Efficient and Facile Glycol Cleavage Oxidation Using Improved Silica Gel-Supportes Sodium Metaperiodate

Full text of DOI:10.1021/jo9621581

2622
J . Org. Chem. 1997, 62, 2622-2624
Ta ble 1. Oxid a tive Clea va ge of 1,2-Diols in to Ald eh yd es
Efficien t a n d F a cile Glycol Clea va ge
Oxid a tion Usin g Im p r oved Silica
by Silica Gel-Su p p or ted Na IO4
Gel-Su p p or ted Sod iu m Meta p er iod a te
Yong-Li Zhong and Tony K. M. Shing*
Department of Chemistry, The Chinese University of Hong
Kong, Shatin, Hong Kong
Received November 19, 1996
Sodium metaperiodate has been an attractive and
popular reagent for the oxidative cleavage of vicinal diols
(R- or 1,2-glycols) and related functional groups into
dicarbonyls.1 The popularity stems from its specificity,
its reactivity under neutral and mild conditions which
is compatible with a wide range of functionalities, its
stability, and its low cost.2 This reagent is particularly
valuable in organic synthesis entailing carbohydrates
because the generation of aldehydes from 1,2-diols is
generally more efficient than those from oxidation of the
corresponding primary alcohols.1a
Glycol scission oxidations using sodium metaperiodate
are generally performed in aqueous alcohols or THF, but
the effectiveness of the oxidant in nonpolar solvents is
limited by its insolubility.3,4 To solve the solubility
problem, Hodge and co-workers employed silica gel-
supported sodium metaperiodate to oxidize R-glycols and
hydroquinones smoothly in dichloromethane, benzene, or
ether.5 However, this early anhydrous silica gel-sup-
ported sodium metaperiodate reagent is of little synthetic
value because its preparation is tedious and the oxidative
cleavage reactions require relatively long reaction times.
Recently, an alternative method using sodium metape-
riodate supported on wet silica gel has appeared.6 This
alternative protocol involves the addition of a freshly
prepared aqueous solution of sodium metaperiodate to a
stirring suspension of silica gel in dichloromethane
followed by the introduction of a solution of the diol in
dichloromethane. However, this method requires vigor-
ous stirring during reaction, and the resultant silica gel
readily forms a colloid that impedes efficient stirring.
Column chromatography is occasionally required to
fractionate the products in order to obtain pure alde-
hydes.6
* Corresponding author: phone, (852)-2609-6367; fax, (852)-2603-
5057; e-mail, tonyshing@cuhk.edu.hk.
Now, we report an improved silica gel-supported meta-
periodate reagent in powder form for the efficient and
facile preparation of aldehydes from vicinal glycols. The
oxidative cleavage reagent, a free-flowing powder, is
easily and conveniently prepared by adding silica gel to
aqueous sodium metaperiodate and can be stored in a
bottle for 1 month with negligible loss of activity. The
scission products obtained from this improved protocol
are pure enough for further synthetic operations without
the need for chromatography.
Glycol oxidative fission reactions are easily carried out
by stirring a suspension of the reagent and the vicinal
diol in dichloromethane at room temperature or below.
The results of a variety of diols (compounds 1-10) are
shown in Table 1. In all cases, we have not encountered
stirring problems due to colloid formation of the silica
gel. The glycol scission reactions generally proceed
smoothly and quickly and, after a simple workup proce-
dure of filtration, afford essentially pure aldehydes in
excellent yields.
(1) (a) Shing, T. K. M. In Comprehensive Organic Synthesis; Trost,
B. M., Fleming, I., Eds.; Pergamon Press: Oxford, 1991; Vol. 7, p 703.
(b) Gundermann, K.-D.; Schwandt, L. In Houben-Weyl; Falbe, J ., Ed.;
Georg Thieme Verlag: Stuttgart, 1983; Vol. E3, p 510. (c) Perlin, A.
S. In The Carbohydrates, Chemistry and Biochemistry; Pigman, W.,
Horton, D., Wander, J . D., Eds.; Academic Press: London, 1980; Vol.
1B, p 1167. (d) Dryhurst, G. Periodate Oxidation of Diols and other
Functional Groups; Pergamon Press: New York, 1970. (e) Bunton, C.
A. In Oxidation in Organic Chemistry; Wiberg, K. E., Ed.; Academic
Press: New York, 1965; Vol. 5A, p 367.
(2) For recent examples of glycol cleavage oxidation using sodium
metaperiodate, see: (a) Marco-Contelles, J .; Destabel, C.; Gallego, P.;
Chiara, J . L.; Bernabe´, M. J . Org. Chem. 1996, 61, 1354. (b) Shing, T.
