Oxidative acetoxylactonisation of alkenoic acids using H2O2 in acetic acid catalysed by KI

Article abstract of DOI:10.3184/174751915X14399788140213

In the presence of a catalytic amount of KI in combination with H₂O₂, a convenient catalytic procedure has been developed for the direct preparation of acetoxylactones from alkenoic acids in acetic acid at room temperature which provides the corresponding cyclic products in good yields. This novel methodology mediated by an in situ generated hypervalent iodine intermediate extends the catalytic application of KI in organic synthesis.

Full text of DOI:10.3184/174751915X14399788140213

518 RESEARCH PAPER
VOL. 39 SEPTEMBER, 518–520
JOURNAL OF CHEMICAL RESEARCH 2015
Oxidative acetoxylactonisation of alkenoic acids using H O in acetic acid
2
2
catalysed by KI
Zhong-Shi Zhou * and Xue-Han He
a
b
a
College of Biological and Environmental Sciences, Zhejiang Shuren University, Hangzhou 310015, P. R. China
Zhejiang Institute of Geology and Mineral Resource Laboratory, Hangzhou 310007, P. R. China
b
In the presence of a catalytic amount of KI in combination with H O , a convenient catalytic procedure has been developed for the direct
2
2
preparation of acetoxylactones from alkenoic acids in acetic acid at room temperature which provides the corresponding cyclic products
in good yields. This novel methodology mediated by an in situ generated hypervalent iodine intermediate extends the catalytic application
of KI in organic synthesis.
Keywords: 3-alkenoic acids, 4-alkenoic acids, acetoxylactonisation, hypervalent iodine intermediate, potassium iodide/hydrogen peroxide
Hypervalent iodine reagents have found broad application
in organic chemistry and nowadays are frequently used in
synthesis as they are non-metallic oxidising agents. Their use
avoids the issues of toxicity that arise by the many transition
0.2 equiv. However, if KI was absent, no desired product was
observed. Under the optimal conditions, the reaction proceeded
smoothly and was complete in only 4 h.
Using these optimal reaction conditions, we investigated the
catalytic acetoxylactonisation of alkenoic acids 1 (1.0 equiv.)
with H O (2.0 equiv.) and of KI (0.1 equiv.) in AcOH at
1-4
metals commonly involved in such processes. In recent
years, the utilisation of catalytic hypervalent iodine reagents
has been increasing in importance, with growing interest
in the development of environmentally benign synthetic
2
2
room temperature for 4 h (Scheme 1). The yields obtained are
summarised in Table 1.
5
-7
transformations. In these reactions, a catalytic amount of
an iodine-containing molecule together with a stoichiometric
amounts of an oxidant are used. More recently, Togo and co-
workers have investigated a new method for the α-tosyloxylation
of ketones using molecular iodine as catalyst, which was
4-Alkenoic acids were easily cyclised in AcOH catalysed
by KI, and a series of the corresponding acetoxyl-g-lactones
were obtained in good yields (entries 1–5). Owing to the
influence of the methyl substituent, 2-methyl-4-pentenoic acid
1b and 3-methyl-4-pentenoic acid 1c resulted in mixtures of
diastereoisomers 2b and 2c (entries 2 and 3). The ratios of trans
to cis for 2b and 2c were near 1:1 as determined by examination
8
shown to occur through a hypervalent iodine intermediate.
This method avoids the need for expensive aryl iodides and
gives good yields. It is well known that molecular iodine can
be easily formed from iodides, but development of a one-pot
reaction mediated by hypervalent iodine species generated in
situ from iodides, especially inorganic iodides which are more
1
of their H NMR spectra. Similar treatment of 3-butenoic acid
1f and trans-3-hexenoic acid 1g, gave g-butyrolactones 2f and
2g in moderate yields 51 and 62%, respectively (entries 6 and 7),
not the analogous four-membered products, which meant that
five-membered lactones were preferred over four-membered
products in the acetoxylactonisation of β,g-unsaturated acids.
