An efficient synthesis of L-allono-1,4-lactone from 2,3:5,6-di-O- isopropylidene-D-mannono-1,4-lactone

Article abstract of DOI:10.1016/j.tetlet.2003.12.113

We reported herein an efficient synthesis of L-allono-1,4-lactone from 2,3:5,6-di-O-isopropylidene-D-mannono-1,4-lactone in five steps. The key feature of this method involved a one-pot, 'double inversion' procedure at the stereocenters of C-4 and C-5 of D-mannono-1,4-lactone to afford the target molecule.

Full text of DOI:10.1016/j.tetlet.2003.12.113

Tetrahedron
Letters
Tetrahedron Letters 45 (2004) 1789–1791
An efficient synthesis of
L
-allono-1,4-lactone from 2,3:5,6-di-O-
-mannono-1,4-lactone
isopropylidene-
D
Tzenge-Lien Shih* and Jui-Huang Tseng
Department of Chemistry, Tamkang University, Tamsui 251, Taipei, Taiwan, ROC
Received 1 September 2003; revised 12 November 2003; accepted 9 December 2003
Dedicated to Professor Leo A. Paquette on the occasion of his 70th birthday
Abstract—We reported herein an efficient synthesis of
tone in five steps. The key feature of this method involved a one-pot, Ôdouble inversionÕ procedure at the stereocenters of C-4 and C-5
of -mannono-1,4-lactone to afford the target molecule.
L-allono-1,4-lactone from 2,3:5,6-di-O-isopropylidene-D-mannono-1,4-lac-
D
Ó 2004 Elsevier Ltd. All rights reserved.
The recent two papers have been demonstrated the
of 3 was protected with TBSCl to provide the silyl ether
45 in 68% yield. This moderate yield was due to inevi-
table receiving the bissilyl ether of 3. The C-5 hydroxy
group of 4 was mesylated to afford 56 in 83% yield. The
resulting compound was dissolved in wet DMF followed
by the addition of 2.1 equiv of sodium hydride (60% in
mineral oil).7 This reaction was completed within 5 min
to provide 6 along with 7.8 A higher yield (85%) of 7
could be achieved by treating the mixture with Amber-
lite-120 (Hþ) resin 5 min after the addition of sodium
hydride in order to complete the removal of silyl ether of
6. Not only 7 is the higher Rf value (EtOAc/Hex ¼ 2:1)
efficient routes to synthesize L
-ribose by Ikegami1 and
Kim2 groups, respectively. It is noteworthy that the
KimÕs group employed 2 equiv of piperidine for opening
the c-lactone then inverted C-4 stereochemistry in a one-
pot procedure after aqueous work up.2 An early report
had described the selective conversion of the mesylated
D
-ribonolactone into L-lyxono-1,4-lactone derivative
under strong aqueous potassium hydroxide condition.3
The above strategies were all used to invert only the C-4
stereochemistry on furanoses. In conjunction with our
ongoing project associated with the efficient prepara-
1
tions of a series of
synthesis of -allono-1,4-lactone 8 from 2,3:5,6-di-O-
isopropylidene- -mannono-1,4-lactone 2. This method
L
-sugars, we will report herein a
relative to 3, but also is its H NMR of H3–H4 distinct
L
from 3, 4, and 5. No coupling between H3 and H4 of 7
has been detected. Furthermore, the relative stereo-
chemistry of protons between C-3 and C-4 of 7 is proven
to be opposite sense by no observance of NOE on the
basis of NOESY spectrum. Finally, the protecting group
of 7 was removed by Amberlite-120 (Hþ) to afford the
target molecule, L
-allono-1,4-lactone 8,9 in 76% isolated
yield. The optical rotation value and melting point of 8
are all consistent with the reported data.10–12
D
was also via a one-pot procedure but invert two ste-
reocenters at C-4 and C-5 of 2 under NaH/80% DMF
(aq) condition through twice the internal SN2 reaction.
Our synthetic strategy is depicted in Scheme 1. 2,3:5,6-
was
Di-O-isopropylidene-
D
-mannono-1,4-lactone
2
obtained from the oxidation of 1 by N-iodosuccinimide/
n-tetrabutylammonium iodide condition in 75% yield.4
Compound 2 was subject to selective acid removal (80%
aq AcOH) of protecting group to afford 3 in 86% yield
after silica gel chromatography. The C-6 hydroxyl group
The plausible mechanism of transformation from 5 to 7
is illustrated in Scheme 2. The similar mechanism could
also be found in the Varela et al. in their preparation of
aldopentono-1,4-thiolactones.13 When compound 5 was
dissolved in 80% DMF (aq), the sodium hydroxide was
generated in situ after sodium hydride was added. The
epoxide formation was through SN2 displacement of
C-5-OMs by oxygen anion on C-4 under this basic
Keywords: L-Allono-1,4-lactone.
* Corresponding author. Tel./fax: +886-2-8631-5024; e-mail: tlshih@
mail.tku.edu.tw
0040-4039/$ - see front matter Ó 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetlet.2003.12.113

