 Oct 2011.
To cite this article: Liumian Gao , Li Li & Min Zhu (2011): Rapid Sulfonyloxylactonization of Alkenoic Acids Under
Microwave and Ultrasound Irradiation, Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry,
41:8, 953-957
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 41:953–957, 2011
Copyright ꢀ Taylor & Francis Group, LLC
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ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2011.591326
Rapid Sulfonyloxylactonization of Alkenoic Acids Under
Microwave and Ultrasound Irradiation
Liumian Gao,1 Li Li,2 and Min Zhu2
1Research Institute of Nanjing Chemical Industrial Group, Nanjing, P. R. China
2College of Biological and Environmental Sciences, Zhejiang Shuren University, Hangzhou, P. R. China
reagents having low solubility in most organic solvents, the de-
velopment of solvent-free reactions and other special reactions
is a big step forward and should lead to an increasing use of this
chemistry.
Fast and convenient reactions were investigated under mi-
crowave and ultrasound irradiation, providing simple methods for
sulfonyloxylactonization of alkenoic acids in good yields in a short
time.
Microwave-assisted organic syntheses have received great
attention because of their fast reaction rates, high purity of
products, and ease of manipulation.[19,20] In particular, the
microwave-irradiated procedures in water medium or in the
absence of solvents for organic synthesis have attracted con-
siderable interest in recent years due to their efficient and en-
vironmentally benign conditions.[21–23] Our recent interest has
been in the development of new synthetic methods using hy-
pervalent iodine reagents. As part of a program, our group
found that some hypervalent iodine reagents, such as Koser’s
reagent, can be transformed from (diacetoxyiodo)benzene by a
microwave-promoted solvent-free ligand exchange reaction.[24]
In order to extend the scope of microwave-promoted reaction,
we have checked the sulfonyloxylactonization of alkenoic acids
under microwave irradiation, and we also have investigated the
same reaction under ultrasound irradiation. We report here the
novel and rapid microwave- and ultrasound-promoted sulfony-
loxylactonization of alkenoic acids.
Keywords hypervalent iodine reagent, microwave irradiation,
sulfonyloxylactonization, ultrasound irradiation
INTRODUCTION
Lactonizations have been studied extensively, and this type
of transformation serves as an important key reaction in a
variety of syntheses.[1–3] Among them, halolactonization and
phenylselenolactonization are general used methods.[4–6] Re-
cently, organic hypervalent iodine reagents have found broad
application in organic chemistry and frequent use in synthe-
sis due to their chemical properties and reactivity being sim-
ilar to those of H (II), Tl(III), and Pb(IV), but without the
toxic and environmental problems of these heavy metal con-
geners.[7–15] Koser et al. (1986) first reported the tosyloxylac-
tonization of alkenoic acids with hypervalent iodine reagent,
[hydroxyl(tosyloxy)iodo]benzene (HTIB, Koser’s reagent), in
which the mechanism was different with those of halolac-
tonization and phenylselenolactonization.[16] The ability of
HTIB to introduce the tosylate ligand into alkenoic acids
prompted us to investigate the camphorsulfonyloxylactonization
of alkenoic acids, and a series of new 5-camphorsulfonyloxy-
4-pentanolactones and 6-camphorsulfonyloxy-5-hexanolactone
was synthesized with the analogous reagent, [hydroxyl (((+)-
10-camphorsulfonyl)oxy)iodo]benzene.[17] The catalytic sul-
fonyloxylactonization of alkenoic acids using hypervalent io-
dine catalyst was also just reported, which extended the scope
of sulfonyloxylactonization.[18] Due to many hypervalent iodine
EXPERIMENTAL
Melting points were determined on a digital melting-
point apparatus and were not corrected. Infrared (IR) spec-
tra were recorded on a Thermo-Nicolet 6700 instrument, nu-
clear magnetic resonance (NMR) spectra were measured on
a Bruker ANANCE III(500-MHz) spectrometer, and mass
spectra were determined on a Thermo-ITQ 1100 mass spec-
trometer. Microwave irradiation was carried out with an
LWMC-201 microwave reactor at full power (650 W) (Nan-
jing, China). Ultrasound irradiation was carried out with an
ultrasonic cleaning bath (50 kHz). Alkenoic acids, (diace-
toxyiodo)benzene, p-toluenesulfonic acid monohydrate, and
(+)-10-camphorsulfonic acid are commercially available.