When 5-hexenoic acid 1h was used as a substrate, the d-lactone
product 2h was obtained in somewhat low yield (entry 8);
however, 6-heptenoic acid 1i was not transformed into the
corresponding seven-membered lactone 2i (entry 9). Therefore,
our new method is best suited for the preparation of five-
membered acetoxylactones.
9
-11
environmentally benign, has been quite limited.
In order to extend the scope of the catalytic use of
hypervalent iodine reagents for organic synthesis, we have
developed a new method for phosphoryloxylactonisation of
alkenoic acids using ammonium iodide as catalyst, and several
12
phosphoryloxylactones have been prepared. Based on this
success, we now report a convenient acetoxylactonisation
of alkenoic acid catalysed by KI which, to the best of our
knowledge, has not been reported previously.
To explore the efficiency and generality of our method,
4
-pentenol 1j, as a representative of an unsaturated alcohol
Results and discussion
was investigated under the same reaction conditions. We found
that it was also easily cyclised, furnishing the five-membered
acetoxyether 2j in excellent yield (entry 10).
First, we examined the cyclisation of 4-pentenoic acid
in the presence of 0.1 equiv. of NH I and 1.2 equiv. of
4
All the products, which were oils and known compounds,
m-chloroperbenzoic acid (mCPBA) in acetic acid at room
temperature. It was found that this reaction proceeded
easily and provided the desired product 5-acetoxymethyl-2-
tetrahydrofuranone in 53% yield after 12 h. Encouraged by this
result, the reaction conditions were optimised. The reaction was
evaluated in several solvents with 5 equiv. of AcOH, giving
the desired product in yields ranging from 19-46%, but in
neat AcOH the yield was higher. Compared with mCPBA, the
oxidant H O was even better and gave the product in 67% yield;
1
13
were characterised by their IR, H NMR, C NMR and MS
spectra.
R3
O
O
OAc
KI, H O2
O
2
OH
AcOH, r.t. 4h
R2
R1
R1
R2 R3
2
2
@
other oxidants, such as Oxone , NaBO and Na S O resulted in
lower yields. The amount of H O was checked and 2.0 equiv. of
3
2
2
8
1
2
2
2
it was optimal. Under the same conditions, several iodides were
tested; KI was the best catalyst, and the optimal amount was
Scheme 1
*
Correspondent. E-mail: jieyan871@163.com

JOURNAL OF CHEMICAL RESEARCH 2015 519
Table 1 Yields of the products 2 of KI-catalysed acetoxylactonisation of alkenoic acids 1 by H O in acetic acid (Scheme 1)
2
2
a
a
Entry
Alkenoic acids (1)
Acetoxylactones (2)
Yield /%
Entry
Alkenoic acids (1)
Acetoxylactones (2)
Yield /%
51
O
O
O
O
OH
1f
O
OAc
O
1
OH
89
6
OAc
1
a
2a
2f
O
O
O
OAc
O
O
O
2
3
4
OH
84
81
92
7
8
9
62
44
0
OH
OAc
1
b
2b
2c
2d
1g
2g
O
OAc
O
O
O
O
O
OH
OAc
OH
1c
1h
2h
O
O
O
OAc
O
O
O
OAc
OH
OH
1d
1i
2i
2j
O
OH
O
O
O
OAc
5
80
10
87
OH
OAc
1e
2e
1j
a
Isolated yields.
(J) in Hz. Mass spectra were determined on a Thermo-ITQ 1100 mass
O
H
O
spectrometer. Alkenoic acids, H O , KI and AcOH were obtained
commercially.