1790
T.-L. Shih, J.-H. Tseng / Tetrahedron Letters 45 (2004) 1789–1791
O
O
HO
HO
O
O
NIS/n-Bu4NI
O
O
80% AcOH(aq)
86%
O
O
O
O
O
O
O
OH
O
O
75%
3
1
2
TBSO
HO
TBSO
MsO
TBSCl/Imid.
DMF, 68%
MsCl/Pyr
83%
NaH/ DMF
85%
O
O
O
O
O
O
O
O
4
5
Amberlite 120-(H+)
H+
O
OH
O
O
OH
O
O
O
O
O
O
+
O
76%
HO
HO
HO
HO
HO
TBSO
8
7
6
Scheme 1.
O-
O
TBSO
MsO
OH
O
O
OH-
O
O
H+
O
TBSO
TBSO
O
7
OH-
O
O
O
O
O
5
9
10
Scheme 2.
condition to provide 9. Consequently the stereocenter of
C-4 of 9 was inverted by the resulting carboxylate 10
through, again, a SN2-type reaction to furnish 7. At this
stage, both the stereochemistry of C-4 and C-5 have
References and notes
1. Takahashi, H.; Iwai, Y.; Hitomi, Y.; Ikegami, S. Org. Lett.
2002, 4, 2401–2403.
2. Seo, M. J.; An, J.; Shih, J. H.; Kim, G. Tetrahedron Lett.
2003, 44, 3051–3052.
been altered to afford the derivative of
lactone sequence.
L-allono-1,4-
3. Godskesen, M.; Lundt, I.; Madsen, R.; Winchester, B.
Bioorg. Med. Chem. 1996, 4, 1857–11865.
4. Hanessian, S.; Wong, D. H.-C.; Therien, M. Synthesis
1981, 394–396.
In conclusion,
synthesized from 2,3:5,6-di-O-isopropylidene-
L
-allono-1,4-lactone 8, was efficiently
-manno-
D
1
1,4-lactone 2 via a one-pot, Ôdouble inversionÕ fashion
reaction in five steps. The resulting product 8 clearly
supports our proposed mechanism that the formation of
epoxide is the first step in this transformation. The merit
of this type of reaction is able to invert the stereo-
5. Compound 4: a clear syrup. H NMR (300 MHz, CDCl3)
d 4.93 (1H, dd, J ¼ 5:2, 3.6 Hz), 4.82 (1H, d, J ¼ 5:2 Hz),
4.37 (1H, dd, J ¼ 8:9, 3.6 Hz), 3.97 (1H, ddd, J ¼ 8:9, 4.0,
3.1 Hz), 3.86 (1H, dd, J ¼ 10:6, 3.1 Hz), 3.77 (1H, dd,
J ¼ 10:6, 4.0 Hz), 1.49 (3H, s), 1.44 (3H, s), 0.91 (9H, s),
0.10 (3H, s), 0.09 (3H, s). 13C NMR (75 MHz, CDCl3) d
173.6, 114.2, 76.8, 76.2, 76.0, 68.6, 63.4, 26.8, 25.9, 25.8,
18.2, )5.5. LRMS (m=z) 333 (M+H, 5%), 275 (17%), 247
(23%), 189 (35%), 117 (100%), 89 (28%), 75 (100%).
chemistry of both C-4 and C-5 in
neously. Thus it will provide a more diversified and
efficient strategy to prepare other -furanoses. Further
employment of this kind of method in pursuit of pre-
paring a series of -sugars is under investigation.
D-furanoses simulta-
L
6. Compound 5: a pale white solid. 1H NMR (300 MHz,
CDCl3) d 4.83–4.91 (3H, m), 4.76 (1H, dd, J ¼ 8:1,
2.9 Hz), 4.14 (1H, dd, J ¼ 12:3, 2.1 Hz), 3.94 (1H, dd,
J ¼ 12:3, 3.7 Hz), 3.10 (3H, s), 1.49 (3H, s), 1.41 (3H, s),
0.90 (9H, s), 0.11 (3H, s), 0.09 (3H, s). 13C NMR (75 MHz,
CDCl3) d 172.7, 114.6, 78.9, 75.9, 75.5, 74.7, 62.1, 38.7,
L
26.8, 25.9, 25.8, 18.3, )5.5. LRMS (m=z) 411 (M+H, 3%),
26
183 (36%), 153 (100%), 135 (31%). ½aꢀ +5.2° (c 0.2,
D
Acknowledgements
MeOH). Mp 116–119 °C.
7. The addition of 2.1 equiv of NaH is necessary to allow the
reaction to be complete within 5 min. The reaction was
extremely slow while the reaction was conducted under
1.1, 1.25 or 1.5 equiv of NaH, respectively.
This work was financially supported from the National
Science Council (NSC 91-2113-M-032-001) of the
Republic of China and Tamkang University.

