Hydroxylamine derivatives as nucleophiles in ferrier glycosylation: Synthesis of aminoxy pseudoglycals

Article abstract of DOI:10.1055/s-2007-1000828

The use of hydroxylamine derivatives as the aminoxy equivalent nucleophiles in Ferrier glycosylation catalyzed by various acid catalysts is described. The reaction of tri-O-protected D-glucal with N-hydroxyphthalimide or N-hydroxysuccinimide was effectively promoted by a catalytic amount of zinc(II) chloride to produce the corresponding aminoxy pseudoglycal in good yields and preferential anomeric selectivity. Georg Thieme Verlag Stuttgart.

Full text of DOI:10.1055/s-2007-1000828

122
PAPER
Hydroxylamine Derivatives as Nucleophiles in Ferrier Glycosylation:
Synthesis of Aminoxy Pseudoglycals1
Synthesis of
Ami
h
noxy
P
seudo
.
glycals Raji Reddy,* Y. Srinivasa Rao, T. Pavan Kumar, K. Venkatram Reddy, S. Chandrasekhar
Organic Division - I, Indian Institute of Chemical Technology, Hyderabad 500007, India
Fax +91(40)27160512; E-mail: rajireddy@iict.res.in
Received 20 July 2007; revised 9 October 2007
the use of hydroxylamine derivatives as the aminoxy
equivalent of nucleophiles in palladium-catalyzed addi-
tion to Baylis–Hillman acetate adducts.13 To further ex-
ploit the applications of hydroxylamine derivatives,14
Abstract: The use of hydroxylamine derivatives as the aminoxy
equivalent nucleophiles in Ferrier glycosylation catalyzed by vari-
ous acid catalysts is described. The reaction of tri-O-protected
D-glucal with N-hydroxyphthalimide or N-hydroxysuccinimide was
effectively promoted by a catalytic amount of zinc(II) chloride to herein we report the nucleophilic addition of hydroxyl-
produce the corresponding aminoxy pseudoglycal in good yields
and preferential anomeric selectivity.
amine derivatives [N-hydroxyphthalimide (1b) or N-hy-
droxysuccinimide (2b)] on tri-O-protected D-glucal,
catalyzed by 2 mol% zinc(II) chloride in dichlo-
romethane, to obtain the corresponding pseudoglycal
products (Scheme 1).
Key words: hydroxylamines, Ferrier glycosylation, pseudoglycals
Aminoxy functionality is gaining importance in organic
chemistry and plays an important role in asymmetric syn-
thesis via its oxime derivatives.2 In particular, carbohy-
drates bearing an aminoxy group have proved to be very
useful synthons in the synthesis of glycoconjugates and in
peptide chemistry.2a–c,3 The replacement of an amino
group with aminoxy functionality in a- and b-amino acids
allows one to visualize extended secondary structures in
short peptides.4 There are a few methods that have been
described for the synthesis of aminoxy carbohydrates us-
ing the glycosylation of penta-O-acetylated glucohalides
with N-hydroxysuccinimide or N-hydroxyphthalimide,
Initially, we surveyed the catalytic activity of various acid
catalysts in the reaction of tri-O-acetyl-D-glucal with
N-hydroxyphthalimide (1b) in dichloromethane at room
temperature (Table 1). Among the catalysts tested,
zinc(II) chloride was found to be more effective than other
catalysts in terms of yield, reaction profile and selectivity
(Table 1, entry 6). However, other catalysts [BF3·OEt2,12
PTSA, FeCl3 and B(C6F5)3] also provided pseudoglycal
Table 1 Catalytic Activity of Various Acid Catalysts in Glycosyla-
tion of Tri-O-acetyl-D-glucal (1a) with N-Hydroxyphthalimide (1b)
however, the products are not the pseudoglycals (Ferrier Entry Lewis acid
Time
(h)
Yield
(%)a
Anomericratio
(2 mol%)
BF3·OEt2
PTSA
(a/b)b
products).2a–c,5 Pseudoglycals (2,3-unsaturated glyco-
sides) are valuable intermediates in the synthesis of glyco-
peptides and represent an important class of compounds
due to the presence of a double bond between C-2 and C-
3 which may be easily modified.6 The prevalent method
with which to obtain pseudoglycals is Ferrier glycosyla-
tion,7 which is known to occur with various nucleophiles
such as carbon,8 nitrogen,9 oxygen10 and/or sulfur
nucleophiles11 in the presence of acid catalysts. The com-
monly used oxygen nucleophiles are alcohols and, inter-
estingly, there is no general report in the literature on the
use of hydroxylamines as nucleophiles in Ferrier glycosy-
lation, except one example.12 We have recently disclosed
1
2
3
4
5
6
3.5
6
73
9:1
9:1
82
I2
15
3
no reaction
–
FeCl3
94
88
96
50:1
15:1
50:1
B(C6F5)3
ZnCl2
5
2.5
a Isolated yields refer to anomeric mixtures after purification.
b The anomeric ratio was determined on the basis of integration of the
anomeric hydrogen in the 1H NMR spectrum.
O
O
O
O
O
ZnCl2 (2 mol%)
CH2Cl2, r.t., 2.5 to 4.5 h
RO
RO
RO
RO
N
HO
N
+
O
O
OR
R = Ac, Bn, allyl or Me
Scheme 1
SYNTHESIS 2008, No. 1, pp 0122–0126
x
x
.
x
x
.2
0
0
7
Advanced online publication: 07.12.2007
DOI: 10.1055/s-2007-1000828; Art ID: Z17707SS
© Georg Thieme Verlag Stuttgart · New York