K. M.; Wong, C. H.; Yip, T. Tetrahedron: Asymmetry 1996, 7, 1323.
(c) Wipf, P.; Kim, Y.; Goldstein, D. M. J . Am. Chem. Soc. 1995, 117,
11106. (d) Panek, J . S.; Xu, F. J . Am. Chem. Soc. 1995, 117, 10587. (e)
Corey, E. J .; Roberts, B. E.; Dixon, B. R. J . Am. Chem. Soc. 1995, 117,
193. (f) Nicolaou, K. C.; Theodorakis, E. A.; Rutjes, F. P. J . T.; Sato,
M.; Tiebes, J .; Xiao, X.-Y.; Hwang, C.-K.; Duggan, M. E.; Yang, Z.;
Couladouros, E. A.; Sato, F.; Shin, J .; He, H.-M.; Bleckman, T. J . Am.
Chem. Soc. 1995, 117, 10239. (g) Clive, D. L. J .; Zhang, C. Z. J . Org.
Chem. 1995, 60, 1413. (h) Kamenecka, T. M.; Overman, L. E.
Tetrahedron Lett. 1994, 35, 4279. (i) Shing, T. K. M.; Fung, W.-C.;
Wong, C. H. J . Chem. Soc., Chem. Commun. 1994, 449. (j) Shing, T.
K. M.; Tsui, H.-C. Tetrahedron: Asymmetry 1994, 35, 1269.
(3) House, H. O. Modern Synthetic Reactions; Benjamin: Menlo
Park, 1972; p 353.
(4) Sklarz, B. Quart. Rev. 1967, 21, 3.
(5) Gupta, D. N.; Hodge, P.; Davies, J . E. J . Chem. Soc., Perkin
Trans. 1 1981, 2970.
(6) Daumas, M.; Vo-Quang, Y.; Vo-Quang, L.; Gaffic, F. L. Synthesis
1989, 64.
S0022-3263(96)02158-5 CCC: $14.00 © 1997 American Chemical Society

Notes
The present protocol is attractive particularly for
vicinal diols that are not readily soluble in aqueous
alcohols or THF and for aldehydes that are water soluble
(product recovery from an aqueous solvent is difficult).
J . Org. Chem., Vol. 62, No. 8, 1997 2623
(55), 243 (79). Anal. Calcd for C17H26O8: C, 56.97; H, 7.31.
Found: C, 56.72; H, 7.10.
Exp er im en ta l Section
Melting points are measured in degrees Celsius and are
uncorrected. IR spectra were recorded on a FT-IR spectropho-
tometer as neat films on KBr plates. Optical rotations were
obtained at 589 nm. 1H and 13C NMR spectra were measured
in CDCl3 solutions at 250 and 62.9 MHz, respectively. High-
resolution mass spectra were obtained using the FAB technique.
All reactions were monitored by analytical TLC on Merck
aluminum-precoated plates of silica gel 60 F254 with detection
by spraying with 5% (w/v) dodecamolybdophosphoric acid in
ethanol and subsequent heating. All reagents and solvents were
of general reagent grade and were used without further purifica-
tion. E. Merck silica gel 60 (230-400 mesh) was used for column
chromatography and as the support for NaIO4.
P r ep a r a tion of Silica Gel-Su p p or ted Na IO4 Rea gen t.
NaIO4 (2.57 g, 12.0 mmol) was dissolved in 5 mL of hot water
(∼70 °C) in a 25 mL round-bottomed flask. To the hot solution
was added silica gel (230-400 mesh, 10 g) with vigorous swirling
and shaking. The resultant silica gel coated with NaIO4 was in
a powder form and was free-flowing. The reagent can be kept
in a bottle for 1 month with negligible loss of activity.
