Oxidation of α,ω-diols using the Dess - Martin periodinane

Article abstract of DOI:10.1055/s-2001-14610

Depending on the length of the carbon tether, α,ω-diols either afford cyclic acetoxy acetals or dialdehydes upon treatment with the Dess - Martin periodinane.

Full text of DOI:10.1055/s-2001-14610

LETTER
789
Oxidation of , -Diols Using the Dess–Martin Periodinane
Jochen Roels, Peter Metz*
Institut für Organische Chemie, Technische Universität Dresden, Mommsenstraße 13, 01062 Dresden, Germany
Fax (+49) 351-463-3162; E-mail: metz@coch01.chm.tu-dresden.de
Received 16 March 2001
Dedicated to Professor Burchard Franck on the occasion of his 75th birthday
erocycles, oxidation of , -diols with a longer carbon
tether (4d-f) led exclusively to the corresponding dialde-
hydes 8,9 99c,10 and 109a,11 in excellent yields.
Abstract: Depending on the length of the carbon tether, , -diols
either afford cyclic acetoxy acetals or dialdehydes upon treatment
with the Dess–Martin periodinane.
Key words: acetals, acylations, diols, heterocycles, oxidations
Table Oxidation of , -diols 4 with the Dess–Martin periodinanea
HO
Yield (%)b
The Dess–Martin periodinane (DMP)1 is a widely used
oxidant for the chemoselective transformation of alcohols
to the corresponding carbonyl compounds under neutral
conditions. In an ongoing synthetic project, we envisioned
to convert meso diol 12 to dialdehyde 2 by twofold Dess–
Martin oxidation. Unexpectedly, the cyclic acetoxy acetal
33 was isolated as the major product upon treatment of 1
with 2.35 equiv DMP instead, while 2 could not be detect-
ed in the crude product by GC/MS (Scheme 1).
Product
OH
n
4a , n = 1
4b , n = 2
5, n = 1
6, n = 2
92
n
79
72c
OAc
O
5 - 7
37d
4c , n = 3
7, n = 3
4d , n = 4
4e , n = 5
4f , n = 6
8, n = 4
9, n = 5
63
91
92
CHO
OHC
n
8 - 10
10 , n = 6
a Conditions: 2.35 equiv DMP, CH2Cl2, 35 min r.t.
b Isolated yield.
c In the presence of 6 equiv pyridine.
d Conditions: 1.2 equiv DMP, CH2Cl2, 2 h r.t.; dialdehyde (21%) and
4c (30%) detected in the crude product by GC/MS.
To elucidate the role of DMP in the acylation step, hemi
acetal 11,12 which is easily obtained by oxidation of 1,5-
pentanediol (4b) with 1.1 equiv PCC,13,14 was stirred with
an equimolar amount of acetic acid in dichloromethane
for 30 min at room temperature. No conversion of hemi
acetal 11 was observed under these conditions. Remark-
ably, subsequent addition of 1 equiv DMP to this mixture
resulted in complete transformation of 11 to 6 within 15
min at room temperature according to GC/MS analysis. In
a similar experiment, 11 was treated with a mixture of 1
equiv acetic acid and 5 equiv propionic acid in the pres-
ence of an equimolar amount of DMP to give a 55:45 mix-
ture (ratio determined by GC) of 6 and propionyloxy
acetal 1215 (Scheme 2).
Scheme 1
Since cyclic acetoxy acetals such as 3 are valuable sub-
strates for C-C as well as C-heteroatom coupling process-
es,4 and methods for the straightforward preparation of
these compounds are rare,4b we screened the behaviour of
, -diols 4a-f towards DMP (Table).5 In case of the diols
4a, 4b and 4c, again acylated cyclic hemi acetals were iso-
lated as the major products. Particularly, 1,4-dihydroxy-
butane (4a) and 1,5-dihydroxypentane (4b) were rapidly
converted to acetoxy acetals 56 and 6,7 respectively, with-
out formation of the dialdehydes using 2.35 equiv DMP.
Addition of 6 equiv pyridine did not affect the formation
of 6. Upon treatment with 1.2 equiv DMP, even diol 4c
preferentially afforded the cyclic acetoxy acetal 7.8 How-
ever, some dialdehyde and unreacted 4c were detected
next to oxepan 7 in the crude product mixture. In contrast
to the smooth formation of five- to seven-membered het-
These results clearly indicate that the presence of DMP is
crucial for the acylation. Scheme 3 depicts a plausible
mechanistic pathway. First, a ligand exchange between 11
and one acetoxy group of DMP leads to 13. Subsequent
dissociation of 13 generates an oxonium ion 14, which in
turn reacts with the acids present to form the acylated lac-
tols 6 or 12, respectively.16
Synlett 2001 No. 6, 789–790 ISSN 0936-5214 © Thieme Stuttgart · New York

