Synthesis of optically active seven-membered 1,5-anhydrocarbasugars and

1,4,5-tribenzoyloxy-2-ethoxy cycloheptanes via [5+2] cycloaddition

Arun A. Yadav
a
, Prajakta S. Sarang
a
, Manishankar Sau
b
, Srinath Thirumalairajan
c,,
, Girish K. Trivedi
b,
,
Manikrao M. Salunkhe
d,
a
Department of Chemistry, The Institute of Science, 15, Madam Cama Road, Mumbai 400 032, India
b
Department of Chemistry, Indian Institute of Technology Bombay, Mumbai 400 076, India
c
Toronto Research Chemicals Inc., 2, Brisbane Road, North York, ON M3J 2J8, Canada
d
Department of Chemistry, Shivaji University, Kolhapur 416 004, India
a r t i c l e i n f o
Article history:
Received 13 January 2012
Revised 30 April 2012
Accepted 3 May 2012
Available online 12 May 2012
Keywords:
Carbasugar
Cyclitol
3-Oxidopyrylium ylide
Cycloaddition
Stereocontrol
a b s t r a c t
[5+2] Cycloaddition followed by asymmetric dihydroxylation procedure have been utilized to prepare
novel cyclitols. Accordingly, rac-2a-hydroxy-6a-ethoxy-1,5-anhydro cyclohept-3-ene, 10 derived from
[5+2] cycloaddition of 3-oxidopyrylium ylide and vinyl ether has been recognized as a seven-membered
carbasugar equivalent and elaborated to 1,4,5-tribenzoyloxy-2-ethoxy cycloheptanes through a exible,
regio- and stereoselective strategy involving Sharpless asymmetric dihydroxylation conditions to resolve
the compounds obtained. The structures and relative congurations of newly synthesized (+)-2a-acet-
oxy-6a-ethoxy-3b,4b-dihydroxy-1,5-anhydro cycloheptane ((+)-12)); ()-1b,4b,5b-tribenzoyloxy-6a-
ethoxy cycloheptane (()-17) and (+)-1a,4a,5a-tribenzoyloxy-6b-ethoxy cycloheptane ((+)-17) are
unambiguously established by single crystal X-ray analysis and duly supported by
1
H and
13
C NMR spec-
troscopy data.
2012 Elsevier Ltd. All rights reserved.
Cyclitol is a generic term used to describe polyhydroxy cycloal-
kanes. Many biologically important molecules and natural products
contain polyhydroxylated carbocycles.
1,2
A number of them have
been used as sweeteners, antibiotics, antiviral, antidiabetic, and
anticancer agents.
3
Inositols (1, Fig. 1) and their derivatives gure
prominently in numerous biological processes.
4
The better known
carbasugar of natural occurrence is pseudo-a-galactose (2).
4
Many
analogues and structural variants of 1 and 2 have been synthesized
and their biological activities, particularly glycosidase inhibition,
have been evaluated.
57
The synthesis of polycyclitols like 3 and 4
as new structural variants embodying the characteristic features
present in 1 and 2 has recently been achieved.
8
Conduritols (5)
(six diastereomers designed AF are known) have generated a great
deal of synthetic interest.
4
Dihydroconduritol-A (6) was found and
isolated by Zeying and Mingzhe fromthe plant Toxocarpus (fromthe
Asclepiadaceae family) which grows in China and some areas of In-
dia.
9
They have named the naturally occurring compound as toxo-
carol and reported that this plant is being used in the treatment
of fractures, contusions, ulcers, and cancers of the cervix, uterus,
and lung.
9
A newand stereocontrolled short method for the synthe-
sis of 6 was described by Balci and co-workers.
10
Various methods are available for the construction of functional-
ized ve- and six-membered rings but only a few approaches have
been reported for the synthesis of seven- and eight-membered ring
cyclitols.
2
Ring-closingmetathesis is commonlyusedfor the synthe-
sis of new polyhydroxylated seven- and eight-membered carbocy-
cles starting from D-arabinose.
2a,11
In particular, polyhydroxylated
seven-membered carbocycles are usually synthesized utilizing rad-
ical reactions,
11
enzymatic hydrolysis,
12
reductive amination,
13
and
sugar-based starting materials.
14
Considering the fundamental
0040-4039/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tetlet.2012.05.014

Corresponding authors.
E-mail addresses: sri@dal.ca (S. Thirumalairajan), snehgkt@yahoo.com
(G.K. Trivedi), mmsalunkhe@hotmail.com (M.M. Salunkhe).

Currently at.
