An efficient catalytic sulfonyloxylactonization of alkenoic acids using hypervalent iodine(III) reagent

Article abstract of DOI:10.1055/s-0029-1217977

A novel and efficient catalytic method for sulfonyloxylactonization of alkenoic acids is reported. (Diacetoxyiodo)benzene could be used as a recyclable catalyst in combination with m-chloroperbenzoic acid as an oxidant in the presence of sulfonic acid to

Full text of DOI:10.1055/s-0029-1217977

LETTER
2669
An Efficient Catalytic Sulfonyloxylactonization of Alkenoic Acids Using
Hypervalent Iodine(III) Reagent
C
J
atalytic
S
i
ulfony
e
loxylactonization
Y
of Alkenoic Acid
a
s
n,* Hong Wang, Zhenping Yang, Yan He
College of Chemical Engineering and Materials Sciences, Zhejiang University of Technology, Hangzhou 310032, Zhejiang, P. R. of China
Fax +86(571)88320238; E-mail: jieyan87@zjut.edu.cn
Received 22 June 2009
In order to extend the scope of catalytic use of organo-
Abstract: A novel and efficient catalytic method for sulfonyloxy-
iodines(III) for organic synthesis, we have investigated a
series of cyclizations of alkenoic acids using catalytic
roperbenzoic acid as an oxidant in the presence of sulfonic acid to amounts of hypervalent iodine(III) reagents and MCPBA
effect the cyclization of various alkenoic acids in CH Cl at room as a stoichiometric chemical oxidant. Herein, we wish to
lactonization of alkenoic acids is reported. (Diacetoxyiodo)benzene
could be used as a recyclable catalyst in combination with m-chlo-
2
2
temperature, giving sulfonyloxylactones in good yields.
report the first example of the catalytic sulfonyloxylacton-
Key words: sulfonyloxylactonization, hypervalent iodine reagent, ization of alkenoic acids.
catalytic cyclization
Initially, we examined the tosyloxylactonization of 4-pen-
tenoic acid (1a) with 0.1 equivalents of (diacetoxy-
iodo)benzene (DIB) in the presence of the equal
equivalent of TsOH (2a) and MCPBA in CH Cl at room
Organic hypervalent iodine reagents have found broad ap-
plication in organic chemistry and frequently used in syn-
thesis due to their chemical properties and reactivity
similarities to those of Hg(II), Tl(III), and Pb(IV), but
without the toxic and environmental problems of these
2
2
temperature. The reaction proceeded smoothly and gave
Table 1 Optimization of the Tosyloxylactonization of 4-Pentenoic
Acid
1
heavy-metal congeners. They are usually used as mild
O
2
O
PhI(OAc)2
MCPBA
oxidants, and also as electrophilic reagents, with them
O
+
HO3S
various cyclizations of unsaturated systems have been
OH
CH2Cl2
r.t.
3
OTs
carried out. Koser and co-workers first reported the tosyl-
1
a
2a
3a
oxylactonization of alkenoic acids with the hypervalent
iodine reagent, [hydroxy(tosyloxy)iodo]benzene (HTIB,
Koser’s reagent), and the ability of HTIB to introduce the
tosylate ligand into alkenoic acids received much atten-
Entry DIB
MCPBA TsOH
Solvent
Time Yield
(h)
(equiv) (equiv) (equiv)a
(%)
45
53
69
72
75
82
84
84
63
51
62
50
54
81
0
b
3
b
1
2
3
4
5
6
7
8
9
0
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.05
0.02
0.1
0.1
0.1
0.1c
0
1
1
1
1
1
1
1
2
1
1
1
1
1
1
1
1
1
1
1
1
1
1
2
1
1
1
1
1
1
1
CH
2
Cl
2
2
2
2
2
2
2
2
2
2
1
tion. Recently, the catalytic utilization of hypervalent io-
dine reagents is increasing in importance, with growing
interest in the development of environmentally benign
CH Cl
2
2
4
CH
2
Cl
4
synthetic transformations. Kita and co-workers used cat-
alytic amounts of hypervalent iodine(III) reagents and
meta-chloroperbenzoic acid (MCPBA) as an oxidant in
the spirocyclization of phenol and amide derivatives.5
Ochiai and co-workers reported the a-acetoxylation of ke-
tones with the combination of a catalytic amount of an
CH Cl
8
2
CH Cl
16
24
92
24
24
24
24
24
24
24
24
2
CH Cl
2
6
CH Cl
aryl iodide and MCPBA as the oxidant. In these catalytic
2
reactions, a catalytic amount of an iodine-containing mol-
ecule together with a stoichiometric oxidant were used.
The oxidant generated the hypervalent iodine reagent in
situ, and after the oxidative transformation, the reduced
iodine-containing molecule was re-oxidized. PhI-cata-
CH Cl
2
CH
Cl
2
1
CH Cl
2
lyzed a-tosyloxylation of ketones with MCPBA and p- 11
MeCN
MeCN
THF
tosylic acid (TsOH) has also received considerable atten-
1
2
7
tion. However, the catalytic sulfonyloxylactonization of
alkenoic acids has not been reported before.
13
1
1
4
5
CH Cl
2
2
CH Cl
2
2
SYNLETT 2009, No. 16, pp 2669–2672
Advanced online publication: 10.09.2009
DOI: 10.1055/s-0029-1217977; Art ID: W09509ST
x
x
.x
x
.2
0
0
9
a
b
c
Ts, 4-MeC H SO .
Isolate yields.
PhI was used instead of DIB.
6
4
2
©
Georg Thieme Verlag Stuttgart · New York