Received 27 January 2011; accepted 18 February 2011.
Financial support from the Zhejiang Province Natural Science
Foundation of China (Project Y4100231) is greatly appreciated.
Address correspondence to Min Zhu, College of Biological and En-
vironmental Sciences, Zhejiang Shuren University, Hangzhou 310015,
P. R. China. E-mail: hzzm60@163.com
Typical Procedure for Sulfonyloxylactonization of
Alkenoic Acids Under Microwave Irradiation
4-Pentenoic acid 1a (50 mg, 0.5 mmol, 1.0 equiv), (di-
acetoxyiodo)benzene (161 mg, 0.5 mmol, 1.0 equiv), and
953

954
L. GAO ET AL.
3e: Oil (Lit.[17]). 1H-NMR (500 MHz, CDCl3): 4.82–4.79 (m,
1H), 4.51 (ddd, J = 22.0, 11.5, 3.0 Hz, 1H), 4.37 (ddd, J = 21.5,
11.0, 4.5 Hz, 1H), 3.62 (dd, J = 15.5, 6.0 Hz, 1H), 3.08 (dd,
J = 15.0, 4.0 Hz, 1H), 2.69–2.52 (m, 2H), 2.43–2.37 (m, 3H),
2.20–2.02 (m, 3H), 1.97 (d, J = 17.5 Hz, 1H), 1.75–1.65 (m,
1H), 1.51–1.45 (m, 1H), 1.10 (s, 3H), 0.88 (s, 3H). 13C-NMR
(125 MHz, CDCl3): 214.2, 176.1, 76.7 (d, J = 7.5 Hz), 70.1,
69.9, 57.8 (d, J = 2.5 Hz), 48.1, 47.2, 42.6 (d, J = 2.5 Hz), 42.4
(d, J = 1.3 Hz), 27.9, 26.8, 24.8 (d, J = 7.5 Hz), 23.3 (d, J =
8.8 Hz), 19.5 (t, J = 2.5 Hz). IR (film): ν = 2963, 1781, 1746,
1456, 1418, 1360, 1282, 1167, 1070, 962 cm−1. MS (EI, m/z,%):
331 (M+1+, 100). HRMS: C15H22O6S calcd.: 330.1137, found:
330.1125.
p-toluenesulfonic acid monohydrate 2a (114 mg, 0.6 mmol,
1.2 equiv) were mixed in a 10-mL glass tube. The mixture tube
was placed inside in an alumina bath and irradiated for 40 s in
a microwave reactor at full power (650 W). After cooling, the
solid residue was then separated on a silica gel plate using 3:1
hexane–ethyl acetate as eluant to give 115 mg of 5-tosyloxy-4-
pentanolactone 3a (85% yield).
Typical Procedure for Sulfonyloxylactonization of
Alkenoic Acids Under Ultrasound Irradiation
4-Pentenoic acid 1a (50 mg, 0.5 mmol, 1.0 equiv), (di-
acetoxyiodo)benzene (161 mg, 0.5 mmol, 1.0 equiv), p-
toluenesulfonic acid monohydrate 2a (95 mg, 0.5 mmol, 1.0
equiv), and 2 mL tetrahydrofuran (THF) were placed in a glass
flask and irradiated for 2 min in an ultrasonic cleaning bath (50
KHz). The mixture was then separated on a silica gel plate using
3:1 hexane–ethyl acetate as eluant to give 117 mg of 5-tosyloxy-
4-pentanolactone 3a (86% yield).
