A novel camphorsulfonyloxylactonization of alkenoic acids

Article abstract of DOI:10.1002/jhet.337

(Chemical Equation Presented) The novel reaction of [hydroxyl (((+)-10-camphorsulfonyl)oxy)iodo]benzene (1) with alkenoic acids was reported. When 1 reacted with various 4-pentenoic acids in CH₃CN, camphorsulfonylactons were obtained in excellent yields in short times, some had two diastereoisomers, whereas 1 reacted with 5-hexenoic acid, giving middle yield of camphorsulfonylacton; however, 3-butenoic and trans-3-hexenoic acids reacted with 1 slowly in CH₂Cl₂, only unsaturated lactones were provided.

Full text of DOI:10.1002/jhet.337

436
A Novel Camphorsulfonyloxylactonization of Alkenoic Acids
Min Zhu,a* Na-Bo Sun,a He Li,a and Jie Yanb
Vol 47
aCollege of Biological and Environmental Sciences, Zhejiang Shuren University, Hangzhou,
Zhejiang 310015, People’s Republic of China
bCollege of Chemical Engineering and Materials Sciences, Zhejiang University of Technology,
Hangzhou, Zhejiang 310032, People’s Republic of China
*E-mail: hzzm60@163.com
Received September 3, 2009
DOI 10.1002/jhet.337
Published online 4 March 2010 in Wiley InterScience (www.interscience.wiley.com).
The novel reaction of [hydroxyl (((þ)-10-camphorsulfonyl)oxy)iodo]benzene (1) with alkenoic acids
was reported. When 1 reacted with various 4-pentenoic acids in CH3CN, camphorsulfonylactons were
obtained in excellent yields in short times, some had two diastereoisomers, whereas 1 reacted with 5-
hexenoic acid, giving middle yield of camphorsulfonylacton; however, 3-butenoic and trans-3-hexenoic
acids reacted with 1 slowly in CH2Cl2, only unsaturated lactones were provided.
J. Heterocyclic Chem., 47, 436 (2010).
INTRODUCTION
pentenoic acid with 1, we found that when the equal
equivalent of both them were mixed and stirred in
CH3CN at room temperature, the reaction was carried
out fluently and finished in 0.5 h, the novel compound
of 5-camphorsulfonyloxy-4-pentanolactone was obtained
in nearly quantitative (Scheme 1). Prompted by the
good result, a series of experiments were performed on
the reaction of 4-pentenoic acid with 1 in order to deter-
mine the suitable reaction conditions, and CH3CN and
CH2Cl2 were found to be the most preferred solvents.
Finally, the reaction of a series of alkenoic acids (2)
with 1 in CH3CN or CH2Cl2 at room temperature were
investigated, several new camphorsulfonylactons (3)
were provided (Scheme 2), the good results are summar-
ized in Table 1.
Lactonizations have been studied extensively, and this
type of transformation serves as an important key reac-
tion in a variety of syntheses [1]. Among them, halolac-
tonization and phenylselenolactonization are general
used methods [2]. Recently, organic hypervalent iodine
reagents have found broad application in organic chem-
istry and frequently used in synthesis due to their chemi-
cal properties and reactivity are similar to those of Hg
(II), Tl (III), and Pb (IV), but without the toxic and
environmental problems of these heavy metal congeners
[3]. Koser and coworkers first reported the tosyloxylac-
tonization of alkenoic acids with the hypervalent iodine
reagent, [hydroxyl(tosyloxy)iodo]benzene (HTIB, Kos-
er’s reagent), which mechanism was different with halo-
lactonization and phenylselenolactonization and received
much attention [4]. The ability of HTIB to introduce the
tosylate ligand into alkenoic acids prompted us to inves-
tigate the camphorsulfonyloxylactonization of alkenoic
acids with the analogous reagent, [hydroxyl (((þ)-10-
camphorsulfonyl)oxy)iodo]benzene (1) [5], a stable and
incorporating a chiral ligand hypervalent iodine reagent.
Here, we would like to report a novel and convenient
camphorsulfonyloxylactonization of alkenoic acids, a
series of new 5-camphorsulfonyloxy-4-pentanolactones
It is shown from Table 1 that 4-pentenoic acid (2a),
2-methyl-4-pentenoic acid (2b), 3-methyl-4-pentenoic
acid (2c) and 2, 2-dimethyl-4-pentenoic acid (2d) all
reacted with 1 fast, and gave the corresponding 5-cam-
phorsulfonyloxy-4-pentanolactones,
respectively,
in
excellent yields (entries 1–4); Similar treatment of 5-
hexenoic acid needed longer time compared with 4-pen-
tenoic acid and provided 6-camphorsulfonyloxy-5-hexa-
nolactone (3e) in middle yield (entry 5), which meant
that five-membered lactone ring was formed easier than
six-membered lactone ring in the camphorsulfonyloxy-
lactonization of alkenoic acids. We also checked the
reaction of 6-heptenoic acid with 1, found that after 48
h it had not been completed and the desired seven-mem-
bered lactone ring was obtained in poor yield. When 3-
butenoic and trans-3-hexenoic acids were treated with 1
and
synthesized.