2
670
J. Yan et al.
LETTER
the desired product of 5-tosyloxy-4-pentanolactone (3a) 10). Similar treatment of 5-hexenoic acid provided 6-sul-
in 45% yield in 1 hour (Table 1, entry 1). Then, the reac- fonyloxy-5-hexanolactones in moderate yields (entries 4
tion conditions were optimized. As the reaction time was and 11). When 3-butenoic acid and trans-3-hexenoic ac-
prolonged, the yield of 3a was increased (entries 1–7) and ids were treated with 2a under the same reaction condi-
2
4 hours was the best suitable reaction time. The amount tions, only the unsaturated lactones were given (entries 5
of catalyst DIB was influential (entries 9 and 10), and 0.1 and 6), but not the desired sulfonylactons. It was revealed
equivalent was the best choice. As a suitable solvent, by H NMR spectroscopy that the desired 3-sulfonyloxy-
1
CH Cl was the most preferred (entries 6, 11–13). When 4-butanolactones were first formed, but then further trans-
2
2
PhI was used instead of DIB, nearly the same result was formed into the unsaturated lactones during workup pro-
obtained (entry 14). In the absence of DIB, the sulfony- cedure.
loxylactonization was not observed (entry 15). Other co-
®
oxidants such as sodium perborate and Oxone [c1] were
also not successful.
O
O
PhI(OAc)2
MCPBA
O
OH + HO3S R
n
n
Under the optimized reaction conditions, we investigated
the catalytic sulfonylactonization of equal equivalent al-
kenoic acids 1, TsOH 2a or (+)-10-camphorsulfonic acid
CH2Cl2
r.t.
1
2
OSO2R
3
Scheme 1 Hypervalent iodine(III) catalyzed sulfonylactonization
(
2b) and MCPBA with 0.1 equivalents DIB (Scheme 1), of alkenoic acids
8
and the results are summarized in Table 2. It was found
that good yields of 5-sulfonyloxy-4-pentanolactones were
obtained for a series of 4-pentenoic acids (entries 1–3, 7–
Table 2 Hypervalent Iodine(III) Catalyzed Sulfonylactonization of Alkenoic Acids
Entry
Alkenoic acid 1
Sulfonic acid 2
Sulfonyloxylactone 3a
Yield (%)b
O
H C=CH(CH ) CO H
TsOH
2a
2
2 2
2
1
O
82
1
a
OTs
3
3
3
a
O
OH
2
3
2a
2a
O
83
83
O
O
OTs
1
b
c
b
O
OH
O
1
OTs
c
O
H C=CH(CH ) CO H
2
2 3
2
4
5
6
2a
2a
2a
O
52
45
30
1
d
OTS
3
3
d
O
H C=CHCH CO H
2
2
2
1
e
O
e
O
O
O
OH
1
f
3
f
Synlett 2009, No. 16, 2669–2672 © Thieme Stuttgart · New York

