Epoxidation of protected (1,4,5)-cyclohex-2-ene-triols and their acid hydrolysis to synthesize quercitols from D-(-)-quinic acid

Article abstract of DOI:10.1081/SCC-200063960

Highly stereoselective epoxidations have been achieved in both cyclohexylidene acetal and butane 2,3-bisacetal (BBA) protection of (1,4,5)-cyclohex-2-ene-triols. These epoxy derivatives are all derived from D-(-)-quinic acid and can be used for the synthe

Full text of DOI:10.1081/SCC-200063960

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Epoxidation of Protected
(1,4,5)‐Cyclohex‐2‐ene‐triols
and Their Acid Hydrolysis to
Synthesize Quercitols from
D‐(-)‐Quinic Acid
Tzenge‐Lien Shih a & Ya‐Ling Lin a
a Department of Chemistry , Tamkang University ,
Tamsui, Taipei County, Taiwan, Republic of China
Published online: 15 Aug 2006.
To cite this article: Tzenge‐Lien Shih & Ya‐Ling Lin (2005) Epoxidation of Protected
(1,4,5)‐Cyclohex‐2‐ene‐triols and Their Acid Hydrolysis to Synthesize Quercitols from
D‐(-)‐Quinic Acid, Synthetic Communications: An International Journal for Rapid
Communication of Synthetic Organic Chemistry, 35:13, 1809-1817, DOI: 10.1081/
SCC-200063960
To link to this article: http://dx.doi.org/10.1081/SCC-200063960
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Synthetic Communicationsw, 35: 1809–1817, 2005
Copyright # Taylor & Francis, Inc.
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1081/SCC-200063960
Epoxidation of Protected
(1,4,5)-Cyclohex-2-ene-triols and Their
Acid Hydrolysis to Synthesize Quercitols
from D-(2)-Quinic Acid
Tzenge-Lien Shih and Ya-Ling Lin
Department of Chemistry, Tamkang University, Tamsui, Taipei County,
Taiwan, Republic of China
Abstract: Highly stereoselective epoxidations have been achieved in both cyclohexy-
lidene acetal and butane 2,3-bisacetal (BBA) protection of (1,4,5)-cyclohex-2-
ene-triols. These epoxy derivatives are all derived from D-(2)-quinic acid and can
be used for the synthesis of muco-, (þ)-epi-, (þ)-vibo, (2)-talo, and (2)-gala-
quercitols.
Keywords: D-(2)-Quinic acid, epoxidation, quercitol
INTRODUCTION
Quercitol has been used as a generic term for deoxyinositol or cyclohexane-
pentol. The quercitol’s family contains 16 stereoisomers[1] that bear
resemblance to the parent carbohydrates. Not only are they considered as
potential inhibitors of glycosidases but they also possess other related
biological activities.[2] Therefore, their syntheses have brought a great deal
of attention to the synthetic community.[3] Recently, we have reported the
synthesis of five quercitols, included neo, (2)-epi-, (2)-allo-, (2)-talo-,
and (þ)-gala-quercitols, from dihydroxylation of intermediates 2, 3, and
5, which were all derived from D-(2)-quinic acid (Figure 1).[4] In that
Received in Japan January 11, 2005
Address correspondence to Tzenge-Lien Shih, Department of Chemistry, Tamkang
University, Tamsui 25137, Taipei County, Taipei, Taiwan, Republic of China.
Tel.; Fax: 886-2-86315024; E-mail: tlshih@mail.tku.edu.tw
1809

