Amberlyst-15-catalyzed efficient synthesis of 1,1-diacetates from aldehydes

Article abstract of DOI:10.1081/SCC-120018771

Amberlyst-15 was found to be an efficient catalyst for acylation reaction of aldehydes with acetic anhydride at room temperature in dichloromethane.

Full text of DOI:10.1081/SCC-120018771

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Amberlyst-15-Catalyzed Efficient Synthesis of 1,1-
Diacetates from Aldehydes
a
a
a
a
A. Vijender Reddy , K. Ravinder , V. L. Niranjan Reddy , V. Ravikanth & Y.
a
Venkateswarlu
a
Organic Chemistry Division-I , Natural Products Laboratory , Indian Institution of Chemical
Technology , Hyderabad, India
Published online: 16 Aug 2006.
To cite this article: A. Vijender Reddy , K. Ravinder , V. L. Niranjan Reddy , V. Ravikanth & Y. Venkateswarlu (2003)
Amberlyst-15-Catalyzed Efficient Synthesis of 1,1-Diacetates from Aldehydes, Synthetic Communications: An International
Journal for Rapid Communication of Synthetic Organic Chemistry, 33:9, 1531-1536, DOI: 10.1081/SCC-120018771
To link to this article: http://dx.doi.org/10.1081/SCC-120018771
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Õ
SYNTHETIC COMMUNICATIONS
Vol. 33, No. 9, pp. 1531–1536, 2003
Amberlyst-15-Catalyzed Efficient Synthesis of
1
#
,1-Diacetates from Aldehydes
A. Vijender Reddy, K. Ravinder, V. L. Niranjan Reddy,
V. Ravikanth, and Y. Venkateswarlu*
Organic Chemistry Division-I, Natural Products
Laboratory, Indian Institution of
Chemical Technology, Hyderabad, India
ABSTRACT
Amberlyst-15 was found to be an efficient catalyst for acylation
reaction of aldehydes with acetic anhydride at room temperature in
dichloromethane.
Key Words: Amberlyst 15; Acetic anhydride; Aldehydes; Ketones;
1
,1-diacetates.
#
IICT Communication No. 01/09/04.
Correspondence: Y. Venkateswarlu, Organic Chemistry Division-I, Natural
Products Laboratory, Indian Institution of Chemical Technology, Hyderabad
*
5
00 007, India; Fax: 0091 40 7160512; E-mail: luchem@iict.ap.nic.in.
1
531
DOI: 10.1081/SCC-120018771
Copyright & 2003 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com

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1
532
Reddy et al.
Selective protection and deprotection of carbonyl groups frequently
represent an important role in the multistep synthesis of complex
[1,2]
[3]
Acetals are the most common derivatives utilized
natural products.
[
4]
to this aim and which are stable in neutral and basic media. However,
in many cases different strategies are desirable where selective
protection of aldehydes in the presence of keto groups are requested.
Further, 1,1-diacetates are useful intermediates in various trans-
[
5,6]
formations, such as nucleophilic substitution reactions
and
[7,8]
Diels-Alder reactions.
A number of methods are available for the synthesis of 1,1-diacetates
[
from aldehydes include the use of strong protic and Lewis acids.
3]
[4]
[
Other catalysts such as Nafion-H, iodine,
9]
[10]
[11]
[12]
zeolite,
are known for the same transformation. The use of
Sc(OTf )3
[13]
and Cu(OTf )3
solid acidic catalysts
[14]
such as ion-exchange resins, clays and zeolites
have received considerable attention in different areas of organic synthe-
sis, due to their environmental compatibility, reusability, greater selectiv-
ity, experimental simplicity, low cost and ease of isolation of the
[
15]
products. In this context ion-exchange resins,
make the reaction pro-
cesses convenient, more economic, non-corrosive, environmentally
benign and act as Bronsted acids enabling them to function as efficient
catalyst for various organic transformations.
In this communication we disclose the reaction of alkyl/aryl alde-
hydes with acetic anhydride in dry dichloromethane in presence of
[16]
amberlyst-15, is one of the most convenient methods for the synthesis
of 1,1-diacetates in excellent yields with high chemoselectivity. On the
basis of its simplicity, reusability and cheapness of the reagent,
we demonstrated the formation of various diacetates in high yields
under mild reaction conditions. Moreover, the work up procedures is
very simple, as the resin can be separated from the reaction mixture
just by filtration. Thus, we become interested in exploring the use
of amberlyst-15 in the synthesis of the 1,1-diacetates from aldehydes
(
Sch. 1).
A variety of aliphatic and aromatic aldehydes are converted into
diacetates using amberlyst-15 (Table 1). Highly deactivated aldehydes
Scheme 1.

