Dess-Martin periodinane mediated synthesis of thioesters from aldehydes

Article abstract of DOI:10.1016/j.tetlet.2006.12.024

Dess-Martin periodinane (DMP) mediated efficient synthesis of thioesters from the corresponding aldehydes under mild conditions is described.

Full text of DOI:10.1016/j.tetlet.2006.12.024

Tetrahedron Letters 48 (2007) 1287–1290
Dess–Martin periodinane mediated synthesis
of thioesters from aldehydes
Sunita B. Bandgar, B. P. Bandgar,* B. L. Korbad and S. S. Sawant
Organic Chemistry Research Laboratory, School of Chemical Sciences, Swami Ramanand Teerth Marathwada University,
Nanded 431 606, India
Received 30 July 2006; revised 29 November 2006; accepted 7 December 2006
Abstract—Dess–Martin periodinane (DMP) mediated efficient synthesis of thioesters from the corresponding aldehydes under mild
conditions is described.
ꢀ 2007 Elsevier Ltd. All rights reserved.
The driving force for the development of new methodol-
ogies in organic synthesis has been the need for simple
and efficient strategies to obtain complex products. Thio-
esters are activated carboxylic acid derivatives, which
exhibit acylating properties similar to those of acid
anhydrides1 and are important functional groups in or-
ganic synthesis.2 Biologically active thioesters play cen-
tral roles in living cells serving as essential metabolic
intermediates due to their ability to act as excellent inter-
mediates for acyl group transfer reactions. In addition,
biosynthesis of polyketides and nonribosomal polypep-
tides is achieved via thioester intermediates of fatty acids
and amino acids.3
the surfactant, cetyltrimethyl ammonium bromide
(CTAB), was found to be the most suitable condition
for the effective and direct synthesis of useful active thio-
esters (pentafluorophenyl thioesters) from the corre-
sponding aldehydes in water.9
In recent years, hypervalent iodine reagents have occu-
pied an important place in the reactions of natural and
synthetic organic chemistry because of their potential
applications in the construction of carbon–carbon and
carbon–heteroatom bonds.10 One of the most significant
advances in the field, discovery of the Dess–Martin peri-
odinane (DMP) reagent,11 opened the door to a mild
oxidation procedure allowing alcohols to be converted
to the corresponding carbonyl compounds. Its wide-
spread use over the past decade attests to its benign nat-
ure and its ability to succeed under difficult oxidation
circumstances. DMP is an oxidizing agent that over-
comes many of the disadvantages associated with oxida-
tive methods developed so far. As a part of our ongoing
Thioesters are usually prepared by condensation of a
thiol and an acid chloride and they have widespread
applications in synthetic chemistry as precursors to alde-
hydes, ketones, acids, esters, lactones, amides, lactams
and heterocycles.4 Surprisingly, in view of the diverse
chemistry this functional group offers, it has attracted
scant interest from combinatorial chemists.5 Due to
the importance of thioesters, various chemical and enzy-
matic methods have been developed for their synthesis
directly from carboxylic acids6 or acid chlorides.7 The
conversion of alkyl halides to thioesters using potassium
thioacetate is well reported in the literature.8 More re-
cently, it has been reported that the combination of
the water-soluble radical initiator, 2,20-azobis[2-(2-imid-
azolinzolyl)propane dihydrochloride (VA-044), and
OAc
AcO
OAc
I
O
O
O
O
H
SR
NaN3, CH2Cl2, 25 oC, RSH
X
X
Keywords: Dess–Martin periodinane (DMP); Thioester; Aldehyde.
1
2
*
Corresponding author. Fax: +91 2462 229245;
bandgar_bp@yahoo.com
e-mail:
Scheme 1.
0040-4039/$ - see front matter ꢀ 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetlet.2006.12.024

1288
S. B. Bandgar et al. / Tetrahedron Letters 48 (2007) 1287–1290
Table 1. Synthesis of thioesters from aldehydes, sodium azide and thiols using Dess–Martin periodinane
Entry
1
Aldehyde 1
Thioester 2
Time (h)
2.75
Yielda,b (%)
O
O
CHO
CHO
CHO
75
SC6H5
MeO
MeO
-p
SC6H4 CH3
2
3
2.75
0.50
74
94
MeO
MeO
MeO
O
O
SC6H5
MeO
OMe
OMe
MeO
MeO
CHO
MeO
MeO
SC6H5
4
0.5
95
OMe
OMe
O
CHO
5
6
1.0
1.8
97
92
SC6H5
Me
Me
O
CHO
SC6H5
(Me)2N
(Me)2N
O
CHO
7
8
2.2
3.5
87
85
SC6H5
Cl
Cl
Cl
Cl
O
CHO
Cl
SC6H5
Cl
O
CHO
SC6H5
9
3.2
72
NO2
NO2
O
CHO
SC6H5
10
11
3.2
2.2
70
60
O2N
O2N
O2N
O2N
CHO
SC6H5