1810
T.-L. Shih and Y.-L. Lin
Figure 1. Compounds 2, 3, and 5 for epoxidation studies.
article, we had demonstrated that the stereochemistry of dihydroxylation of 2,
3, and 5 could be controlled by choosing appropriate protecting groups. When
the isopropylidene group was used for protection racemic 2 instead of
cyclohexyl acetal moiety, its epoxidation was highly stereoselective. The
resulting epoxy derivative was later used for the synthesis of (+)-vibo- and
(+)-talo-quercitols.[5] It prompted us that we could further investigate the
epoxidation of 3 and 5 to determine how the cyclohexylidene acetal or
butane 2,3-bisacetal (BBA) groups were able to control the outcomes of
their stereochemistry as in compound 2. Therefore, compounds, 2, 3, and 5
were subjected to oxidation with mCPBA (1.2 eq) to provide epoxy
compounds 6 (59%), 11 (65%), and 16 (81%), respectively (Scheme 1).
During this course, either enone 1 or 4 was always formed in yields
of 12–13%. Compounds 6, 11, and 16 were hydrolyzed under Ac2O/H2SO4
(cat) condition, and then deacetylated to afford the muco-, (þ)-epi-,
(þ)-vibo-, (2)-talo-, and (2)-gala-quercitols (vide infra).
RESULTS AND DISCUSSION
When 2 was oxidized with mCPBA (1.2 eq), the required epoxy 6 along with 1
were received in yields of 59% and 12% respectively. (A higher yield (94%)
was obtained in isopropylidene protection of racemic 2 instead of cyclohexyl
acetal group with sonication condition. See Ref. 5.) Effort had been made to
isolate the other stereoisomer of 6 but failed. We suspected that enone 1
might be derived from this unstable minor stereoisomer or 6 after elimi-
nation.[6] This kind of phenomen also occurred for compounds 3 and 5 in
their epoxidation (vide infra). Thus, we could not rule out the possibility of

Epoxidation and Acid Hydrolysis of (1,4,5)-Cyclohex-2-ene-triols
1811
.
Scheme 1. Reagents and conditions: (a) mCPBA (1.2 eq), NaHPO4 12H2O, CH2Cl2;
(b) Ac2O, H2SO4 (cat), reflux; (c) 7N NH3/MeOH.
the formation of the other diastereoisomers during the epoxidation of
compounds 2, 3, and 5, respectively. The stereochemistry of epoxy 6 was
determined by no NOE (Nuclear Overhausier Enhancement) between H2
and H3. The acid hydrolysis of 6 with a catalytic amount of concentrated
sulfuric acid in acetic anhydride under reflux condition[5] afforded the (þ)-
vibo-quercitol pentaacetate (7)[1,7] and (2)-talo-quercitol pentaacetate
(8)[1,8] in a ratio of 1.46:1. It was not surprising that the hydrolysis favored
attacking at the less-hindered site at C4 over C3. Deacetylation of 7 and 8

1812
T.-L. Shih and Y.-L. Lin
provided the ( þ )-vibo-quercitol (9)[1,5,9] and (2)-talo-quercitol (10),[1,5,8,10]
respectively. However, at least in our present results, the ratio between 7 and
8 were in contrast to those of Balci’s method.[5] The ratio of (+)-vibo-
quercitol pentaacetate versus (+)-talo-quercitol pentaacetate from their prep-
aration was 1:4, although O-isopropylidene group was employed instead of
cyclohexylidene acetal group in 6 before acid hydrolysis.
When compound 3 underwent epoxidation, epoxy 11 along with enone 1
were isolated in yields of 65% and 13%, respectively. The stereochemistry of
11 could be unambiguously determined by its NOESY spectrum because of
no observance of NOE between H2 and H3. The highly stereoselective epoxi-
dation of 2 was claimed to be hydrogen-bond-directing effect.[5] However,
the epoxidation of 3 occurred at the opposite face to the C5-OH and cyclo-
hexylidene acetal groups. We suggested that the reaction of 5 might not
involve a directing effect from the hydrogen bond. Meanwhile, out result
strongly supported the theory that the steric effect arising from cyclohexy-
lidene acetal group controlled the outcome of stereochemistry. Whereas
epoxy 11 was treated with the same manner as previous,[5] pentaacetates
12 and 13 were isolated in yields of 45% and 15%, respectively. (For
physical data for muco-quercitol pentaacetate and (þ)-epi-quercitol pentaa-
cetate, See Ref. 1.) Subsequently, compounds 12 and 13 were deacetylated
by 7N NH3 in methanol to provide the muco-quercitol (14)[11] and (þ)-
epi-quercitol (15),[1,12] respectively. Their spectroscopic data were all in
accordance with the reported values.
The oxidation of 5 gave epoxy 16 as well as enone 4 in yields of 81% and
13%, respectively. The indicated stereochemistry of 16 was based on the
observance of NOE between H2 and H3, and also H3/H4 and H6a. The highly
regioselective opening of oxirane ring of 16 occurred exclusively at C4,
resulting in 17[1,13] as the role product in 63% yield. This result was contrast
to the cases in 6 and 11 in which low regioselectivity was obtained. The sub-
sequent deacetylation of 17 gave the (2)-gala-quercitol (18).[10b,12b,13,14]
The overall results were summarized in Table 1.
CONCLUSION
In conclusion, we have successfully synthesized five quercitols in eight steps
each from acid hydrolysis of epoxy 6, 11, and 16, which were all derived
from the highly stereoselective oxidation, of 2, 3, and 5, respectively. It is
worth noting that the epoxidation of 2 and 3 was highly stereoselective to
the anti sense of the cyclohexylidene acetal group but not related to the stereo-
chemistry of C5-OH. Therefore, the steric effect arising from the cyclohexyli-
dene acetal group did play an important role to the results. Despite 5 being
dihydroxylated to give moderate stereoselective products,[4] to our surprise it
was oxidized in high stereoselectivity to give 16 in which oxirane was the