6-camphorsulfonyloxy-5-hexanolactone
were
Initially, we prepared [hydroxyl (((þ)-10-camphorsul-
fonyl)oxy)iodo]benzene (1) according to the literature
procedure [5]. Then, we investigated the reaction of 4-
C
V
2010 HeteroCorporation

March 2010
A Novel Camphorsulfonyloxylactonization of Alkenoic Acids
437
Scheme 1
in same reaction conditions, the reaction was somewhat
difficult to carry out in CH3CN and slowly; then using
CH2Cl2 in place of CH3CN, we found that after 24 h
the reaction was finished. However, the products were
not the desired camphorsulfonylactons, two unsaturated
lactones were found (entries 6 and 7). It was revealed
fonylactonization at room temperature. Solvents also
had small effect on the stereoselectivity, we found that
CH3CN was better than CH2Cl2 to get high diastereom-
ers ratio for 2b in the reaction.
[Hydroxyl
(((þ)-10-camphorsulfonyl)oxy)iodo]ben-
zene was made from (diacetoxyiodo)benzene and (þ)-
10-camphorsulfonic acid in CH3CN. To extend the
scope of camphorsulfonylactonization, find simpler and
more convenient camphorsulfonylactonization, the ‘‘one-
pot’’ reaction was investigated; when equal equivalent
of (diacetoxyiodo)benzene, (þ)-10-camphorsulfonic acid
and 4-pentenoic acid were mixed in CH3CN at room
temperature and stirred the mixture, we found that the
reaction was completed in 0.5 h, giving the desired 3a
in 95% of yield. When [bis(trifluoroacetoxy)iodo]ben-
zene was used in place of (diacetoxyiodo)benzene, the
same result was obtained in 94% of yield. Therefore,
the simpler and more convenient ‘‘one-pot’’ camphorsul-
fonylactonization was found (Scheme 3). Further inves-
tigation of the reaction will be reported later.
1
by H-NMR technique that the desired 3-sulfonyloxy-4-
butanolactones were first formed, but then transformed
into the unsaturated lactones during workup procedure
by elimination. 2-Cyclopenteneacetic acid reacted with
1 also fluently, but gave another unsaturated lactone
(entry 8), which agreed with Koser and coworkers report
[4].
Koser et al. in 1988 reported another lactonizaton
using the similar hypervalent iodine reagent, [hydroxyl
((bis(phenyloxy)phosphoryl)oxy)iodo]benzene, and they
found that when 2-methyl-4-pentenoic acid was treated
with the hypervalent iodine reagent, the products were a
mixture of diastereomers, with a ratio varied from 1.2 to
1.4:1 [6]. Because of [hydroxyl (((þ)-10-camphorsulfo-
nyl)oxy)-iodo]benzene is a chiral hypervalent iodine rea-
gent, the lactonizaton of it may be stereoselectivity, and
The plausible mechanism is similar to the literature
procedure [4], which included the electrophilic addition
of hypervalent iodine reagent 1 on the alkene, then an
intramolecular nucleophilic displacement was happened,
followed by another nucleophilic displacement to give
the camphorsulfonylactone (Scheme 4).
1
some evidence was obtained by examination of the H-
NMR spectrum of camphorsulfonylactons: when 2-
methyl-4-pentenoic acid (2b) and 3-methyl-4-pentenoic
acid (2c) were treated with 1 at room temperature, the
provided products were mixtures of diastereomers, the
ratios of them were 3.1:1 and 2.3:1, respectively. Then,
we checked the effect of temperature on the stereoselec-
tivity of 2b and found that the camphorsulfonylactoniza-
tion got diastereomers with higher ratio at lower of tem-
perature; The reaction was investigated at room temper-
ature, ꢀ20ꢁC and ꢀ50ꢁC, respectively, the ratios of dia-
stereomers varied from 3.1, 4.0 to 4.8:1. However,
except 2b and 2c, other alkenoic acids were not
observed having the stereoselectivity in the camphorsul-
In conclusion, we have successfully developed a
novel and convenient reaction of [hydroxyl-(((þ)-10-
camphorsulfonyl)oxy)iodo]benzene with alkenoic acids,
several new 5-camphorsulfonyloxy-4-pentanolactones in
excellent yields and 6-camphorsulfonyloxy-5-hexanolac-
tone in middle yield were prepared. The camphorsulfo-
nylactonization has some advantages, such as, mild reac-
tion conditions, simple procedure, and good yields. Fur-
thermore, the scope of hypervalent iodine reagents in
organic synthesis could be extended.