PAPER
Synthesis of Aminoxy Pseudoglycals
123
products, albeit with moderate yields and selectivity. No chromatography (Table 2, entry 2). Glycosylation of tri-
reaction proceeded with iodine catalyst (Table 1, entry 3). O-benzyl-D-glucal (2a) with 1b and 2b under the de-
scribed reaction conditions provided the corresponding
Encouraged by this observation, various tri-O-protected
products 3c and 4c in 94% and 86% yields, respectively,
D-glucals were treated with 1b or 2b, in the presence of 2
with the a-anomer being formed as the major product
mol% ZnCl2, typically at room temperature in dichlo-
romethane; the observed results are presented in Table 2.
(Table 2, entries 3 and 4).
The reaction of tri-O-acetyl-D-glucal (1a) with N-hy- Tri-O-allyl and tri-O-methyl-D-glucals were also equally
droxyphthalimide (1b) was completed in 2.5 hours to give participative to the present reaction conditions to afford
the corresponding pseudoglycal 1c in 96% yield with the the corresponding pseudoglycals 5c–8c (Table 2, entries
a-anomer formed as the major product (Table 2, entry 5–8). The a/b ratio of the products was determined by
1
1).15 Similarly, N-hydroxysuccinimide (2b) reacted well analysis of the H NMR spectrum of the crude product;
with 1a under the same reaction conditions to afford the stereochemistry of predominant product was con-
pseudoglycal 2c in 90% yield after purification by column firmed by NOESY measurements to be the a-anomer.
Table 2 ZnCl2-Catalyzed Ferrier Glycosylation of Tri-O-protected D-Glucosals with Hydroxylamine Derivates
Entry
Glucal
Hydroxylamine derivate Time
(h)
Pseudoglycal
Yield
(%)a
Anomeric ratio
(a/b)b
O
O
AcO
AcO
O
O
O
AcO
NPhth
NSuc
HO
N
1
2.5
3.5
96
90
50:1
20:1
AcO
OAc
O
1c
1a
1a
1b
O
O
AcO
HO
N
2
AcO
O
2c
2b
1b
O
O
O
O
BnO
BnO
BnO
NPhth
NSuc
NPhth
3
4
5
3
4
3
94
86
94
40:1
16:1
30:1
BnO
OBn
3c
2a
2a
O
BnO
2b
1b
BnO
4c
O
AllylO
AllylO
O
O
AllylO
AllylO
OAllyl
5c
3a
3a
O
O
AllylO
NSuc
6
7
8
2b
1b
2b
4.5
4
82
91
78
15:1
40:1
15:1
AllylO
6c
O
O
O
MeO
MeO
MeO
NPhth
NSuc
MeO
OMe
7c
4a
4a
O
O
MeO
4.5
MeO
8c
a Isolated yields refer to anomeric mixtures after purification.
b The anomeric ratio was determined on the basis of integration of the anomeric hydrogen in the 1H NMR spectrum.
Synthesis 2008, No. 1, 122–126 © Thieme Stuttgart · New York