Epoxidation and Acid Hydrolysis of (1,4,5)-Cyclohex-2-ene-triols
1813
Table 1. Physical data for quercitols and their corresponding pentaacetate derivatives
[a]D, Mp (8C)
(literature)
[a]D, Mp (8C)
(literature)
Compound
Pentaacetate
Quercitol
6
7
þ20 (222)a
9
þ47.6, 183–185
(250, 181)c
8
225.4, 184–187
(þ28, 183)b
10
265, 238–248
(þ61, 248)d
11
12
13
172–174 (168)e
14
15
229–232
(230–232)g
þ5, 188–190
(þ7, 197–199)h
þ16.2 (214.5)f
16
17
222.4 (224, 117)e
18
253, 249–256
(248, 258)e
aRef. 1 for (2)-vibo-quercitol pentaacetate.
bRef. 1 for (þ)-talo-quercitol pentaacetate.
cRef. 1 for (2)-vibo-quercitol.
dRef. 1 for (þ)-talo-quercitol.
eRef. 1.
fRef. 4 for (2)-epi-quercitol pentaacetate.
gRef. 11a.
hRef. 15b.
same face with its C2 stereochemistry. The acid-promoted ring opening of
oxirane 6 and 11 had low regioselectivity that favored C4 over C3 and
resulted in 7 and 12 as the major products, respectively. On the contrary, the
ring opening attacked exclusively at C4 over C3 in 16 to give pentaacetate
17 as the only isolated molecule. Among these synthesized quercitols, to the
best of our knowledge, the (þ)-vibo- and (2)-talo-quercitols have never
been prepared until now.
EXPERIMENTAL
General Procedure for Epoxidation
The reaction was conducted in 0.2 M of solution. To a stirred solution of 2, for
.
example, in CH2Cl2 was added 55% mCPBA (1.2 eq) and Na2HPO4 12H2O
(1.2 eq) at ambient temperature. The reaction was monitored by TLC until
completion. The resulting mixture was diluted with CH2Cl2 and washed
with NaHCO3 (sat.). The organic layer was dried (MgSO4), concentrated,
and purified by flash column chromatography.