Scheme 2
Journal of Heterocyclic Chemistry
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M. Zhu, N.-B. Sun, H. Li, and J. Yan
Vol 47
Table 1
The result of the camphorsulfonylactonization of alkenoic acids.
Entry
Alkenoic acids (2)
Camphorsulfonyloxylactones (3)a
Time (h)
0.5
Yield (%)b
1
2
3
98
95
93
0.5
0.5
4
1.0
95
5
6
7
2.5
63
52c
41c
24
24
8
1.0
81
a Cs, (þ)-10-camphorylsulfonyl.
b Isolated yield.
c CH2Cl2 was used as solvent.
Journal of Heterocyclic Chemistry
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A Novel Camphorsulfonyloxylactonization of Alkenoic Acids
439
Scheme 3
EXPERIMENTAL
972, 931 cmꢀ1. MS (EI, m/z, %): 344 (Mþ, 100). HRMS:
C16H24O6S calcd.: 344.1294, found: 344.1289.
3c: Oil. 1H-NMR (500 MHz, CDCl3): 4.75–4.30 (m, 3H),
3.63 (dd, J ¼ 15.0, 4.5 Hz, 1H), 3.07 (dd, J ¼ 15.5, 4.0 Hz,
1H), 2.85–2.78 (m, 1H), 2.72–2.66 (3c1) and 2.56–2.49 (3c2)
(m, 1H), 2.45–2.22 (m, 3H), 2.15–2.13 (m, 1H), 2.11–2.02 (m,
1H), 1.97 (d, J ¼ 18.5 Hz, 1H), 1.75–1.65 (m, 1H), 1.51–1.44
(m, 1H), 1.23 (dd, J ¼ 6.5, 3.0 Hz, 3c1) and 1.17 (d, J ¼ 7.5
Hz, 3c2) (3H), 1.10 (s, 3H), 0.88 (s, 3H). 13C-NMR (125
MHz, CDCl3): 214.3, 175.7(d, J ¼ 2.5 Hz), 175.4, 83.3 (d, J
¼ 2.5 Hz), 79.2 (d, J ¼ 5.0 Hz), 68.8, 68.6, 68.2, 68.0, 57.9
(d, J ¼ 3.8 Hz), 48.2, 47.4 (d, J ¼ 3.8 Hz), 47.2 (d, J ¼ 2.5
Hz), 42.7 (d, J ¼ 3.8 Hz), 42.5 (d, J ¼ 2.5 Hz), 36.4 (d, J ¼
3.8 Hz), 36.2, 31.9, 31.8, 31.7, 26.9, 24.9 (d, J ¼ 2.5 Hz),
24.8, 19.6 (d, J ¼ 3.8 Hz), 18.0, 13.5. IR (film): m ¼ 2965,
1785, 1747, 1456, 1418, 1361, 1283, 1214, 1166, 1054, 975,
General procedure for the iodination of terminal
alkynes. To CH3CN or CH2Cl2 (2 mL), alkenoic acid 2 (0.3
mmol), [hydroxyl (((þ)-10-camphorsulfonyl)oxy)iodo]benzene
1 (0.3 mmol) were added. The mixture was stirred at room
temperature for 0.5–24 h (shown in Table 1) and then sepa-
rated on a silica gel plate using (3:1, hexane–ethyl acetate) as
eluant to give camphorsulfonyloxylacton 3 in good to excellent
yields.
3a: Oil. 1H-NMR (500 MHz, CDCl3): 4.82–4.79 (m, 1H),
4.51 (ddd, J ¼ 22.0, 11.5, 3.0 Hz, 1H), 4.37 (ddd, J ¼ 21.5,
11.0, 4.5 Hz, 1H), 3.62 (dd, J ¼ 15.5, 6.0 Hz, 1H), 3.08 (dd, J
¼ 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 ¼ 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 ¼ 7.5 Hz), 70.1,
69.9, 57.8 (d, J ¼ 2.5 Hz), 48.1, 47.2, 42.6 (d, J ¼ 2.5 Hz),
42.4 (d, J ¼ 1.3 Hz), 27.9, 26.8, 24.8 (d, J ¼ 7.5 Hz), 23.3 (d,
J ¼ 8.8 Hz), 19.5 (t, J ¼ 2.5 Hz). IR (film): m ¼ 2963, 1781,
1746, 1456, 1418, 1360, 1282, 1167, 1070, 962 cmꢀ1. MS (EI,
m/z, %): 330 (Mþ, 100). HRMS: C15H22O6S calcd.: 330.1137,
found: 330.1125.