2
2
O
OH
KI catalytic acetoxylactonisation of alkenoic acids; typical procedure
I
O
An alkenoic acid (0.3 mmol), H O (30%, 0.6 mmol) and KI (0.06
mmol) were dissolved in AcOH (2 mL), and the mixture was stirred
2
2
O
HOI
at room temperature for 4 h. When the reaction was complete, H O
I
2
(
5 mL), sat.aq Na S O (2 mL) and sat. aq Na CO (2 mL) were
O
2
2
3
2
3
H
2
O
2
AcOH
OAc
H
2
O
2
added. The mixture was extracted with CH Cl (3×5 mL) and the
2
2
I2
O
combined organic layer was dried over anhydrous Na SO , filtered,
2
4
H
2
O
2
and concentrated under reduced pressure. The residue was purified on
silica gel plate using (4:1 hexane-ethyl acetate) as eluant to afford the
pure product.
I
O
KI
OH
O
1
6
-1
5
-Acetoxymethyl-2-tetrahydrofuranone (2a): Oil; IR (neat, cm ):
1776, 1742, 1189; H NMR: d 4.77–4.71 (m, 1H), 4.40–4.10 (m, 2H),
.63–2.32 (m, 3H), 2.23–1.95 (m, 1H), 2.12 (s, 3H); C NMR: d 176.6,
OAc
1
1
3
2
Scheme 2
+
1
70.5, 77.4, 65.3, 28.1, 23.9, 20.6; MS (EI, m/z, %): 158 (M , 43.3), 85
100).
5-Acetoxymethyl-3-methyl-2-tetrahydrofuranone (2b): Oil;
(
12
16
A plausible reaction pathway is shown in Scheme 2. KI is
first oxidised to iodine and then to HOI by H O , which reacts
with the alkenoic acid to afford an iodolactone. The iodolactone
is transformed into a hypervalent iodine intermediate in
situ further oxidation.
acetoxylactone with regeneration of HOI.
In summary, we have developed a novel and efficient
procedure for acetoxylactonisation of alkenoic acids using a
catalytic amount of KI with H O in AcOH at room temperature.
The present results highlight the advantageous role of inorganic
iodide as catalyst as a replacement for expensive aryl iodides.
Moreover, it extends the scope of hypervalent iodine reagents
in organic synthesis, as well as being more environmentally
benign.
IR
neat, cm ): 1770, 1173; H NMR: d 4.78–4.66 (m, 0.5H), 4.62–4.56
(m, 0.5H), 4.40–4.04 (m, 2H), 2.85–2.63 (m, 1H), 2.59–2.46 (m,
.5H), 2.41–2.25 (m, 0.5H), 2.19–2.03 (m, 0.5H), 2.08 (s, 3H),
-1
1
(
2
2
1
3
0
13
14,15
1.79–1.65 (m. 0.5H), 1.28 (d, J = 7.0 Hz, 3H); C NMR: d 178.0, 169.8,
This intermediate collapses to the
1
-3
74.9, 74.2, 64.8, 64.3, 34.5, 33.1, 31.8, 31.2, 20.0, 15.3, 14.3; MS (EI,
+
m/z, %): 172 (M , 34.8), 43 (100).
17
5
-Acetoxymethyl-4-methyl-2-tetrahydrofuranone (2c): Oil;
IR
neat, cm ): 1756, 1190, 1029; H NMR: d 4.68–4.62 (m, 0.5H),
4.40–4.35 (m, 0.5H), 4.32–4.08 (m, 2H), 2.80–2.62 (m, 1.5H),
.43–2.33 (m, 0.5H), 2.26 (dd, J = 16.4, 6.4 Hz, 0.5H), 2.21 (dd, J =
-1
1
(
2
2
2
1
=
6.8, 8.6 Hz, 0.5H), 2.08 (s, 3 H), 1.19 (d, J = 6.6 Hz, 1.5H), 1.08 (d, J
13
7.0 Hz, 1.5H); C NMR: d 176.1, 175.7, 170.4, 83.5, 79.4, 63.6, 62.7,
+
36.2, 36.0, 31.8, 31.6, 20.4, 20.2, 17.2, 13.5; MS (EI, m/z, %): 172 (M ,
1
1.2), 43 (100).