124
Ch. R. Reddy et al.
PAPER
O
(Boc)2O,
Et3N
THF
O
O
O
O
O
O
N2H4⋅H2O
AcO
AcO
N
AcO
AcO
NH2
AcO
AcO
NHBoc
CH2Cl2–MeOH (1:1)
O
r.t., 3 h, 90%
r.t., 30 min, 65%
1c
1d
1e
PhCHO, CH2Cl2
r.t., 24 h, 60%
O
O
N
Ph
O
O
N
Ph
OsO4 (cat.), NMO
acetone–H2O (4:1),
AcO
AcO
AcO
OH
AcO
r.t., 48 h, 86%
OH
1g
1f
Scheme 2
Pseudoglycals 1c–8c; General Procedure
Having developed a useful Ferrier glycosylation, we next
examined the transformations of the product 1c obtained
from the reaction described above (Scheme 2). Accord-
ingly, the product 1c was subjected to deprotection of the
phthalimide group using hydrazine hydrate in a mixture of
dichloromethane–methanol (1:1) to give the aminoxy
compound 1d in 65% yield, which was treated with di-
tert-butyl dicarbonate in the presence of triethyl amine to
obtain the N-Boc derivative 1e in 90% yield. Subsequent-
ly, the compound 1d was treated with benzaldehyde in
dichloromethane for 24 hours at room temperature to pro-
vide the corresponding oxime 1f in 60% yield, which was
further subjected to dihydroxylation using catalytic osmi-
um tetroxide in N-methylmorpholine N-oxide (OsO4/
NMO) for 48 hours to yield the dihydroxy oxime deriva-
tive 1g (Scheme 2).16 The aminoxy compounds 1d and 1e
can be used as intermediates for the synthesis of bio-ac-
tive molecules via amide formation with an acid, followed
by a dihydroxylation reaction.17 This study indicates the
utility of the resulting products in the synthesis of more
advanced intermediates for the preparation of bio-active
molecules or in peptide chemistry. Further applications of
these products are underway in our laboratory and will be
reported in the near future.
To a stirred solution of tri-O-protected D-glucal 1a–4a (1 mmol) in
CH2Cl2 (5 mL) was added hydroxylamine derivative 1b–2b (1.1
mmol) followed by ZnCl2 (0.02 mmol). The reaction mixture was
stirred at r.t. for the given time (see Table 1). After complete con-
version (monitored by TLC), the reaction mixture was diluted with
H2O (5 mL) and extracted with CH2Cl2 (2 × 10 mL). The organic
layers were dried over anhydrous Na2SO4 and purified by column
chromatography on silica gel (60–120 mesh) to afford the corre-
sponding pseudoglycal 1c–8c.
Spectral and physical data for the new products (major anomers, a)
were found as follows:
1c
Colorless solid; mp 121–124 °C; [a]D +204.0 (c 1.0, CHCl3).
1H NMR (CDCl3, 200 MHz): d = 7.86–7.81 (m, 2 H), 7.77–7.73 (m,
2 H), 6.16 (d, J = 10.2 Hz, 1 H), 6.10–6.04 (m, 1 H), 5.56 (s, 1 H),
5.42 (d, J = 9.5 Hz, 1 H), 4.66–4.60 (m, 1 H), 4.33 (dd, J = 3.2, 12.4
Hz, 1 H), 4.15 (dd, J = 3.4, 12.4 Hz, 1 H), 2.13 (s, 3 H), 2.06 (s,
3 H).
13C NMR (CDCl3, 50 MHz): d = 170.6, 170.1, 163.3 (2C), 134.4
(2C), 133.5 (2C), 128.8 (2C), 123.5, 123.2, 99.0, 68.1, 64.3, 61.9,
20.8, 20.6.
HRMS (ESI): m/z [M + Na]+ calcd for C18H17NO8Na: 398.0851;
found: 398.0841.
IR (KBr): 3449, 2935, 1734, 1376, 1225, 1150, 904, 703 cm–1.
In summary, we have described the use of hydroxylamine
derivatives as the oxygen atom nucleophiles in the Ferrier
glycosylation reaction. This transformation, efficiently
catalyzed by zinc(II) chloride, affords aminoxy pseudo-
glycal products in good yields and with high a-selectivity.
The products were also successfully transformed into use-
ful oxime derivatives and may find use in organic synthe-
sis.
2c
Viscous liquid; [a]D +254.6 (c 0.25, CHCl3).
1H NMR (CDCl3, 300 MHz): d = 6.15 (d, J = 9.8 Hz, 1 H), 6.0 (dt,
J = 2.6, 9.8 Hz, 1 H), 5.55 (s, 1 H), 5.43 (d, J = 9.0 Hz, 1 H), 4.57
(d, J = 9.8 Hz, 1 H), 4.35–4.26 (m, 1 H), 4.18–4.11 (m, 1 H), 2.73
(s, 4 H), 2.12 (s, 3 H), 2.09 (s, 3 H).
13C NMR (CDCl3, 75 MHz): d = 170.9, 170.5, 170.0 (2C), 133.5,
123.0, 98.0, 68.3, 64.2, 61.7, 25.4 (2C), 20.8, 20.7.
HRMS (ESI): m/z [M + Na]+ calcd for C14H17NO8Na: 350.0851;
found: 350.0864.
IR (KBr): 3490, 2923, 1730, 1234, 1051, 909, 651 cm–1.
Tri-O-acetyl-D-glucal, N-hydroxyphthalimide, N-hydroxysuccin-
imide and other catalysts were purchased from Aldrich and used as
received. CH2Cl2 was distilled over CaH. The optical rotations were
recorded using a Jasco Dip 360 digital polarimeter. IR spectra were
1
3c
recorded on Perkin–Elmer 683 spectrometer. H NMR (200 MHz
and 300 MHz) and 13C NMR (50 MHz and 75 MHz) spectra of sam-
ples in CDCl3 were recorded on Bruker Avance spectrometers.
Chemical shifts (d) were reported in ppm with respect to internal
TMS. Coupling constants (J) are quoted in Hz. Mass spectra were
obtained on an Agilent Technologies LC/MSD Trap SL.
Colorless solid; mp 103–105 °C; [a]D +188.0 (c 0.5, CHCl3).
1H NMR (CDCl3, 200 MHz): d = 7.85–7.77 (m, 2 H), 7.76–7.69 (m,
2 H), 7.32–7.17 (m, 10 H), 6.29 (d, J = 9.8 Hz, 1 H), 5.99–5.91 (d,
J = 10.5 Hz, 1 H), 5.54 (s, 1 H), 4.65–4.32 (m, 6 H), 3.89 (d,
J = 10.5 Hz, 1 H), 3.65 (d, J = 11.3 Hz, 1 H).
Synthesis 2008, No. 1, 122–126 © Thieme Stuttgart · New York