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Amberlyst-15-Catalyzed Efficient Synthesis
Table 1. Amberlyst-15 catalyzed diacetates formation.
Time Isolated yield
1533
a
Entry
Substrates
Product (min)
(%)
1
2
3
4
5
6
7
8
9
p-NO
2
-Benzaldehyde
1a
2a
45
60
60
45
45
45
45
45
60
45
45
60
60
60
60
60
60
98
95
95
90
95
90
85
90
80
90
90
85
80
80
80
85
80
p-Me-Benzaldehyde
p-Cl-Benzaldehyde
Anisaldehyde
3a
4a
Benzaldehyde
5a
6a
2-Cl-Benzaldehyde
3-OMe-Benzaldehyde
2-Cl-5-F-Benzaldehyde
Cyclohexanecarboxaldehyde
3,4,5-Trimethoxybenzaldehyde
2-Furaldehyde
7a
8a
9a
1
1
1
1
1
1
1
1
0
1
2
3
4
5
6
7
10a
11a
12a
13a
14a
15a
16a
17a
Dihydrocinnamaldehyde
Cinnamaldehyde
Buteraldehyde
Valeraldehyde
8-Methyl nonanal
2,3-O-Isopropylidene-R-glyceraldehyde
a
Isolated yields and all compounds were characterized by study of their IR,
H NMR and mass spectral data.
1
also gave excellent yields of diacetates (Entries 4, 10, 12). Long chain
aliphatic aldehydes also gave good yields (Entry 16). In a typical experi-
ment a mixture of aldehyde and ketone in (1:1) ratio was reacted with
acetic anhydride in presence of amberlyst-15 catalyst in dichloromethane
at room temperature to give exclusively diacetates of aldehyde, which
demonstrated the chemoselectivity of the method. (Sch. 2). After the
completion of the reaction the catalyst, amberlyst-15 was recovered by
filtration and reused after activation for three cycles without significant
loss of activity.
In conclusion, we have demonstrated that amberlyst-15 is a novel
and reusable catalyst for the synthesis of 1,1-diacetates as compared
[13]
[14]
to Sc(OTf3)
and Cu(OTf3).
In addition to its simplicity and
milder reaction conditions, the method affords high yields of pro-
ducts with greater chemoselectivity. The catalyst is inexpensive,
easily available and reusable, non-corrosive, which makes the reac-
tion process convenient, more economical and environmentally
friendly.

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534
Reddy et al.
Scheme 2.
GENERAL PROCEDURE
To a solution of aldehyde (1 mmol), and acetic anhydride (3 mmol) in
dry dichloromethane (5 mL) was added amberlyst-15 (0.5 g) and stirred at
room temperature for a stipulated time as indicated in Table 1. After
completion of the reaction as indicated by TLC, the catalyst was recov-
ered by filtration from the reaction mixture. The filtrate was diluted with
CH Cl (20 mL), washed with saturated aqueous NaHCO , brine
2
2
3
solution, dried over anhydrous Na SO and concentrated to give crude
4,
2
product. The crude product was purified on silica gel column chromatog-
raphy for analytically pure samples of 1,1-diacetates (Table 1). All
1
compounds were characterized by IR, H-NMR, and mass spectral
analysis.
ꢀ
1a: M.p. 123–124 C; IR (KBr) ꢀ : 3123, 3012, 1764, 1610, 1530,
432, 1349, 1205, 1062, 975, 943, 856 and 752 cm ; H-NMR (200 MHz,
max
ꢁ
1 1
1
CDCl , ꢁ): 2.16 (s, 6H), 7.72 (s, 1H), 7.70 (d, 2H, J ¼ 8.2 Hz), 8.20 (d, 2H
3
þ
J ¼ 8.2 Hz); EIMS: m/z (%): 194 [M -OAc] (8), 151 (78), 134 (14), 105
(
22), 77 (48) and 43 (100).
ꢀ
3
a: M.p. 79–80 C; IR (KBr) ꢀ
3126, 3021, 1771, 1595, 1495, 1437,
max:
ꢁ1
1
374, 1203, 1068, 961, 936, 855 and 725 cm ; H-NMR (200 MHz,
1
CDCl , ꢁ): 2.04 (s, 6H), 7.28 (d, 2H, J ¼ 8.0 Hz), 7.36 (d, 2H,
3
þ
J ¼ 8.0 Hz), 7.54 (s, 1H); EIMS: m/z (%): 242 [M ] (4), 201 (9), 199
(
36), 139 (100), 111 (28), 77 (30) and 43 (100).
ꢀ
4
a: M.p. 64–65 C; IR (KBr) ꢀ : 3010, 2938, 1756, 1682, 1600, 1576,
max
463, 1394, 1315, 1260, 1216, 1161, 1109, 1025, 833 and 760 cm ;
H-NMR (200 MHz, CDCl , ꢁ): 2.04 (s, 6H), 3.78 (s, 3H), 6.84 (d, 2H,
ꢁ
1
1
1
3