790
J. Roels, P. Metz
LETTER
(5) General procedure: To a solution of DMP (4.7 mmol) in
CH2Cl2 (40 mL) was added a solution of the diol (2 mmol) in
a small amount of CH2Cl2 within 5 min. Stirring at r.t. was
continued for the time listed in the Table. Diethyl ether (100
mL) was added, and the mixture was washed twice with 1 N
NaOH and once with sat. aq NH4Cl. The organic layer is dried
over MgSO4, and the solvent is evaporated to leave an oily
residue, which is purified by flash chromatography.
(6) a) Kruse, C. G.; Jonkers, F. L.; Dert, V.; Van der Gen, A. Recl.
Trav. Chim. Pays-Bas 1979, 98, 371; b) 5: Rf 0.48 (ethyl
acetate/cyclohexane, 1:1); 13C NMR (CDCl3, 75 MHz):
= 21.19 (q), 22.72 (t), 31.90 (t), 68.74 (t), 98.78 (d), 170.42
(s); MS (70 eV) m/z (relative intensity): 87 (4) [M+ CH3CO],
70 (62) [M+ CH3CO2H], 43 (100).
(7) a) Quedraogo, A.; Lessard, J. Can. J. Chem. 1991, 69, 474;
b) 6: Rf 0.57 (cyclohexane/ethyl acetate, 1:1).
(8) a) Shine, H. J.; Snyder, R. H. J. Am. Chem. Soc. 1958, 80,
3064; b) 7: Rf 0.61 (cyclohexane/ethyl acetate, 1:1); IR (neat):
1731 cm−1; 1H NMR (CDCl3, 300 MHz): = 1.31 1.89 (m,
6 H), 2.02 2.10 (m, 4 H), 2.41 2.64 (m, 1 H), 3.68 3.76
(m, 1 H), 3.81 3.91 (m, 1 H), 5.97 6.02 (m, 1 H); 13C NMR
(CDCl3, 75 MHz): = 21.30 (q), 22.64 (t), 28.30 (t), 30.56 (t),
33.23 (t), 64.22 (t), 96.86 (d), 170.14 (s); MS (70 eV) m/z
(relative intensity): 98 (79) [M+ CH3CO2H], 43 (100).
(9) a) Ried, W.; Deuschel, G.; Kote ko, A. Liebigs Ann. Chem.
1961, 642, 121; b) Seebach, D.; Corey, E. J.; Beck, A. K.
Chem. Ber. 1974, 107, 367; c) Moeller, K. D.; Tinao, L. V. J.
Am. Chem. Soc. 1992, 114, 1033; d) 8: Rf 0.37 (pentane/ethyl
acetate, 1:1); IR (neat): 1727 cm−1; 1H NMR (CDCl3, 300
MHz): = 1.19 1.32 (m, 2 H), 1.47 1.61 (m, 4 H), 2.35
Scheme 2
(dt, Jd = 1.6 Hz, Jt = 7.3 Hz, 4 H), 9.65 (t, J = 1.6 Hz, 2 H); 13
C
NMR (CDCl3, 75 MHz): = 21.50 (t), 28.33 (t), 43.33 (t),
Scheme 3
202.18 (d); MS (70 eV) m/z (relative intensity): 128 (1) [M+],
57 (100).
(10) a) Huisgen, R.; Palacios Gambra, F. Chem. Ber. 1982, 115,
2242; b) Trzeciak, A. M.; Ziolkowski, J. J. J. Organomet.
Chem. 1994, 464, 107; c) 9: Rf 0.58 (diethyl ether).
(11) a) Bedenbaugh, A. O.; Bedenbaugh, J. H.; Bergin, W. A.;
Adkins, J. D. J. Am. Chem. Soc. 1970, 92, 5774; b) Petrier, C.;