16
5
-Acetoxymethyl-3,3-dimethyl-2-tetrahydrofuranone (2d): Oil; IR
Experimental
IR spectra were recorded on a Thermo-Nicolet 6700 instrument. NMR
spectra were obtained on a Bruker AC 200 spectrometer ( H NMR
at 200 Hz, C NMR at 50 Hz) in CDCl using TMS as an internal
-1
1
(neat, cm ): 1747, 1186, 1025; H NMR: d 4.68 (ddt, J = 9.8, 6.4, 3.0 Hz,
1H), 4.33 (dd, J = 12.3, 3.0 Hz, 1H), 4.15 (dd, J = 12.3, 6.4 Hz, 1H), 2.18
(dd, J = 12.8, 6.4 Hz, 1H), 2.12 (s, 3H), 1.94 (dd, J = 12.8, 9.8 Hz, 1H),
1
13
13
1.30 (s, 3 H), 1.26 (s, 3 H); C NMR: d 180.9, 170.3, 73.9, 64.8, 39.6,
3
+
standard. Chemical shifts (d) are given in ppm and coupling constants
38.6, 24.7, 24.4, 20.2; MS (EI, m/z, %): 186 (M , 18.7), 43 (100).

520 JOURNAL OF CHEMICAL RESEARCH 2015
1
8
-1
8
-Acetoxy-2-oxabicyclo[3.3.0]-3-octanone (2e): Oil; IR (neat, cm ):
Received 20 July 2015; accepted 4 August 2015
Paper 1503500 doi: 10.3184/174751915X14399788140213
Published online: 1 September 2015
1
1
1
1
1
5
759, 1178, 1013; H NMR: d 5.25–5.18 (m, 1H), 4.82 (d, J = 6.9 Hz,
H), 3.22–2.97 (m, 1H), 2.85 (dd, J = 18.3, 10.2 Hz, 1H), 2.3 (dd, J =
8.3, 3.0 Hz, 1H), 2.31–1.56 (m, 4H), 2.05 (s, 3H); C NMR: d 176.2,
1
3
+
References
69.6, 87.4, 78.0, 36.2, 34.7, 30.7. 29.1, 20.8; MS (EI, m/z, %): 184 (M ,
2.3), 43 (100).
1
2
3
4
5
P. J. Stang and V. V. Zhdankin, Chem. Rev., 1996, 96, 1123.
V. V. Zhdankin and P. J. Stang, Chem. Rev., 2002, 102, 2523.
T. Okuyama, Acc. Chem. Res., 2002, 35, 12.
V. V. Grushin, Chem. Soc. Rev., 2000, 29, 315.
M. Ochiai, Y. Takeuchi, T. Katayama, T. Sueda and K. Miyamoto, J. Am.
Chem. Soc., 2005, 127, 12244.
T. Dohi, A. Maruyama, M. Yoshimura, K. Morimoto, H. Tohma and Y.
Kita, Angew. Chem. Int. Ed., 2005, 44, 6193.
R. D. Richardson and T. Wirth, Angew. Chem. Int. Ed., 2006, 45, 4402.
A. Tanaka, K. Moriyama and H. Togo, Synlett, 2011, 1853.
M. Uyanik, D. Suzuki and T. Yasui, Angew. Chem. Int. Ed., 2011, 50, 5331.
16
-1
4
-Acetoxy-2-tetrahydrofuranone (2f): Oil; IR (neat, cm ): 1770,
1
1171, 1012; H NMR: d 5.47 (ddt, J = 6.5, 4.8, 1.5 Hz, 1H), 4.50 (dd, J
=
11.2, 4.8 Hz, 1H), 4.36 (dd, J = 11.0, 1.5 Hz, 1H), 2.94 (dd, J = 18.4,
1
3
7.0 Hz, 1H), 2.60 (dd, J = 18.2, 1.7 Hz, 1H), 2.08 (s, 3H); C NMR: d
+
6
174.5, 170.1, 72.7, 69.8, 34.3, 20.6; MS (EI, m/z, %): 144 (M , 10.8), 43
(100).