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Amberlyst-15-Catalyzed Efficient Synthesis
1535
J ¼ 8.2 Hz), 7.38 (d, 2H, J ¼ 8.2 Hz), 7.54 (s, 1H); EIMS: m/z (%): 238
þ
[
M ] (6), 137 (98), 135 (100), 105 (50), 92 (10), 77 (22), and 43 (68).
8a: M.p. 103–104 C; IR (KBr) ꢀ : 3086, 2924, 1762, 1609, 1576,
458, 1376, 1238, 1198, 1074, 1008, 950, 884, 795 and 733 cm ; H-NMR
ꢀ
max
ꢁ
1 1
1
(
8
200 MHz, CDCl , ꢁ): 2.14 (s, 6H), 6.98–7.10 (m, 1H), 7.18–7.38 (m, 2H),
3
.02 (s, 1H); EIMS: m/z (%): 225 [M -Cl] (35), 183 (9), 159 (67), 157 (84),
þ
and 43 (100).
0a: M.p. 114–115 C; IR (KBr) ꢀ : 3015, 2947, 1753, 1595, 1466,
ꢀ
1
424, 1364, 1243, 1120, 988, 931, 828 and 716 cm ; H-NMR (200 MHz,
max
ꢁ1 1
1
CDCl , ꢁ): 2.14 (s, 6H), 3.82 (s, 3H), 3.9 (s, 6H), 6.7 (s, 2H), 7.56 (s, 1H);
3
þ
EIMS: m/z (%): 298 [M ] (20), 262 (10), 197 (76), 169 (44), 141 (40), 111
10), 69 (14), and 43 (100).
1a: Liquid; IR (KBr) ꢀmax: 3150, 3125, 1775, 1625, 1500, 1375, 1275,
(
1
ꢁ
210, 1150, 1090, 1010, 875 and 775 cm ; H-NMR (200 MHz, CDCl ,
3
1 1
1
ꢁ
): 2.12 (s, 6H), 6.38 (br s, 1H), 6.44 (br s, 1H), 7.40 (br s, 1H), 7.60
þ
(
s, 1H); EIMS: m/z (%): 198 [M ] (3), 155 (6), 149 (8), 141 (10), 97 (36),
6
9 (28), and 43 (100).
12a: Liquid; IR (neat) ꢀmax: 3130, 2950, 1770, 1600, 1500, 1245, 1205,
010, 945 and 750 cm ; H-NMR (200 MHz, CDCl , ꢁ): 1.98 (s, 6H),
ꢁ1 1
1
3
2
.04 (m, 2H), 2.65 (m, 2H), 6.78, (t, 1H J ¼ 6.2 Hz ), 7.10–7.24 (m, 5H);
þ
EIMS: m/z (%): 177 [M -OAc] (17), 134 (48), 105 (70), 91 (66), and
43 (100).
ACKNOWLEDGMENTS
We thank to the Director, Indian Institute of Chemical Technology
and Dr. J. S. Yadav for their encouragement. AVR, KR, VLNR and VR
thankful for CSIR, New Delhi for providing fellowships.
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Received in the UK February 11, 2002