1814
T.-L. Shih and Y.-L. Lin
(1R,2R,3R,4S,5R)-3,4-Epoxy-5-hydroxy-1,2-O-cyclohexylidene-l,2-dihydroxy-
1
cyclohexane (6): H NMR (300 MHz, CDCl3): d 4.20–4.40 (m, 3H), 3.37
(d, J ¼ 4.5 Hz, 1H), 3.20 (dd, J ¼ 4.5, 1.2 Hz, 1H), 2.17 (ddd, J ¼ 14.5, 6.3,
3.0 Hz, 1H), 1.41–1.72 (m, 9H), 1.39 (br, 2H). 13C NMR (75.4 MHz, CDCl3):
d 109.8, 73.1, 69.6, 64.1, 55.9, 55.4, 37.4, 34.8, 27.2, 25.0, 24.0, 23.7.
Mp 78–798C.
(1)-Vibo-quercitol
pentaacetate
[(1)-penta-O-acetyl-1-deoxy-myo-
inositol] (7): [a]2D7 þ 20 (c 0.2, CHCl3) [lit.[1] 222 for (2)-vibo-quercitol
1
pentaacetate]. H NMR (300 MHz, CDCl3): d 5.39–5.49 (m, 2H), 5.20–
5.31 (m, 1H) 5.16 (t, J ¼ 9.7 Hz, 1H), 4.95 (dd, J ¼ 10.4, 3.1 Hz, 1H),
2.29 (dt, J ¼ 14.3, 4.1 Hz, 1H), 2.15 (s, 3H), 2.02 (s, 6H), 2.01 (s, 3H),
1.99 (s, 3H), 1.74 (ddd, J ¼ 14.3, 11.6, 2.5 Hz, 1H). 13C NMR (75.4 MHz,
CDCl3): d 169.9 (ꢀ2), 169.8, 169.7, 73.2, 71.4, 69.6, 68.4, 66.8, 30.7,
20.9, 20.8, 20.6.
(2)-Talo-quercitol pentaacetate [(2)-penta-O-acetyl-l-deoxy-l-neo-inositol]
(8): [a]D24 2 25.4 (c 0.3, CHCl3) (lit.[1] þ 28, lit.[8] þ 24 for (þ)-talo-quercitol
pentaacetate). 1H NMR (300 MHz, CDCl3): d 5.62 (br s, 1H), 5.52 (dd,
J ¼ 6.3, 3.3 Hz, 1H), 5.31 (dd, J ¼ 10.6, 2.8 Hz, 1H), 5.23 (ddd, J ¼ 11.3,
5.1, 2.8Hz, 1H), 5.20 (dd, J ¼ 10.6, 3.3 Hz, 1H), 1.90–2.20
(m þ 5 ꢀ CH3CO, 17H). 13C NMR (75.4MHz, CDCl3): d 170.1, 170.0,
169.9, 169.6, 69.6, 69.0, 67.7, 66.8, 66.1, 28.9, 20.9, 20.7, 20.6, 20.5. Mp
184–1878C. (lit.[1] 1838C, lit.[8] 172–1788C, lit.[10c] 182–1838C). HRMS
(FAB) calcd. for C13H26O10 (Mþ þ H) 375.1291. Found 375.1281.
(1)-Vibo-quercitol [(1)-1-deoxy-myo-inositol] (9): [a]2D6 þ 47.6 (c 0.2,
1
H2O) (lit.[1] 250 for (2)-vibo-quercitol). H NMR (300 MHz, D2O): d 3.96
(m, 1H), 3.67 (ddd, J ¼ 14.0, 9.3, 4.7 Hz, 1H), 3.48 (dd, J ¼ 18.6, 9.0 Hz,
1H), 3.39 (dd, J ¼ 9.8, 3.0 Hz, 1H), 3.15 (t, J ¼ 9.2 Hz, 1H), 2.00 (dt,
J ¼ 14.0, 3.9 Hz, 1H), 1.45 (ddd, J ¼ 14.4, 12.3, 2.5 Hz, 1H). 13C NMR
(75.4 MHz, D2O þ CD3OD): d 78.3, 74.6, 73.6, 69.2, 36.0. Mp 183–1858C.
(lit.[1] 1818C). HRMS (FAB) calcd. for C6H13O5 (Mþ þ H) 165.0763.
Found 165.0754.
(2)-Talo-quercitol [(2)-1-deoxy-allo-inositol] (10): [a]2D4 265 (c 0.5, H2O)
(lit.[1] þ 61, lit.[10a] þ 56.4, lit.[8] þ 34 for (þ)-talo-quercitol). 1H NMR
(300 MHz, D2O): d 3.82–4.05 (m, 3H), 3.52–3.57 (br. s, 2H), 1.78 (dd,
J ¼ 10.0, 3.2 Hz, 2H). 13C NMR (75.4 MHz, D2O þ CD3OD): d 73.7, 71.4,
70.8, 68.8, 66.8, 33.2. Mp 238–2488C (lit.[1] 2488C, lit.[10c] 245–2488C).
HRMS (FAB) calcd. for C6H13O5 (Mþ þ H) 165.0763. Found 165.0764.
(1R,2R,3R,4R,5S)-3,4-Epoxy-5-hydroxy-1,2-O-cyclohexylidene-1,2-dihydroxy-
1
cyclohexane (11): H NMR (300 MHz, CDCl3): d 4.36 (d, J ¼ 5.6 Hz, 1H),
4.27–4.33 (m, 1H), 4.12–4.22 (m, 1H), 3.50 (d, J ¼ 10.9 Hz, OH), 3.34