1
3f: Oil (Lit.[17]). H-NMR (500 MHz, CDCl3): 4.79–4.72
(3h1) and 4.68–4.62 (3h2) (m, 1H), 4.51 (ddd, J = 19.0, 11.5, 3.0
Hz, 1H), 4.37–4.31 (m, 1H), 3.66–3.59 (m, 1H), 3.09–3.03 (m,
1H), 2.83–2.78 (3h1) and 2.77–2.70 (3h2) (m, 1H), 2.56–2.49
(m, 1H), 2.46–2.37 (m, 2H), 2.16–2.13 (m, 1H), 2.10–2.03 (m,
1H), 1.97 (d, J = 18.0 Hz, 1H), 1.79–1.68 (m, 2H), 1.50–1.44
(m, 1H), 1.31 (d, J = 5.5 Hz, 3h1) and 1.30 (d, J = 6.0 Hz,
3h2) (d, 3H), 1.10 (3h1) and 1.09 (3h2) (s, 3H), 0.89 (3h1) and
0.88 (3h2) (s, 3H). 13C-NMR (125 MHz, CDCl3): 214.4, 214.3,
179.2, 178.3, 74.9, 74.5 (d, J = 7.5 Hz), 70.5, 70.4, 69.7, 69.4,
57.9 (d, J = 3.8 Hz), 48.2 (d, J = 3.8 Hz), 47.4, 47.3 (d, J =
6.3 Hz), 42.7, 42.5 (d, J = 2.5 Hz), 35.2, 33.7, 32.2 (d, J = 8.8
Hz), 31.6 (d, J = 6.3 Hz), 26.9, 24.9 (t, J = 3.8 Hz), 19.6 (d,
J = 5.0 Hz), 16.1, 15.1 (d, J = 3.8 Hz). IR (film): ν = 2966,
1775, 1747, 1456, 1360, 1286, 1168, 1069, 972, 931 cm−1. MS
(EI, m/z,%): 345 (M+1+, 48), 109 (100). HRMS: C16H24O6S
calcd.: 344.1294, found: 344.1289
3a: M.p. 79–81◦C (Lit.[16] 80.5–81.5◦C). 1H-NMR (500
MHz, CDCl3): 7.78 (d, J = 8.5 Hz, 2H), 7.37 (d, J = 8.5
Hz, 2H), 4.72–4.65 (m, 1H), 4.19 (dd, J = 11.0, 3.0 Hz, 1H),
4.13 (dd, J = 11.0, 4.0 Hz, 1H), 2.61–2.48 (m, 2H), 2.46 (s,
3H), 2.39–2.31 (m, 1H), 2.15–2.10 (m, 1H). 13C-NMR (125
MHz, CDCl3): 176.0, 145.4, 132.2, 130.0, 127.9, 76.4, 70.0,
27.8, 23.5, 21.6. MS (EI, m/z,%): 271 (M+1+, 100).
3b: M.p. 91–95◦C (Lit. [16] 92–95◦C). 1H-NMR (500 MHz,
CDCl3): 7.77 (d, J = 8.5 Hz, 2H), 7.37 (d, J = 8.0Hz, 2H),
4.68–4.62 (3b1) and 4.58–4.52 (3b2) (m, 1H), 4.21(dd, J =
11.0, 3.5 Hz, 0.73 H), 4.14–4.09 (m, 1.27 H), 2.77–2.66 (m,
1H), 2.51–2.47 (3b1) and 2.41–2.35 (3b2) (m, 1H), 2.46 (s,
3H), 2.06–2.00 (3b1) and 1.74–1.66 (3b2) (m, 1H), 1.27 (d, J =
7.0Hz, 3H). 13C-NMR (125 MHz, CDCl3): 178.2, 145.4 (d, J =
12.5 Hz), 132.3, 130.0 (d, J = 6.3 Hz), 127.9 (d, J = 6.3 Hz),
74.5, 74.1, 70.2, 69.4, 35.0, 33.6, 32.1, 31.7, 21.6, 16.0, 15.0.
MS (EI, m/z,%): 285 (M+1+, 100).