Diol 3a . A solution of the enoate 11 (716 mg, 2.0 mmol) in
90% aqueous AcOH (5 mL) was stirred at rt for 24 h. The AcOH
was removed in vacuo, and the residue was chromatographed
on silica gel (Et2O:hexane ) 2:1) to give diol 3a (572 mg, 90%)
as a colorless syrup: Rf 0.10 (Et2O:hexane ) 3:1); [R]20 -32.8
D
(c 1.0, CHCl3); IR (KBr) 3433, 1722, 1645 cm-1; 1H NMR δ 1.31
(3H, s), 1.48 (3H, s), 2.17 (2H, brs, D2O exchangeable), 3.74 (3H,
s), 3.70-3.78 (1H, m), 3.86 (1H, dd, J ) 11.3, 3.0 Hz), 4.00 (1H,
m), 4.05 (1H, d, J ) 3.6 Hz), 4.13 (1H, dd, J ) 8.4, 3.0 Hz), 4.23-
4.41 (2H, m), 4.56 (1H, d, J ) 3.6 Hz), 5.90 (1H, d, J ) 4.8 Hz),
6.10 (1H, dt, J ) 15.8, 2.1 Hz), 6.94 (1H, dt, J ) 15.8, 4.2 Hz);
13C NMR δ 26.1, 26.6, 51.6, 64.3, 68.7 (2C), 80.8, 82.1, 82.6, 105.1,
111.8, 121.2, 143.6, 166.6; MS m/ z (rel int) 319 [(M + H)+, 38],
301 (8), 261 (100), 243 (21). Anal. Calcd for C14H22O8: C, 52.82;
H, 6.97. Found: C, 52.50; H, 6.87.
Ald eh yd e 3b. Glycol cleavage oxidation of 3a afforded
aldehyde 3b as a colorless syrup in 98% yield: Rf 0.25 (Et2O:
hexane ) 2:1); [R]20 -77.6 (c 1.0, CHCl3); IR (KBr) 1746, 1683,
D
1634 cm-1
;
1H NMR δ 1.34 (3H, s), 1.48 (3H, s), 3.74 (3H, s),
Gen er a l P r oced u r e for Glycol Clea va ge Oxid a tion s. To
a vigorously stirred suspension of silica gel-supported NaIO4
reagent (2.0 g) in CH2Cl2 (5 mL) in a 25 mL round-bottomed
flask was added a solution of the vicinal diol (1.0 mmol) in CH2-
Cl2 (5 mL). The reaction was monitored by TLC until disap-
pearance of the starting material (generally 10-30 min). The
mixture was filtered through a sintered glass funnel, and the
silica gel was thoroughly washed with CHCl3 (3 × 10 mL).
Removal of solvents from the filtrate afforded the aldehyde that
was pure enough for most purposes.
4.13 (1H, ddd, J ) 15.9, 4.3, 2.0 Hz), 4.25 (1H, ddd, J ) 15.9,
4.3, 2.0 Hz), 4.28 (1H, d, J ) 3.7 Hz), 4.58 (1H, dd, J ) 3.7, 1.2
Hz), 4.61 (1H, d, J ) 3.5 Hz), 5.97 (1H, dt, J ) 15.7, 2.0 Hz),
6.12 (1H, d, J ) 3.5 Hz), 6.84 (1H, dt, J ) 15.7, 4.3 Hz), 9.69
(1H, d, J ) 1.2 Hz); 13C NMR δ 26.1, 26.7, 51.5, 68.7, 81.9, 84.3,
84.5, 105.9, 112.5, 121.3, 142.5, 166.1, 199.6; HRMS m/ z calcd
for C13H19O7 (M + H)+ 287.1125, found 287.1116.
Ald eh yd e 4b. Diol 4a 2b was oxidatively cleaved to give
aldehyde 4b as colorless needles in quantitative yield: mp 75-
76 °C; Rf 0.21 (EtOAc:CH2Cl2 ) 1:1); [R]20D +14.7 (c 1.0, CHCl3);
IR (KBr) 1731, 1644 cm-1; 1H NMR δ 1.24 (3H, s), 1.38 (3H, s),
1.58 (3H, s), 3.04 (1H, s, D2O exchangeable), 4.19 (1H, d, J )
3.6 Hz), 4.25 (1H, d, J ) 0.8 Hz), 5.90 (1H, d, J ) 3.6 Hz), 9.70
(1H, d, J ) 0.8 Hz); 13C NMR δ 19.0, 26.4, 26.5, 79.0, 84.2, 85.4,
103.8, 113.2, 198.9; HRMS m/ z calcd for C9H15O5 (M + H)+
203.0914, found 203.0925.