Epoxidation and Acid Hydrolysis of (1,4,5)-Cyclohex-2-ene-triols
1815
(d, J ¼ 3.3 Hz, 1H), 3.09 (d, J ¼ 3.3 Hz, 1H), 2.7 (dt, J ¼ 15.7, 2.6 Hz, 1H),
1.84 (ddd, J ¼ 15.7, 4.1, 1.6 Hz, 1H), 1.52–1.72 (m, 8H), 1.31–1.46 (br,
2H). 13C NMR (75.4 MHz, CDCl3): d 109.7, 71.5, 70.2, 64.2, 54.0, 52.2,
37.9, 34.7, 24.9, 24.8, 24.0, 23.6.
Muco-quercitol pentaacetate [penta-O-aetyl-3-deoxy-epi-inositol] (12): 1H
NMR (300 MHz, CDCl3): d 5.65 (t, J ¼ 9.4 Hz, 1H), 5.35 (dd, J ¼ 7.2, 3.5 Hz,
2H), 4.99 (dd, J ¼ 9.4, 3.5 Hz, 2H), 2.33 (dt, J ¼ 15.7, 4.1 Hz, 1H), 2.10
(s, 6H), 2.04 (s, 3H), 2.02 (s, 6H), 1.89 (dt, J ¼ 15.7, 3.6 Hz, 1H). 13C
NMR (75.4 MHz, CDCl3): d 170.0, 169.8, 169.6, 70.9, 67.6, 67.5, 28.7,
20.9, 20.7, 20.6. Mp 172–1748C. (lit.[1] 1688C).
(1)-Epi-quercitol pentaacetate [(2)-penta-O-acetyl-2-deoxy-epi-inositol]
1
(13): [a]2D6 þ 16.2 (c 1.1, CHCl3). H NMR (300 MHz, CDCl3): d 5.50–
5.60 (m, 1H), 5.40 (t, J ¼ 10.2Hz, 1H), 4.85–5.10 (m, 3H), 2.20–2.30
(m, 1H), 2.18 (s, 3H), 2.14 (dd, J ¼ 7.7, 6.7 Hz, 1H), 2.04 (s, 3H), 2.02
(s, 3H), 2.00 (s, 3H), 1.99 (s, 3H). 13C NMR (75.4 MHz, CDCl3): d 170.1,
169.9, 169.8, 169.6, 169.5, 70.7, 69.3, 69.2, 68.7, 66.0, 29.4, 20.8, 20.7, 20.6,
20.5. HRMS (FAB) calcd. for C13H26O10 (Mþ þ H) 375.1291. Found 375.1295.
1
Muco-quercitol [3-deoxy-epi-inositol] (14): H NMR (300 MHz, D2O): d
3.96 (dd, J ¼ 6.6, 3.2 Hz, 2H), 3.79 (t, J ¼ 9.3 Hz, 1H), 3.41 (dd, J ¼ 9.3,
3.2 Hz, 2H), 2.03 (dt, J ¼ 15.4, 4.0 Hz, 1H), 1.64 (dt, J ¼ 15.4, 3.0 Hz, 1H).
13C NMR (75.4 MHz, D2O þ CD3OD): d 74.9 ( ꢀ 2), 71.5 ( ꢀ 2), 71.2,
32.6. Mp 229–2328C. (lit.[10a] 230–2328C). HRMS (FAB) calcd. for
C13H26O10 (Mþ þ H) 375.1291. Found 375.1295.
(1)-Epi-quercitol [(1)-2-deoxy-epi-inositol] (15): [d]2D5 þ5.2 (c 0.3, H2O)
1
(lit.[12] þ7). H NMR (300 MHz, D2O): d 3.88 (dd, J ¼ 2.9, 1.4 Hz, 1H),
3.60–3.75 (m, 1H), 3.35–3.40 (m, 2H), 3.31 (dd, J ¼ 10.2, 2.9 Hz, 1H),
1.82–1.92 (m, 1H), 1.64 (dt, J ¼ 11.8, 5.9 Hz, 1H). 13C NMR (75.4 MHz,
D2O þ CD3OD): d 75.2, 73.8, 72.7, 70.2, 67.4, 34.8. Mp 188–1908C.
(lit.[12] 197–1998C).
(1R,2R,3S,4R,5S)-3,4-Epoxy-5-hydroxy-1,2-[(2S,3S)-2,3-dimethoxybutane-
1
2,3-diyldioxy]cyclohexane (16): H NMR (300 MHz, CDCl3): d 4.18 (ddd,
J ¼ 10.2, 6.5, 2.3 Hz, 1H), 3.74 (d, J ¼ 9.7 Hz, 1H), 3.41 (ddd, J ¼ 12.5,
9.7, 2.8 Hz, 1H), 3.30–3.47 (m, 1H), 3.32 (s, 3H), 3.26 (d, J ¼ 3.7 Hz, 1H),
3.24 (s, 3H), 1.95 (ddd, J ¼ 12.5, 6.5, 2.8 Hz, 1H), 1.70 (br, OH), 1.36 (dd,
J ¼ 12.5, 10.2 Hz, 1H), 1.33 (s, 3H), 1.29 (s, 3H). 13C NMR (75.4 MHz,
CDCl3): d 100.3, 99.8, 68.7, 67.9, 66.3, 56.1 ( ꢀ 2), 48.0, 47.9, 30.7, 17.6.
Mp 134–1358C. LRMS (FAB) m/z 259 (Mþ-H, 9%)
(2)-Gala-quercitol pentaacetate [(2)-penta-O-acetyl-2-deoxy-allo-inositol]
(17): [a]2D4 222.4 (c 0.6, CHCl3) (lit.[1] 224). 1H NMR (300MHz, CDCl3): d