T.-L. Shih, J.-H. Tseng / Tetrahedron Letters 45 (2004) 1789–1791
1791
8. Typical procedure: All of the reactions were conducted on
the basis of 0.1–0.2 M. To a solution of compound 5 in 80%
DMF (aq) was added 2.1 equiv 60% NaH at ambient
temperature. The reaction was complete within 5 min and
followed by addition of Amberlite-120 (Hþ) to quench the
reaction as well as to cleave the silyl ether. The resulting
mixture was filtered, evaporated and purified by column
chromatography (230–400 mesh SiO2, EtOAc/Hex ¼ 2:1).
Compound 7: a pale white solid. 1H NMR (300 MHz,
CD3OD) d 4.91 (1H, d, J ¼ 5:6 Hz), 4.77 (1H, d, J ¼
5:6 Hz), 4.65 (1H, d, J ¼ 2:7 Hz), 3.82 (1H, ddd, J ¼ 6:6,
5.6, 2.5 Hz), 3.69 (1H, dd, J ¼ 11:3, 5.6 Hz), 3.61 (1H, dd,
J ¼ 11:3, 6.6 Hz), 1.41 (3H, s), 1.36 (3H, s). 13C NMR
(75 MHz, CD3OD) d 176.8, 113.9, 85.2, 77.8, 76.9, 72.3,
63.4, 27.1, 25.6. LRMS (m=z) 219 (M+H, 8%), 203 (100%),
9. Compound 8: Crystallized from MeOH/CH2Cl2. a white
solid. 1H NMR (300 MHz, CD3OD) d 4.57 (d, J ¼ 5:4 Hz,
1H), 4.41 (d, J ¼ 5:4 Hz, 1H), 4.40 (d, J ¼ 3:9 Hz, 1H),
3.79 (ddd, J ¼ 6:1, 5.5, 3.9 Hz, 1H), 3.60 (d, J ¼ 6:1 Hz,
2H). 13C NMR (75 MHz, CD3OD) d 178.6, 87.5, 72.2,
25
20–25
70.3, 69.3, 63.8. ½aꢀ +5.8° (c 0.03, H2O). lit.10 ½aꢀ
D
D
20–25
D
+6.32° to +4.34° (H2O). lit.11 ½aꢀ
+3.7° (H2O). Mp
128–129 °C. lit.10 mp 130 °C.
10. Austin, W. C.; Humoller, F. L. J. Am. Chem. Soc. 1934,
56, 1153–1155.
11. Humoller, F.; McManus, W. F.; Austin, W. C. J. Am.
Chem. Soc. 1936, 58, 2479–2481.
12. The ½aꢀ for its corresponding d-lactone isomer is )46.9.11
D
It is not likely to receive d-lactone at this stage.
13. Varela, O.; Zunszain, P. A. J. Org. Chem. 1993, 58, 7860–
7864.
115 (40%), 59 (62%). ½aꢀ25 +54.3° (c 0.1, MeOH). Mp 124 °C.
D