LETTER
Catalytic Sulfonyloxylactonization of Alkenoic Acids
2671
Table 2 Hypervalent Iodine(III) Catalyzed Sulfonylactonization of Alkenoic Acids (continued)
Entry
7
Alkenoic acid 1
Sulfonic acid 2
Sulfonyloxylactone 3a
Yield (%)b
O
(
+)-10-camphorsulfonic acid
1a
O
83
2
b
OCs
3
3
3
g
h
i
O
O
8
9
1b
1c
2b
2b
76
75
OCs
O
O
O
OCs
OH
O
1
1
0
1
2b
2b
87
57
O
OCs
1
g
3
3
j
O
1d
O
OCs
k
a
Ts, 4-MeC H SO ; Cs, (+)-10-camphorylsulfonyl.
Isolated yield.
6
4
2
b
In 1988, Koser and co-workers reported another lacton-
izaton using the hypervalent iodine reagent,
–OSO2R
HSO3
O
H
{hydroxy[(bis(phenyloxy)phosphoryl)oxy]iodo}benzene,
O
and they found when 2-methyl-4-pentenoic acid (1b) was
treated with the hypervalent iodine reagent, the products
were a mixture of diastereomers, with a ratio varied from
O
O
O
R
OH
I+
Ph
3
c
OH
2
OSO R
1
.2 to 1.4:1. In our reaction protocol, we also found
when 1b was used the corresponding 5-sulfonyloxy-4-
pentanolactones were obtained as a mixture of diastereo-
mers, with a ratio varied from 2.7:1 for p-tosylic acid to
OH
I
Ph
PhI
OSO2R
2
.4:1 for camphorsulfonic acid, respectively, as deter-
1
mined by examination of the H NMR spectra of sulfony-
lactones. When 3-methyl-4-pentenoic acid (1c) was
reacted under the same conditions, the ratios of the mix-
ture of diastereomers were 1.7:1 and 2.0:1 for p-tosylic
acid and camphorsulfonic acid, respectively, which were
somewhat lower as compared to compound 1b.
RSO2OH
MCBA
MCPBA
Scheme 2 The possible catalytic cycle for the hypervalent io-
dine(III) catalyzed sulfonylactonization of alkenoic acids
A proposed mechanism for the catalytic cycle of sulfony-
In conclusion, we have successfully developed an effi-
cient catalytic sulfonyloxylactonization of alkenoic acids
using hypervalent iodine catalyst DIB and MCPBA in
presence of sulfonic acids. This new protocol has some
advantages such as mild reaction conditions, simple pro-
cedure, and good product yields. Furthermore, the scope
of catalytic use of hypervalent iodine reagents in organic
synthesis could be extended. Further investigation of the
cyclizations of alkenoic acids using catalytic amounts of
3
b
lactonization is depicted in Scheme 2, which included
an electrophilic addition of hypervalent iodine reagent to
the double bond, and then an intramolecular nucleophilic
cyclization happened, followed by another nucleophilic
sulfonyloxylation. The reduced byproduct of PhI was then
regenerated into hypervalent iodine reagent by the oxida-
tion of MCPBA and used in the next reaction cycle.
Synlett 2009, No. 16, 2669–2672 © Thieme Stuttgart · New York

2
672
J. Yan et al.
LETTER
hypervalent iodine(III) reagents and MCPBA as a stoi-
chiometric chemical oxidant will be reported in due
course.
(4) (a) Dohi, T.; Kita, Y. Kagaku 2006, 61, 68. (b) Richardson,
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Supporting Information for this article is available online at
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(
5) (a) Dohi, T.; Maruyama, A.; Yoshimura, M.; Morimoto, K.;
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ation of China (Project Y4080068) are greatly appreciated.
(
(
b) Yamamoto, Y.; Kawano, Y.; Toyb, P. H.; Togo, H.
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Synlett 2009, No. 16, 2669–2672 © Thieme Stuttgart · New York