Ald eh yd e 1b. Diol 1a 7 was oxidatively cleaved to give 1b
as a colorless syrup in 99% yield: Rf 0.45 (EtOAc:CH2Cl2 ) 2:1);
[R]20 -46.1 (c 1.0, CHCl3); IR (KBr) 1737, 1633 cm-1; 1H NMR
D
δ 1.32 (3H, s), 1.34 (3H, s), 1.42 (3H, s), 1.49 (3H, s), 3.93 (1H,
d, J ) 2.8 Hz), 4.01 (1H, dd, J ) 8.7, 5.2 Hz), 4.06-4.16 (2H,
m), 4.28 (2H, s), 4.32 (1H, dd, J ) 5.8, 2.8 Hz), 4.65 (1H, d, J )
3.6 Hz), 5.91 (1H, d, J ) 3.6 Hz), 9.72 (1H, s); 13C NMR δ 25.3,
26.2, 26.8 (2C), 67.5, 72.3, 76.3, 81.2, 83.0, 83.7, 105.2, 109.2,
112.0, 199.8; HRMS m/ z calcd for C14H23O7 (M + H)+ 303.1438,
found 303.1417.
Ald eh yd e 5b. Glycol cleavage oxidation of 5a 2b afforded
aldehyde 5b as a colorless syrup in 98% yield: Rf 0.47 (Et2O:
hexane ) 1:1); [R]20 +70.8 (c 0.4, CHCl3); IR (KBr) 1739, 1648
D
cm-1
;
1H NMR δ 1.22 (3H, s), 1.34 (3H, s), 1.34 (3H, s), 4.12
Ald eh yd e 2b. Diol 2a 8 was oxidatively cleaved to give 2b
as a colorless syrup in 96% yield: Rf 0.29 (Et2O:hexane ) 1:1);
(2H, dt, J ) 5.5, 1.4 Hz), 4.32 (1H, d, J ) 3.5 Hz), 4.59 (1H, s),
5.18 (1H, dd, J ) 10.3, 1.4 Hz), 5.32 (1H, dq, J ) 19.2, 1.4 Hz),
5.82 (1H, d, J ) 3.5 Hz), 5.96 (1H, m), 9.67 (1H, s); 13C NMR δ
17.0, 26.6, 27.0, 66.0, 83.4, 83.5, 85.1, 104.5, 113.6, 116.8, 134.7,
198.7; HRMS m/ z calcd for C12H19O5 (M + H)+ 243.1227, found
243.1236.
[R]20 -56.1 (c 1.4, CHCl3); IR (KBr) 1740, 1643 cm-1; 1H NMR
D
δ 1.33 (3H, s), 1.48 (3H, s), 3.94 (1H, ddt, J )12.9, 5.8, 1.4 Hz),
4.07 (1H, ddt, J ) 12.9, 5.4, 2.1 Hz), 4.29 (1H, d, J ) 3.7 Hz),
4.56 (1H, dd, J ) 3.7, 1.6 Hz), 4.61 (1H, d, J ) 3.5 Hz), 5.18-
5.29 (2H, m), 5.79 (1H, m), 6.11 (1H, d, J ) 3.5 Hz), 9.67 (1H, d,
J ) 1.6 Hz); 13C NMR δ 26.2, 26.9, 71.2, 82.3, 83.6, 84.5, 106.1,
112.4, 118.0, 133.2, 199.8; HRMS m/ z calcd for C11H17O5 (M +
H)+ 229.1071, found 229.1082.
Ald eh yd e 6b. Glycol cleavage oxidation of diisopropyl L-
tartrate (6a ) afforded aldehyde 6b9 as a colorless oil in 90%
yield: Rf 0.27 (EtOAc:hexane ) 2:1); IR (KBr) 3567-3211 (br),
1733, 1633 cm-1 1H NMR δ 1.27 (3H, s), 1.29 (3H, s), 3.78-
;
En oa te 11. To a solution of aldehyde 1b (1.21 g, 4.0 mmol)
in CH2Cl2 (10 mL) was added Ph3PdCHCO2Me (1.47 g, 4.4
mmol), and the resultant solution was stirred at rt for 12 h. The
reaction mixture was then filtered through a silica gel pad and
the filtrate concentrated. The residue was chromatographed
(Et2O:hexane ) 2:3) to give enoate (E)-11 (773 mg, 54%) as a
colorless syrup: Rf 0.40 (Et2O:hexane ) 1:1); [R]20D -37.8 (c 1.0,
CHCl3); IR (KBr) 1724, 1661 cm-1; 1H NMR δ 1.31 (3H, s), 1.35
(3H, s), 1.42 (3H, s), 1.49 (3H, s), 3.74 (3H, s), 3.95 (1H, d, J )
3.2 Hz), 3.98-4.14 (3H, m), 4.26-4.33 (3H, m), 4.54 (1H, d, J )
3.8 Hz), 5.88 (1H, d, J ) 3.8 Hz), 6.17 (1H, dt, J ) 15.7, 1.6 Hz),
6.93 (1H, dt, J ) 15.7, 4.0 Hz); 13C NMR δ 25.2, 26.2, 26.7 (2C),
51.4, 67.5, 68.8, 72.2, 81.2, 82.2, 82.7, 105.2, 109.1, 111.8, 121.1,
143.6, 166.5; MS m/ z (rel int) 359 [(M + H)+, 71], 315 (73), 301
4.48 (2H, brs, D2O exchangeable), 5.08-5.12 (1H, m), 5.20-5.28
(1H, m); 13C NMR δ 21.3 (2C), 69.8, 87.0, 170.1.