Gemal, A. L.; Luche, J.-L. Tetrahedron Lett. 1982, 23, 3361;
c) 10: Rf 0.61 (diethyl ether); IR (neat): 1737 cm−1; 1H NMR
(CDCl3, 300 MHz): = 1.27 1.37 (m, 6 H), 1.55 1.64 (m,
4 H), 2.39 (dt, Jd = 1.7 Hz, Jt = 7.3 Hz, 4 H), 9.73 (t, J = 1.7
Hz, 2 H); 13C NMR (CDCl3, 75 MHz): = 21.89 (t), 28.85 (t),
29.03 (t), 43.78 (t), 202.72 (d); MS (70 eV) m/z (relative
intensity): 138 (3) [M+ H2O], 41 (100).
Acknowledgement
Financial support of this work by the Deutsche Forschungsgemein-
schaft and the Fonds der Chemischen Industrie is gratefully ack-
nowledged.
References and Notes
(1) a) Dess, D. B.; Martin, J. C. J. Org. Chem. 1983, 48, 4155;
b) Dess, D. B.; Martin, J. C. J. Am. Chem. Soc. 1991, 113,
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d) Speicher, A.; Bomm, V.; Eicher, T. J. Prakt. Chem./Chem.-
Ztg. 1996, 338, 588; e) Boeckman Jr., R. J. In Handbook of
Reagents for Organic Synthesis, Oxidizing and Reducing
Agents; Burke, S. D.; Danheiser, R. L., Eds.; Wiley: New
York; 1999; p 468.
(2) de Napoli, L.; Messere, A.; Palomba, D.; Piccialli, V.;
Evidente, A.; Piccialli, G. J. Org. Chem. 2000, 65, 3432.
(3) a) Lopez Aparicio, F. J.; Lopez Sastre, J. A.; Isac Garcia, J.;
Robles Diaz, R. Carbohydr. Res. 1984, 132, 19; b) 3: Rf 0.37
(ethyl acetate/pentane, 1:1); MS (70 eV) m/z (relative
intensity): 187 (41) [M+ CH3], 143 (32) [M+ CH3CO2], 43
(100).
(12) Baer, S., Brinkman; E. A., Brauman, J. I. J. Am. Chem. Soc.
1991, 113, 805.
(13) Lin, Y.-T.; Houk, K. N. Tetrahedron Lett. 1985, 26, 2517.
(14) For a chemoselective oxidation of 1,4-diols to -lactols with
o-iodoxybenzoic acid, see: a) Corey, E. J.; Palani, A.
Tetrahedron Lett. 1995, 36, 3485; b) Corey, E. J.; Palani, A.
Tetrahedron Lett. 1995, 36, 7945.
(15) Hall, C. D.; Le, V. T. J. Chem. Soc., Perkin Trans. 2 1998,
1483.
(16) As a referee suggested, an additional internal transfer of
acetate might be operative in 13 to account for the ratio
6:12 = 55:45.
Article Identifier:
(4) a) Reetz, M. T.; Müller-Starke, H. Liebigs Ann. Chem. 1983,
1726; b) Dahanukar, V. H.; Rychnovsky, S. D. J. Org. Chem.
1996, 61, 8317.
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Synlett 2001, No. 6, 789–790 ISSN 0936-5214 © Thieme Stuttgart · New York