1
3g: Oil (Lit.[17]). H-NMR (500 MHz, CDCl3): 4.75–4.30
(m, 3H), 3.63 (dd, J = 15.0, 4.5 Hz, 1H), 3.07 (dd, J = 15.5, 4.0
Hz, 1H), 2.85–2.78 (m, 1H), 2.72–2.66 (3i1) and 2.56–2.49 (3i2)
(m, 1H), 2.45–2.22 (m, 3H), 2.15–2.13 (m, 1H), 2.11–2.02 (m,
1H), 1.97 (d, J = 18.5 Hz, 1H), 1.75–1.65 (m, 1H), 1.51–1.44
(m, 1H), 1.23 (dd, J = 6.5, 3.0 Hz, 3i1) and 1.17 (d, J = 7.5
Hz, 3i2) (3H), 1.10 (s, 3H), 0.88 (s, 3H). 13C-NMR (125 MHz,
CDCl3): 214.3, 175.7(d, J = 2.5 Hz), 175.4, 83.3 (d, J = 2.5
Hz), 79.2 (d, J = 5.0 Hz), 68.8, 68.6, 68.2, 68.0, 57.9 (d, J = 3.8
Hz), 48.2, 47.4 (d, J = 3.8 Hz), 47.2 (d, J = 2.5 Hz), 42.7 (d, J
= 3.8 Hz), 42.5 (d, J = 2.5 Hz), 36.4 (d, J = 3.8 Hz), 36.2, 31.9,
31.8, 31.7, 26.9, 24.9 (d, J = 2.5 Hz), 24.8, 19.6 (d, J = 3.8 Hz),
18.0, 13.5. IR (film): ν = 2965, 1785, 1747, 1456, 1418, 1361,
1283, 1214, 1166, 1054, 975, 933 cm−1. MS (EI, m/z,%): 345
(M+1+, 61), 109 (100). HRMS: C16H24O6S calcd.: 344.1294,
found: 344.1277.
1
3c: Oil (Lit.[25]). H-NMR (500 MHz, CDCl3): 7.79 (d,
J = 8.0 Hz, 2H), 7.37 (d, J = 8.0 Hz, 2H), 4.61–4.57 (3c1)
and 4.17–4.13 (3c2) (m, 1H), 4.22–4.17 (m, 2H), 2.81–2.71 (m,
1H), 2.61 (dd, J = 17.5, 8.5 Hz) (3c1) and 2.52–2.45 (m) (3c2)
(1H), 2.46 (s, 3H), 2.28 (dd, J = 17.5, 8.0 Hz) (3c1) and 2.18
(dd, J = 17.5, 8.0 Hz) (3c2) (1H), 1.17 (d, J = 6.5 Hz) (3c1) and
1.11 (d, J = 6.5 Hz) (3c2) (3H). 13C-NMR (125 MHz, CDCl3):