1816
T.-L. Shih and Y.-L. Lin
5.38 (dd, J ¼ 5.3, 3.4 Hz, 1H), 5.20–5.30 (m, 3H), 5.11 (ddd, J ¼ 13.4, 8.8,
4.6 Hz, 1H), 2.15–2.25 (m, 1H), 2.09 (s, 3H), 2.08 (s, 3H), 1.97–2.06
(m þ 3 ꢀ CH3CO, 10H). 13C NMR (75.4MHz, CDCl3): d 169.8, 169.4 (ꢀ2),
69.8, 68.2, 67.7, 66.7, 29.1, 20.9, 20.8, 20.7.
(2)-Gala-quercitol [(2)-2-deoxy-allo-inositol] (18): [a]2D5 253 (c 0.3, H2O)
(lit.[1] 248, lit.[10b,14] 250). 1H NMR (300 MHz, D2O): d 3.87–3.97 (m, 2H),
3.82 (t, J ¼ 3.3 Hz, 1H), 3.70 (ddd, J ¼ 11.2, 9.0, 4.5 Hz, 1H), 3.58 (dd,
J ¼ 9.0, 3.3 Hz, 1H), 1.90 (dt, J ¼ 11.6, 4.5 Hz, 1H), 1.62 (dt, J ¼ 11.6,
11.2 Hz, 1H). 13C NMR (75.4 MHz, D2O þ CD3OD): d 73.1, 72.9,
72.6, 68.8, 67.3, 34.4. Mp 249–2568C, (lit.[1] 2588C, lit.[10b,14] 256–
2578C). HRMS (FAB) calcd. for C6H13O5 (Mþ þ H) 165.0763. Found
165.0771.
ACKNOWLEDGMENT
We gratefully acknowledge the National Science Council (NSC92-2113-M-
032-004) and Tamkang University for supporting this work.
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