OH
OH
OH
OH
HO
HO HO
HO
OH
OH
OH
HO
HO
OH
HO
OH
OH
OH
OH
OH
HO
HO
OH
OH
OH
OH
OH
OH
HO
HO
OH
OH
HO
HO
1
2 3
4 5 6
Figure 1. Structures of polyhydroxy carbocycles.
Tetrahedron Letters 53 (2012) 35993602
Contents lists available at SciVerse ScienceDirect
Tetrahedron Letters
j our nal homepage: www. el sevi er. com/ l ocat e/ t et l et
importance of cyclitols, we have devised the synthesis of seven-
membered cyclitol mimics. We report herein our approaches to
the efcient synthesis of cycloheptane polyol analogues based on
3-oxidopyrylium ylide-alkene cycloaddition.
In the present approach, a well established asymmetric dihydr-
oxylation methodology
1520
has been adapted for the optical reso-
lution of rac-6a-ethoxy-2a-acetoxy-1,5-anhydro cyclohept-3-ene
(11). While undertaking this exercise it was assumed that the ste-
rically constrained olen would offer additional assistance in
achieving the desired selectivity.
Our approach to the seven-membered carbocycles starts with an
Achmatowicz reaction.
21
A number of research groups have
exploited Achmatowicz reaction to achieve the synthesis of natu-
rallyoccurringtarget molecules.
22,23e
The reactionhas alsobeenem-
ployed in diversity oriented synthesis fashion.
24
An aza-variant of
the reaction is also reported in the literature.
25
Thus Achmatowicz
reaction was employed to obtain compound 7, which was then con-
verted into rac-seven-membered bicyclic enone 9 via [5+2] cycload-
dition procedure reported previously.
23l,26
The oxa-bridged a,b-
unsaturated ketone 9 was reduced under Luches conditions. The
resultant racemic mixture of allylic alcohols 10was acetylatedusing
Ac
2
O/Et
3
N in the presence of a catalytic amount of DMAP to yield a
racemic mixture of oxa-bridged acetate 11, which upon treatment
with AD mixb gave a mixture of seven-membered 1,5-anhydro
O O
7 8
9
AcO
O O
O
O
EtO
a
O
O
OEt
b
O
OAc
EtO
O
OAc
EtO
( )-12
d
HO
OH
( )-11
+
e
O
AcO
OEt
( )-12
+
OH
OH
10 (R = H)
O
OR
EtO
O
RO
OEt
11 (R = Ac)
c
Scheme 1. Synthesis of optically active 1,5-anhydro carbasugars, ()-12 and (+)-
12. Reagents and conditions: (a) Refs. 12,13; (b) NaBH
4
, CeCl
3
7H
2
O, MeOH, 0 C to
rt, 4 h, 94%; (c) Ac
2
O, Et
3
N, DCM, 0 C to rt, 5 h, 80%; (d) AD mix-b, MeSO
2
NH
2
,
t
BuOH:H
2
O (1:1), 0 C, 24 h, 42% (()-12) and 45% ((+)-11); (e) OsO
4
, NMO,
t
BuOH:H
2
O (1:1), rt, 12 h, 87%.
9
b a
EtO
HO
c
EtO
RO
OR
OR
EtO
BzO
OBz
OBz
( )-17
g
d
16 (R = H)
17 (R = Bz)
EtO
RO
OR
OR
EtO
( )-17
BzO
OBz
OBz
f
18 (R = H)
19 (R = Bz)
f
e
g
()-15
O
OH
EtO
O
HO
OEt
13
O
Cl
EtO
O
Cl
OEt
14
OEt
OH
Scheme 2. Synthesis of ()-1b,4b,5b-tribenzoyloxy-2a-ethoxy cycloheptane, ()-17, and (+)-1a,4a,5a-tribenzoyloxy-2b-ethoxy cycloheptane, (+)-17. Reagents and
conditions: (a) NaBH
4
, NiCl
2
6H
2
O, THF, rt, 0.5 h; (b) SOCl
2
, DMF (cat), DCM, rt, 24 h; (c) Na, anhyd Et
2
O, rt, 16 h; (d) AD mix-b, MeSO
2
NH
2
,
t
BuOHH
2
O (1:1), 0 C, 24 h, then rt,
1 h, 85%; (e) AD mix-a, MeSO
2
NH
2
,
t
BuOHH
2
O (1:1), 0 C, 24 h, then rt, 1 h, 85%; (f) benzoyl chloride, pyridine, overnight, 95%; (g) fractional crystallization from EtOAc/
hexane (90% v/v).