175.6, 175.2, 145.4 (d, J = 6.3 Hz), 132.1 (d, J = 23.8 Hz),
130.1 (d, J = 22.5 Hz), 127.9 (d, J = 2.5 Hz), 82.9, 78.8, 68.6,
67.7, 36.2 (d, J = 23.8 Hz), 31.8 (d, J = 25.0 Hz), 21.6, 17.0,
13.5. MS (EI, m/z,%): 285 (M+1+, 100).
1
3h: Oil (Lit.[17]). H-NMR (500 MHz, CDCl3): 4.73–4.69
3d: M.p. 77–79◦C (Lit. [16] 78–79◦C). 1H-NMR (500 MHz,
CDCl3): 7.81–7.78 (m, 2H), 7.38–7.35 (m, 2H), 4.52–4.48 (m,
1H), 4.15–4.09 (m, 2H), 2.60–2.55 (m, 1H), 2.47 (s, 3H),
2.46–2.43 (m, 1H), 2.00–1.94 (m, 1H), 1.88–1.82 (m, 1H),
1.72–1.65 (m, 1H). 13C-NMR (125 MHz, CDCl3): 170.1, 145.3,
132.3, 130.0, 128.0 (d, J = 6.3 Hz), 77.0, 70.1, 29.4, 24.0, 21.7,
18.1. MS (EI, m/z,%): 285 (M+1+, 100).
(m, 1H), 4.51 (ddd, J = 20.0, 11.5, 3.5 Hz, 1H), 4.33 (ddd,
J = 19.5, 11.5, 5.5 Hz, 1H), 3.63 (dd, J = 15.5, 8.0 Hz, 1H),
3.08 (d, J = 15.0 Hz, 1H), 2.45–2.37 (m, 2H), 2.20–2.13 (m,
2H), 2.10–2.01 (m, 1H), 1.99–1.95 (m, 2H), 1.75–1.67 (m, 1H),
1.51–1.45 (m, 1H), 1.32 (s, 3H), 1.30 (s, 3H), 1.10 (s, 3H), 0.89
(s, 3H). 13C-NMR (125 MHz, CDCl3): 214.3 (d, J = 8.8 Hz),
180.8, 73.6 (d, J = 3.8 Hz), 69.9, 69.6, 57.9, 48.2, 47.4 (d, J =

SULFONYLOXYLACTONIZATION OF ALKENOIC ACIDS
955
10.0 Hz), 42.7, 42.5 (d, J = 2.5 Hz), 40.0 (d, J = 2.5 Hz), 38.4
O
O
(d, J = 7.5 Hz), 26.9, 24.9 (d, J = 3.8 Hz), 24.8 (d, J = 3.8 Hz),
24.7 (d, J = 2.5 Hz), 19.6. IR (film): ν = 2967, 1775, 1747,
1457, 1361, 1280, 1207, 1169, 1130, 1067, 983, 926 cm−1. MS
(EI, m/z,%): 359 (M+1+, 25), 109 (100). HRMS: C17H26O6S
calcd.: 358.1451, found: 358.1441.
PhI(OAc)2
microwave
O
HOTs H2O
OH
OTs
2a
1a
3a
SCH. 1.
1
3i: Oil (Lit.[17]). H-NMR (500 MHz, CDCl3): 4.65–4.55
(m, 1H), 4.45–4.34 (m, 2H), 3.64 (dd, J = 15.0, 8.5 Hz, 1H),
3.09 (d, J = 15.0 Hz, 1H), 2.65–2.60 (m, 1H), 2.52–2.35 (m,
3H), 2.15–1.85 (m, 6H), 1.80–1.70 (m, 2H), 1.51–1.42 (m, 1H),
1.10 (s, 3H), 0.89 (s, 3H). 13C-NMR (125 MHz, CDCl3): 214.4,
170.1, 70.4, 70.2, 57.9, 48.2 (d, J = 2.5 Hz), 47.4 (d, J = 2.5
Hz), 42.7 (d, J = 3.8 Hz), 42.5, 29.5, 26.9, 24.9 (d, J = 11.3
Hz), 23.9 (d, J = 6.3 Hz), 19.6, 18.2. IR (KBr): ν = 2961,
1744, 1456, 1360, 1240, 1169, 1081, 1054, 963 cm−1. MS (EI,
m/z,%): 345 (M+1+, 34), 109 (100). HRMS: C16H24O6S calcd:
344.1294, found: 344.1288.
O
O
PhI(OAc)2
microwave
n
O
HSO3
R
OH
n
OSO2R
1
2
3
SCH. 2.
O
O
THF
n
O
HSO3
R
PhI(OAc)2
OH
n
ultrasound
OSO2R
1
2
3
RESULTS AND DISCUSSION
SCH. 3.
At the beginning, we mixed equal equivalents of 4-pentenoic
acid (1a), (diacetoxyiodo)benzene (DIB), and p-toluenesulfonic
acid monohydrate (HOTs.H2O) (2a) to examine the sulfony-
loxylactonization of 4-pentenoic acid. We found that when the
mixture was heated in a glass tube by a microwave irradiation
for only 20 s, the sulfonyloxylactonization was nearly com-
plete and the desired product of 5-tosyloxy-4-pentanolactone
(3a) was afforded in 78% of yield (Scheme 1). Then a series of
experiments was performed on the reaction of 4-pentenoic acid
with DIB and HOTs.H2O to determine the optimum reaction
conditions. It was found when one equivalent of 4-pentenoic
acid and DIB with 1.2 equivalents of HOTs.H2O was heated
in a microwave reactor for 40 s, the highest yield of 85% was
reached. Under the optimum reaction conditions, the sulfony-
loxylactonization of alkenoic acids (1) with p-toluenesulfonic
acid monohydrate (2a) or (+)-10-camphorsulfonic acid (2b)
was investigated (Scheme 2); the good results are summarized
in Table 1.