7
8
9
16
-1
4
-Acetoxy-5-ethyl-2-tetrahydrofuranone (2g): Oil; IR (neat, cm ):
1
1750, 1156, 1024; H NMR: d 5.49 (dd, J = 6.0, 5.2 Hz, 1H), 4.48 (ddd,
J = 8.4, 5.2, 4.0 Hz, 1H), 2.92 (dd, J = 18.4, 6.0 Hz, 1H), 2.58 (d, J =
8.4 Hz, 1H), 2.09 (s, 3H), 1.98–1.66 (m, 2H), 1.06 (t, J = 7.5 Hz, 3H);
10 K. V. V. Krishna Mohan, N. Narender and S. J. Kulkarni, Tetrahedron Lett.,
004, 45, 8015.
2
1
1
1
M. Uyanik, H. Okamoto and T. Yasui, Science, 2010, 328, 1376.
Z. S. Zhou and X. H. He, J. Chem. Res., 2014, 38, 630.
H. Ohta, Y. Sakata and T. Takeuchi, Chem. Lett., 1990, 19, 733.
1
3
C NMR: d 174.0, 170.0, 84.2, 70.5, 36.8, 21.9, 20.6, 9.8; MS (EI, m/z,
12
3
+
%
): 172 (M , 30.5), 43 (100).
1
1
9
-1
6
-Acetoxymethyl-2-tetrahydropyranone (2h): Oil; IR (neat, cm ):
14 G. Asensio, C. Andreu, C. Boix-Bernardini, R. Mello and M. E. Gonzalez-
Nunez, Org. Lett., 1999, 1, 2125.
15 D. Nicoletti, A. A. Ghini and G. Burton, J. Org. Chem., 1996, 61, 6673.
1
1
2
1
758, 1203; H NMR: d 4.76–4.70 (m, 1H), 4.38–4.14 (m, 2H),
13
.57–2.35 (m, 2H), 2.10 (s, 3H), 1.98–1.80 (m, 4H); C NMR: d 175.8,
16
M. Tiecco, L. Testaferri, M. Tingoli and D. Bartoli,
+
70.9, 77.1, 65.8, 28.3, 25.6, 23.2, 20.4; MS (EI, m/z, %): 172 (M , 4.8),
Tetrahedron, 1990, 46, 7139.
17 H.-J. Ha, K.-N. Yoon, S.-Y. Lee, Y.-S. Park, M.-S. Lim and Y.-G. Yim, J.
Org. Chem., 1998, 63, 8062.
4
3 (100).
2
0
-1
2
-Acetoxymethyltetrahydrofuran (2j): Oil; IR (neat, cm ): 1745,
1
18 M. Tiecco, L. Testaferri and M. Tingoli, Tetrahedron, 1993, 49, 5351.
1
3
1
237, 1043; H NMR: d 4.14–4.02 (m, 2H), 4.00–3.90 (m, 1H),
.85–3.72 (m, 2H), 2.09 (s, 3H), 2.05–1.85 (m, 3H), 1.70–1.57 (m,
H); C NMR: d 170.8, 78.4, 71.5, 65.7, 27.5, 23.9, 20.1; MS (EI, m/z,
19
S. Wang, G. Chen, M. M. Kayser, H. Iwaki, P. C. K. Lau and Y. Hasegawa,
Can. J. Chem., 2002, 80, 613.
13
2
0
A. Kamal, M. N. A. Khan, K. S. Reddy, Y. V. V. Srikanth and T. Krishnaji,
Tetrahedron Lett., 2007, 48, 3813.
+
%
): 144 (M , 23.3), 43 (100).