A general procedure for a one-pot oxidative cleavage/Wittig reaction of glycols

Article abstract of DOI:10.1016/S0040-4039(02)00661-5

Oxidative cleavage of a series of glycols using NaIO₄ on silica gel in the presence of a series of stabilized ylides provides access to a number of synthetically useful alkenes. The ease and general utility of this reaction is demonstrated here using several carbohydrates and amino acid derived glycols.

Full text of DOI:10.1016/S0040-4039(02)00661-5

TETRAHEDRON
LETTERS
Pergamon
Tetrahedron Letters 43 (2002) 3923–3925
A general procedure for a one-pot oxidative cleavage/Wittig
reaction of glycols
Norma K. Dunlap,* Wosenu Mergo, James M. Jones and Jesse D. Carrick
Department of Chemistry, Middle Tennessee State University, Murfreesboro, TN 37132, USA
Received 15 March 2002; accepted 28 March 2002
Abstract—Oxidative cleavage of a series of glycols using NaIO4 on silica gel in the presence of a series of stabilized ylides provides
access to a number of synthetically useful alkenes. The ease and general utility of this reaction is demonstrated here using several
carbohydrates and amino acid derived glycols. © 2002 Elsevier Science Ltd. All rights reserved.
In connection with the synthesis of several pepti-
domimetics of -alanine– -alanine, we needed to pre-
The reactions of three different carbohydrate deriva-
tives (3–5), as well as diol 1, and phenylethane-1,2-diol
were carried out in the presence of excess sodium
periodate on silica and one of three ylides. The ylides
chosen were the ethyl triphenylphosphoranylidene ace-
D
D
pare an unsaturated ester as a common intermediate.
Oxidative cleavage of amino acid-derived glycols simi-
lar to 1 have been utilized by Datta in the synthesis of
azimic acid.1 We found that in situ trapping of the
intermediate aldehyde provided by cleavage of 1 with
NaIO4 on silica gel proceeded smoothly to afford the
ester 2 (Fig. 1).2
tate,
triphenylphosphoranylidene
acetone
and
triphenylphosphoranylidene acetaldehyde (6a–c). Reac-
tion conditions are non-aqueous, proceed readily at
room temperature and involve no aqueous workup.
The preparation of fifteen different alkenes is summa-
rized in Table 1.
We have found few references to conditions for this
oxidative cleavage/Wittig reaction which involve an in
situ sequence.3 Other one-pot oxidation/Wittig
sequences have been reported for the oxidation of
primary alcohols using various oxidants including
Swern oxidation, manganese-based oxidants, Dess–
Martin reagent, o-iodoxybenzoic acid and lead tetra-
acetate.4–8 Given the ease of utility of the sodium
periodate/silica gel reagent as a non-aqueous oxidant,
we felt that it would be worthwhile to investigate the
general utility of the oxidative cleavage/Wittig sequence
with some carbohydrate-derived glycols.
This sequence results in a comparable or improved
yield in the preparation of several compounds that have
previously demonstrated synthetic utility. For instance,
9a has most often been prepared from the DIBAl-H
reduction and Wittig olefination of the corresponding
protected tartrate. This compound has been used in the
syntheses of C2-symmetric cyclic ureas, insecticides and
antifungals as well as other useful structures.9,10 Com-
pounds 8a and 10a have been used in the synthesis of
C2-symmetric cyclic ureas, tetronomycin, and piperidine
alkaloids.11–13
Typical conditions are described for the oxidation/Wit-
tig of diol 1: compound 1 (33 mg, 0.12 mmol) was
dissolved in 1.0 ml of anhydrous CH2Cl2. Sodium
periodate on silica gel (332 mg, 20% by weight) was
added along with ylide 6d (80 mg, 0.24 mmol). The
mixture was stirred vigorously for 20 h, then filtered,
washing twice with CH2Cl2. Evaporation and column
Figure 1.
1
chromatography afforded 29 mg (80%) of 5b. H NMR
(CDCl3) l 1.40 (d, 3H, J=6.2 Hz), 1.48 (s, 9H), 1.56 (s,
3H), 1.63 (s, 3H), 3.74 (s, 3H), 5.33 (m, 1H, CH
6 O), 5.44
* Corresponding author. Tel.: 615-898-2954; fax: 615-898-5182;
e-mail: ndunlap@mtsu.edu
(m, 1H, CHN), 5.92 (dd, 1H, J=1.1, 11.7 Hz), 6.32
6
0040-4039/02/$ - see front matter © 2002 Elsevier Science Ltd. All rights reserved.
PII: S0040-4039(02)00661-5

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N. K. Dunlap et al. / Tetrahedron Letters 43 (2002) 3923–3925
Table 1.
(dd, 1H, J=8, 11.7 Hz); IR (CHCl3) 3037, 2940, 1723,
1689 cm−1; HRMS (FAB) m/z calcd for C15H25NO5
(M++H): 300.1811, found 300.1838.
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In conclusion, the general utility of a simultaneous,
one-pot oxidative cleavage/Wittig reaction of glycols
has been demonstrated. The reactions involve inexpen-
sive reagents and should be amenable to large-scale
preparations as there are no requirements for low tem-
peratures or inert atmosphere and the workup requires
only filtration.
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