It is shown from Table 1 that all 4-pentenoic acids reacted
with DIB and 2a or 2b rapidly, and gave the corresponding 5-
sulfonyloxy-4-pentanolactones in good to excellent yields (en-
tries 1–3, 5–8). Among them, 3b, 3c, 3f, and 3g were found to be
the mixtures of diastereomers by 1H-nuclear magnetic resonance
(NMR) technique. Similar treatment of 5-hexenoic acid with 2a
or 2b provided 6-sulfonyloxy-5-hexanolactones (3d, 3i) in mid-
dle yields (entries 4, 9), which meant that the five-membered
lactone ring was formed more easily than the six-membered lac-
tone ring in the sulfonyloxylactonization. We also checked the
reactions of 3-butenoic acid and trans-3-hexenoic acid with 2a
in the same reaction conditions; the products were not the de-
sired sulfonyloxylactones, and two corresponding unsaturated
lactones were obtained.
of 4-pentenoic acid (1a), (diacetoxyiodo)benzene (DIB), and
p-toluenesulfonic acid monohydrate (HOTs.H2O) (2a) in THF
was irradiated under ultrasound only 2 min, an 86% yield of
5-tosyloxy-4-pentanolactone (3a) was afforded. After several
reactions, the optimal reaction conditions were determined: The
suitable equivalent ratio for 2a, DIB, and HOTs.H2O was 1:1:1,
THF was the most preferred solvent, and in only 2 min of ultra-
sound irradiation all reactions were complete. Under the optimal
reaction conditions, the sulfonyloxylactonization of alkenoic
acids was investigated (Scheme 3); the good results are summa-
rized in Table 2.
Table 2 shows that good to excellent yields of five-membered
sulfonyloxylactones were obtained for a series of 4-pentenoic
acids (entries 1–3, 5–8). The yields of six-membered 6-
sulfonyloxy-5-hexanolactones were increased to 77% and 73%
for 3d and 3i, respectively (entries 4, 9) compared with Table 1,
which meant that ultrasound irradiation favoured the synthesis
of sulfonyloxylactones.
OSO2R
O
H
O
O
O
O
PhI(OAc)2
OH
I
Ph
I
Ph
OAc
O
OAc
O
O
HSO3
R
O
–PhI
-AcOH
I
Ph
OSO2R
OSO2R
SCH. 4.
The sonochemical reaction was carried out in a thermostat-
ted (20◦C) ultrasonic cleaning bath of frequency 50 kHz in
‘The plausible mechanism is similar to the literature proce-
air. It was found that when the mixture of equal equivalents dure,[16] which included the electrophilic addition of hypervalent

956
L. GAO ET AL.
TABLE 1
The sulfonylactonization of alkenoic acids under microwave irradiation
Entry
Alkenoic acid (1)
Sulfonic acid (2)
Sulfonyloxylactone (3)a
Yield (%)b
O
O
OTs
CH2=CH(CH2)2CO2H
1
p-Tosylic acid monohydrate 2a
85
1a
3a
O
Me
O
Me
CH2=CHCH2CHCO2H
1b
OTs
2
2a
86
3b
O
O
Me
CH2=CHCHCH2CO2H
1c
OTs
Me
3
4
2a
2a
80
63
3c
O
O
OTs
CH2=CH(CH2)3CO2H
1d
3d
O
O
OCs
5
6
1a
1b
(+)-10-Camphorsulfonic acid
81
83
2b
3e
O
Me
O
OCs
2b
2b
3f
O
O
OCs
Me
7
1c
74
3g
O
Me
Me
Me
O
CH2=CHCH2CCO2H
OCs
Me
8
9
2b
2b
84
56
1e
3h
O
O
OCs
1d
3i
aTs, p-Me-C6H4SO2; Cs, (+)-10-camphorylsulfonyl.
bIsolated yield.