3b: Oil. 1H-NMR (500 MHz, CDCl3): 4.79–4.72 (3b1) and
4.68–4.62 (3b2) (m, 1H), 4.51 (ddd, J ¼ 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 (3b1) and 2.77–2.70 (3b2) (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 ¼ 18.0 Hz, 1H), 1.79–1.68 (m, 2H), 1.50–1.44
(m, 1H), 1.31 (d, J ¼ 5.5 Hz, 3b1) and 1.30 (d, J ¼ 6.0 Hz,
3b2) (d, 3H), 1.10 (3b1) and 1.09 (3b2) (s, 3H), 0.89 (3b1) and
0.88 (3b2) (s, 3H). 13C-NMR (125 MHz, CDCl3): 214.4,
214.3, 179.2, 178.3, 74.9, 74.5 (d, J ¼ 7.5 Hz), 70.5, 70.4,
69.7, 69.4, 57.9 (d, J ¼ 3.8 Hz), 48.2 (d, J ¼ 3.8 Hz), 47.4,
47.3 (d, J ¼ 6.3 Hz), 42.7, 42.5 (d, J ¼ 2.5 Hz), 35.2, 33.7,
32.2 (d, J ¼ 8.8 Hz), 31.6 (d, J ¼ 6.3 Hz), 26.9, 24.9 (t, J ¼
3.8 Hz), 19.6 (d, J ¼ 5.0 Hz), 16.1, 15.1 (d, J ¼ 3.8 Hz). IR
(film): m ¼ 2966, 1775, 1747, 1456, 1360, 1286, 1168, 1069,
.
933 cmꢀ1 MS (EI, m/z, %): 344 (Mþ, 100). HRMS:
C16H24O6S calcd.: 344.1294, found: 344.1277.
3d: Oil. 1H-NMR (500 MHz, CDCl3): 4.73–4.69 (m, 1H),
4.51 (ddd, J ¼ 20.0, 11.5, 3.5 Hz, 1H), 4.33 (ddd, J ¼ 19.5,
11.5, 5.5 Hz, 1H), 3.63 (dd, J ¼ 15.5, 8.0 Hz, 1H), 3.08 (d, J
¼ 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 ¼ 8.8 Hz),
180.8, 73.6 (d, J ¼ 3.8 Hz), 69.9, 69.6, 57.9, 48.2, 47.4 (d, J
¼ 10.0 Hz), 42.7, 42.5 (d, J ¼ 2.5 Hz), 40.0 (d, J ¼ 2.5 Hz),
38.4 (d, J ¼ 7.5 Hz), 26.9, 24.9 (d, J ¼ 3.8 Hz), 24.8 (d, J ¼
3.8 Hz), 24.7 (d, J ¼ 2.5 Hz), 19.6. IR (film): m ¼ 2967, 1775,
1747, 1457, 1361, 1280, 1207, 1169, 1130, 1067, 983, 926
cmꢀ1. MS (EI, m/z, %): 358 (Mþ, 100). HRMS: C17H26O6S
calcd.: 358.1451, found: 358.1441.
3e: Oil. 1H-NMR (500 MHz, CDCl3): 4.65–4.55 (m, 1H),
4.45–4.34 (m, 2H), 3.64 (dd, J ¼ 15.0, 8.5 Hz, 1H), 3.09 (d, J ¼
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 ¼ 2.5 Hz), 47.4 (d, J ¼ 2.5 Hz), 42.7 (d, J
¼ 3.8 Hz), 42.5, 29.5, 26.9, 24.9 (d, J ¼ 11.3 Hz), 23.9 (d, J ¼
6.3 Hz), 19.6, 18.2. IR (KBr): m ¼ 2961, 1744, 1456, 1360,
1240, 1169, 1081, 1054, 963 cmꢀ1. MS (EI, m/z, %): 344 (Mþ,
100). HRMS: C16H24O6S calcd: 344.1294, found: 344.1288.
Scheme 4
Acknowledgments. Financial support from the Natural Science
Foundation of China (Project 20672100) is greatly appreciated.
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