Ald eh yd e 7b. Diol 7a 7a was oxidatively cleaved to give
aldehyde 7b,6,10,11 obtained as a colorless oil in 98% yield: Rf
0.45 (EtOAc:hexane ) 1:2); IR (KBr) 3062, 1732, 1636 cm-1; 1H
NMR δ 4.10 (2H, s), 4.63 (2H, s), 7.34 (5H, m), 9.71 (1H, s); 13
C
NMR δ 72.3, 73.6, 128.1 (2C), 128.4, 128.5 (2C), 136.8, 200.4.
Ald eh yd e 8b. Diol 8a 12 was oxidatively cleaved to give
aldehyde 8b12,13 as a colorless oil in 95% yield: Rf 0.27 (Et2O:
hexane ) 2:1); [R]20D +61.6 (c 2.3, CH2Cl2); 1H NMR δ 1.41 (3H,
s), 1.48 (3H, s), 4.06 (1H, dd, J ) 13.6, 4.8 Hz), 4.14 (1H, dd, J
(9) Waldner, A. Tetrahedron Lett. 1986, 27, 6059.
(10) Arndt, H. C.; Carroll, S. A. Synthesis 1979, 202.
(11) Walkup, R. D.; Cunningham, R. T. Tetrahedron Lett. 1987, 28,
4019.
(12) Kierstead, R. W.; Faraone, A.; Mennona, F.; Mullin, J .; Guthrie,
R. W.; Crowley, H.; Simko, B.; Blaber, T. C. J . Med. Chem. 1983, 26,
1561.
(7) (a) Shing, T. K. M.; Tam, E. K. W.; Tai, V. W. F.; Chung, I. H.
F.; J iang, Q. Chem. Eur. J . 1996, 2, 50. (b) Shing, T. K. M.; Tai, V. W.
F.; Tam, E. K. W. Angew. Chem., Int. Ed. Engl. 1994, 33, 2312.
(8) Datta, S.; Chattopadhyay, P.; Mukhopadhyay, R.; Bhattacharjya,
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(13) Fisher, H. O. L.; Baer, E. Helv. Chim. Acta 1934, 17, 622.

2624 J . Org. Chem., Vol. 62, No. 8, 1997
Notes
) 13.6, 7.1 Hz), 4.36 (1H, ddd, J ) 7.1, 4.8, 1.8 Hz), 9.68 (1H, d,
J ) 1.8 Hz); 13C NMR δ 25.1, 26.2, 65.5, 79.8, 111.3, 201.7.
Ald eh yd e 9b. Glycol cleavage oxidation of 9a 7 provided keto
aldehyde 9b14 as a colorless oil in 95% yield: Rf 0.57 (EtOAc:
Ald eh yd e 10b. Glycol cleavage oxidation of 10a 7 provided
aldehyde 10b6 as a colorless oil in 98% yield: Rf 0.49 (EtOAc:
1
hexane ) 2:1); IR (KBr) 1717 cm-1; H NMR δ 1.59-1.65 (4H,
m), 2.42-2.47 (4H, m), 9.73 (2H, t, J ) 1.5 Hz); 13C NMR δ 21.3
(2C), 43.4 (2C), 201.9 (2C).
hexane ) 1:1); [R]20 +33.3 (c 1.0, CHCl3); 1H NMR δ 1.13 (3H,
D
s), 1.28 (3H, s), 1.37 (1H, dd, J ) 14.6, 8.4 Hz), 1.57 (1H, dd, J
) 8.4, 5.6 Hz), 1.80-2.05 (2H, m), 2.09 (3H, s), 2.43 (2H, t, J )
7.2 Hz), 9.48 (1H, d, J ) 5.6 Hz); 13C NMR δ 14.8, 18.4, 28.9,
29.8, 30.0, 36.8, 38.3, 43.3, 199.6, 201.6.
Ack n ow led gm en t. This research was supported by
a RGC Earmarked grant (CUHK457/95P).
(14) Kula, J . Synth. Commun. 1986, 16, 833.
J O9621581