SULFONYLOXYLACTONIZATION OF ALKENOIC ACIDS
957
TABLE 2
REFERENCES
1. Dowle, M.D.; Davies, D.I. Chem. Soc. Rev. 1979, 171.
The sulfonylactonization of alkenoic acids under ultrasound
irradiation
2. Harding, K.E.; Tiner, T.H. In Comprehensive Organic Synthesis; B. M.
Trost, I. Fleming, Eds.; Pergamon Press: Oxford, 1991; Vol. 4, p. 363.
3. Rousseau, G.; Robin, S. Tetrahedron 1998, 54, 13681.
4. Bartlett, P.A.; Meyerson, J. J. Am. Chem. Soc. 1978, 100, 3950.
5. Haas, J.; Piguel, S.; Wirth, T. Organic Lett. 2002, 4, 297.
6. Nicolaou, K.C.; Seitz, S.P.; Sipio, W.J.; Blount, J.F. J. Am. Chem. Soc. 1979,
101, 3884.
Alkenoic
acid (1)
Sulfonic Sulfonyloxylactone Yield
acid (2)
Entry
(3)a
(%)b
1
2
3
4
5
6
7
8
9
1a
1b
1c
1d
1a
1b
1c
1e
1d
2a
2a
2a
2a
2b
2b
2b
2b
2b
3a
3b
3c
3d
3e
3f
3g
3h
3i
86
88
85
77
83
85
80
85
73
7. Varvoglis, A. Tetrahedron 1997, 53, 1179.
8. Stang, P.J.; Zhdankin, V.V. Chem. Rev. 1996, 96, 1123.
9. Zhdankin, V.V.; Stang, P.J. Chem. Rev. 2002, 102, 2523.
10. Wirth, T.; Hirt, U.H. Synthesis 1999, 1271.
11. Kirschning, A. Eur. J. Org. Chem. 1998, 11, 2267.
12. Ochiai, M. J. Organomet. Chem. 2000, 611, 494.
13. Okuyama, T. Acc. Chem. Res. 2002, 35, 12.
14. Zhdankin, V.V.; Stang, P.J. Tetrahedron 1998, 54, 10927.
15. Grushin, V.V. Chem. Soc. Rev. 2000, 29, 315.
16. Shah, M.; Taschner, M.J.; Koser, G.F.; Rach, N. L. Tetrahedron Lett. 1986,
27, 4557.
aTs, p-Me-C6H4SO2; Cs, (+)-10-camphorylsulfonyl.
bIsolated yield.
17. Zhu, M.; Sun, N.B.; Li, H.; Yan, J. J. Hetrocyclic Chem. 2010, 47, 436.
18. Yan, J.; Wang, H.; Yang, Z.P.; He, Y. Synlett 2009, 2669.
19. Lidstrom, P.; Tierney, J.; Wathey, B.; Westman, J. Tetrahedron 2001, 57,
9225.
iodine reagent DIB on the double bond, then an intramolecu-
lar nucleophilic displacement, followed by another nucleophilic 20. Perreux, L.; Loupy, A. Tetrahedron 2001, 57, 9199.
21. Deshayes, S.; Liagre, M.; Loupy, A. Tetrahedron 1999, 55, 10851.
22. Arvela, R.K.; Leadbeater, N.E. J. Org. Chem. 2005, 70, 1786.
23. Wang, J.X.; Liu, Z.; Hu, Y.; Wei, B.; Bai, L. J. Chem. Res. (S) 2000, 484.
24. Zhou, Z.S.; He, X.H. J. Chem. Res. (S) 2009, 30.
displacement to give the sulfonyloxylactone (Scheme 4).
In summary, rapid and convenient methods for sulfonyloxy-
lactonization of alkenoic acids are afforded by the microwave-
and ultrasound-promoted reactions. They are simple, fast, and
afford good yields for synthesis of sulfonyloxylactones.
25. Vigneron, J.P.; Me´ric, R.; Larcheveˆque, M.; Debal, A.; Lallemand, J.Y.;
Kunesch, G.; Zagatti, P.; Gallois, M. Tetrahedron 1984, 40, 3521.