O
OAc
EtO
HO
OH
( )-12
+
Figure 2. ORTEP drawing of X-Ray structure of (+)-12.
3600 A. A. Yadav et al. / Tetrahedron Letters 53 (2012) 35993602
carbasugar ()-12 and unreacted (+)-11 (Scheme 1). Flash column
chromatography of the mixture on silica gel afforded the separation
of optically active seven-membered carbasugar ()-12 [C
11
H
18
O
6
found: 269.1341 (MNa
+
), Calcd: 269.1336; a
D
= 14.9 (c 0.2,
CHCl
3
)] in 42% yield, and the acetate (+)-11 (approx. 45%);
a
D
= +48.28 (c 1.0, CHCl
3
).
Osmylation of the unreacted compound (+)-11 using catalytic
amounts of OsO
4
in
t
BuOH:H
2
O(1:1) using NMOas a co-oxidant gave
compound (+)-12. The structure and relative conguration of the
resultant dihydroxy mono acetate (+)-12 [a
D
= +18.91 (c 0.25,
CHCl
3
)] was unambiguously established by single crystal X-ray anal-
ysis (see Fig. 2) to be (+)-2a-acetoxy-6a-ethoxy-3b,4b-dihydroxy-
1,5-anhydro cycloheptane ((+)-12).
27
Based on literature analogies,
on comparison of signs and magnitude of optical rotations, and
NMR data of (+)-12, and the corresponding data of the optically re-
solved seven-membered ()-1,5-anhydrocarbasugar ()-12, it was
deduced that they are enantiomerically related to each other. Com-
pound ()-12, therefore, has been identied as ()-2a-acetoxy-6a-
ethoxy-3b,4b-dihydroxy-1,5-anhydro cycloheptane (()-12). The
ORTEP drawing of X- ray structure of (+)-12 is given in Figure 2.
After the successful synthesis of optically active seven-mem-
bered 1,5-anhydro carbasugars ()-12 and (+)-12, we extended
the methodology to synthesize conformationally exible tetra-
hydroxy cycloheptane derivatives. Thus rac-6a-ethoxy-8-oxabicy-
clo[3.2.1]oct-3-en-2-one (9) was transformed to stereochemically
well dened 2a-ethoxy-1b-hydroxy cyclohept-4-ene (15) follow-
ing the known procedure.
23l
We, therefore, resorted to asymmetric
dihydroxylation of 15 for the synthesis of optically active 2-eth-
oxy-1,4,5-trihydroxy cycloheptanes (Scheme 2). In principle, reac-
tion of ()-15 with either of the AD mix reagents may give a
mixture of four chiral cis-dihydroxylated compounds. The mixture
of compounds so obtained may comprise of two pairs of enantio-
mers and one of the pairs may correspond to (+)-17 and ()-17.
Keeping the above in mind, compound ()-15 was treated with
AD mix-b in
t
BuOHH
2
O (1:1) to give an inseparable mixture of tri-
hydroxy compounds 16. The mixture 16 was subsequently con-
verted into a mixture of tribenzoates 17 which upon fractional
crystallization furnished a colorless crystalline compound
[a
D
= 181.28 (c 0.1, CHCl
3
); mp 7778 C], which showed
1
H
NMR signals at d 8.08 (m, 6H), 7.57 (m, 3H), 7.44 (m, 6H), 5.69
(m, 1H), 5.62 (dd, J = 3.3, 2.7 Hz, 1H), 5.31 (m, 1H), 3.96 (m, 1H),
3.58 (m, 2H), 2.63 (m, 1H), 2.17 (m, 5H), 1.22 (t, J = 6.96 Hz, 3H),
and
13
C NMR signals at d 165.6, 165.5, 165.4, 133 (x3), 130.3
(x3), 129.6 (x3), 128.4 (x6), 76.7, 76.6, 73.4, 70.4, 65.1, 30.0, 25.3,
25.2, and 15.4. The structure and relative conguration of the sep-
arated optically active crystalline tribenzoate was established to be
()-1b,4b,5b-tribenzoyloxy-2a-ethoxy cycloheptane (()-17) by
single crystal X-ray analysis.
28
The ORTEP drawing of the same is
given in Figure 3.
Similarly, compound ()-15 was transformed into colorless
crystalline tribenzoate (+)-17 [mp 7779 C; a
D
= +190.84 (c
0.1, CHCl
3
)] by reaction with AD mix-a followed by benzoylation
and fractional crystallization of the mixture of tribenzoates 19.