S. B. Bandgar et al. / Tetrahedron Letters 48 (2007) 1287–1290
1289
Table 1 (continued)
Entry
Aldehyde 1
Thioester 2
Time (h)
2.5
Yielda,b (%)
O
CHO
SC6H5
12
70
H5C6S
OHC
O
SC6H5
S
13
14
3.1
3.1
75
70
CHO
S
O
SC6H5
O
CHO
CHO
O
O
O
SC6H5
15
16
4.1
2.1
80
85
N
N
SC6H5
CHO
O
a Yields of isolated pure products.
b The products were characterized by IR, 1H NMR and mass spectroscopies and by elemental analysis.
program on the development of novel methods in organ-
ic synthesis under mild conditions,12 we describe a new
efficient and practical route for the one-step conversion
of aldehydes into the corresponding thioesters using
Dess–Martin periodinane and sodium azide in dichloro-
methane at 25 ꢁC in high yield under mild conditions
(Scheme 1).
Reaction of sodium azide with DMP furnished the azido
derivative, which reacted with the aldehyde to form an
azido-hydrin intermediate. This intermediate on further
oxidation resulted in an acyl azide, which on nucleo-
philic substitution with the thiol furnished the corres-
ponding thioester. In order to support the nucleophilic
activation mechanism, we thought that NaCN might
be a better activator than NaN3 because cyanide is
known as a good nucleophile as well as a good leaving
group. When we performed the reaction with NaCN
and thiophenol with 3,4-dimethoxy benzaldehyde, the
corresponding thioester was formed in low yield (40%)
and required a longer reaction time (6 h). Therefore,
we have selected NaN3 as an additive for the synthesis
of thioesters (Table 1).
To the best of our knowledge, the applicability of DMP
in the synthesis of thioesters from aldehydes has not
been reported. Attempts to prepare thioesters using
DMP without any additive or with NaBr or KBr or I2
as an additive furnished very poor yields (5–10%). The
best results were obtained using DMP and NaN3 in
dichloromethane. To explore the generality and scope
of this methodology, diverse aldehydes were studied to
illustrate this novel and general method for the synthesis
of thioesters and the results are summarized in Table 1.
It is important to note that aldehydes possessing
electron-donating groups furnished excellent yields of
the corresponding thioesters in short reaction times
(Table 1, entries 1–6), whereas aldehydes with elec-
tron-withdrawing substituents resulted in comparatively
low yields and required longer times (Table 1, entries
7–12). Dialdehydes as well as aliphatic aldehydes were
also converted smoothly to the corresponding thioesters
in good yields (Table 1, entries 12 and 16). Heterocyclic
aldehydes were transformed into the corresponding
thioesters in good yields under these mild and neutral
conditions; this can be problematic under acidic condi-
tions (Table 1, entries 13–15).
A successful attempt was made to prepare thioesters
from the corresponding aldehydes using Dess–Martin
periodinane (DMP), NaN3 and diphenyldisulfide in
dichloromethane (Scheme 2). Excellent yields of the cor-
responding thioesters were obtained in a short reaction
time.
In conclusion, the mild reaction conditions, simple
work-up, short reaction time and good to excellent
yields are important features of this novel methodology
as compared to other reported methods.
In a typical experimental procedure, p-methoxybenzal-
dehyde (1.0 mmol) was treated with Dess–Martin peri-
odinane (6 mmol), sodium azide (6.5 mmol) and

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DMP, NaN , 25 °C
H
SPh
3
PhSSPh, CH Cl
2
2
R
R
R
H
Time
(h)
Yield
(%)
1.5
1.0
1.0
2.5
2.5
80
90
92
85
88
Me
OMe
Cl
NO2
Scheme 2.
thiophenol (1 mmol) in CH2Cl2 (10 ml) at 0 ꢁC. Then
the reaction mixture was stirred at 25 ꢁC for 2.75 h.
The progress of the reaction was monitored by TLC.
After completion of the reaction, the mixture was
washed with H2O (3 · 5 ml) and extracted with CH2Cl2
(2 · 10 ml). The combined organic layer was dried over
anhydrous Na2SO4 and the solvent was removed under
vacuum to afford the crude product, which was purified
by column chromatography on silica gel (petroleum
ether–ethyl acetate = 9:1) to furnish phenyl p-methoxy-
phenyl thioester (95%).
Compound 2a, IR: 780, 820, 1030, 1600, 1730,
2930 cmꢀ1 1H NMR (300 MHz, CDCl3): d 3.80 (s,
;
3H, OMe), 6.9 (d, 2H, J = 8 Hz, ArH), 7.50 (m, 5H,
ArH), 8.00 (d, 2H, J = 8 Hz, ArH). Anal. Calcd for
C14H12O2S: C, 68.82; H, 4.95; S, 13.12. Found: C,
68.74; H, 5.02; S, 13.05.
Acknowledgement
B.P.B. thanks CSIR, New Delhi, for financial assistance
(Project No. 1/2023/05/EMR-II) and B.L.K. thanks
CSIR, New Delhi, for a Junior Research Fellowship.
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