As before, the structure and relative conguration of (+)-17 was as-
signed on the basis of single crystal X-ray analysis as (+)-1a,4a,5a-
tribenzoyloxy-2b-ethoxy cycloheptane ((+)-17).
29
The ORTEP
drawing of the X-ray structure of (+)-17 is given in (Fig. 4).
It is apparent from the NMR data, and the signs and orders of
optical rotations of ()-17 and (+)-17 that they ought to be optical
antipodes of each other. In addition to the work presented here, it
EtO
BzO
OBz
OBz
( )-17
Figure 3. ORTEP drawing of ()-1b,4b,5b-tribenzoyloxy-2a-ethoxy cycloheptane, ()-17.
EtO
( )-17
BzO
OBz
OBz
Figure 4. ORTEP drawing of the X-ray structure of (+)-1a,4a,5a-tribenzoyloxy-2b-ethoxy cycloheptane, (+)-17.
A. A. Yadav et al. / Tetrahedron Letters 53 (2012) 35993602 3601
is noteworthy that to the best of our knowledge there are only a
few reports in the literature
16,30
on the asymmetric dihydroxyla-
tion of cycloheptene systems using AD mix-a and AD mix-b.
In summary, synthesis of optically active 1,4,5-tribenzoyloxy-2-
ethoxy-cycloheptanes (()-17 and (+)-17) and seven-membered
1,5-anhydrocarbasugars (()-12 and (+)-12) from readily accessi-
ble starting materials has been devised and successfully achieved.
Acknowledgments
P.S.S. thanks CSIR for senior research fellowship. Financial sup-
port from DRDO, CSIR, UGC, New Delhi, India, is gratefully
acknowledged. We sincerely thank National Single Crystal X-ray
Diffraction facility at IIT Bombay for the X-ray crystal structures
of (+)-12, ()-17 and (+)-17.
Supplementary data
Supplementary data (synthesis of compounds 10(+)-17 along
with
1
H ,
13
C NMR, optical rotation, and mass spectrometry data,
where applicable, are specied. Synthesis of compound 9 and other
starting materials were reported previously.
23l
X-ray crystallo-
graphic data for compounds (+)-12, ()-17, and (+)-17 can be ac-
cessed from Cambridge Crystallographic Data Centre (CCDC),
Cambridge, UK.) associated with this article can be found, in the
online version, at http://dx.doi.org/10.1016/j.tetlet.2012.05.014.
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27. Selected X-ray crystallographic data for (+)-12 (C
11
H
18
O
6
): Space group:
Triclinic, P-1; unit cell dimensions: a = 5.3401(5) , b = 8.763(4) ,
c = 12.8726(18) ; V = 577.4(3) A
3
; Z = 2, D
calcd
= 1.416 Mg/m
3
; absorption
coefcient = 0.115 mm
1
. Complete crystallographic data (excluding
structure factors) for this structure have been deposited with the Cambridge
Crystallographic Data Centre as supplementary publication number CCDC
869019. Copies of the data can be obtained, free of charge, on application to
CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax: +44 1223 336033 or e-
mail: deposit@ccdc.cam.ac.uk).
28. Selected X-ray crystallographic data for ()-17 (C
30
H
30
O
7
): Space group:
Monoclinic, P 21/a; unit cell dimensions: a = 13.2741(9) , b = 13.2808(10) ,
c = 16.0052(10) ; V = 2753.4(3) A
3
; Z = 4, D
calcd
= 1.212 Mg/m
3
; absorption
coefcient = 0.086 mm
1
. Complete crystallographic data (excluding
structure factors) for this structure have been deposited with the Cambridge
Crystallographic Data Centre as supplementary publication number CCDC
869020. Copies of the data can be obtained, free of charge, on application to
CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax: +44 1223 336033 or e-
mail: deposit@ccdc.cam.ac.uk).
29. Selected X-ray crystallographic data for (+)-17 (C
30
H
30
O
7
): Space group:
Monoclinic, P 21/a; unit cell dimensions: 13.2558(7) , b = 13.2950(7) ,
c = 15.9991(6) ; V = 2751.9(2) A
3
; Z = 4, D
calcd
= 1.213 Mg/m
3
; absorption
coefcient = 0.086 mm
1
. Complete crystallographic data (excluding
structure factors) for this structure have been deposited with the Cambridge
Crystallographic Data Centre as supplementary publication number CCDC
869021. Copies of the data can be obtained, free of charge, on application to
CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax: +44 1223 336033 or e-
mail: deposit@ccdc.cam.ac.uk).
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