PAPER
Synthesis of Aminoxy Pseudoglycals
125
13C NMR (CDCl3, 50 MHz): d = 163.1 (2C), 138.0, 137.9, 135.4
(2C), 134.0 (2C), 129.3 (2C), 128.3, 128.2, 127.8 (4C), 127.7 (2C),
127.5 (2C), 123.3, 121.8, 99.5, 73.3, 71.5, 70.7, 69.6, 67.9.
1H NMR (CDCl3, 300 MHz): d = 6.30 (d, J = 10.3 Hz, 1 H), 5.88
(dt, J = 3.2, 10.8 Hz, 1 H), 5.47 (s, 1 H), 5.32 (s, 1 H), 4.21 (d,
J = 9.5 Hz, 1 H), 3.60–3.33 (m, 8 H), 2.69 (s, 4 H).
HRMS (ESI): m/z calcd for C28H25N06Na: 494.1579; found:
HRMS (ESI): m/z calcd for C12H17N06Na: 294.0953; found:
494.1561.
294.0951.
IR (KBr): 3446, 2913, 2845, 1720, 1451, 1371, 1115, 997, 746
cm–1.
IR (KBr): 3741, 3444, 2926, 1789, 1733, 1463, 1378, 1291, 1187,
1124, 965, 901, 703 cm–1.
4c
1d
Colorless solid; mp 116.1 °C; [a]D +126.7 (c 1.7, CHCl3).
To a stirred solution of compound 1c (0.375 g, 1 mmol) in CH2Cl2–
MeOH (1:1, 10 mL), was added hydrazine hydrate (3 mmol) at r.t.
and the reaction mixture was stirred for 30 min. The reaction was
quenched with sat. aq NaHCO3 (5 mL) and the aqueous layer was
extracted with CH2Cl2 (3 × 10 mL). The combined organic layers
were washed with brine (10 mL), dried over anhydrous Na2SO4 and
concentrated under reduced pressure to obtain the aminoxy com-
pound 1d.
1H NMR (CDCl3, 300 MHz): d = 7.39–7.17 (m, 10 H), 6.29 (d,
J = 10.3 Hz, 1 H), 5.88 (d, J = 10.3 Hz, 1 H), 5.55 (s, 1 H), 4.68–
4.32 (m, 6 H), 3.83 (d, J = 10.3 Hz, 1 H), 3.62 (d, J = 11.0 Hz, 1 H),
2.67 (s, 4 H).
13C NMR (CDCl3, 75 MHz): d = 171.2 (2C), 137.9 (2C), 135.4 (2C),
128.4 (2C), 128.3 (2C), 128.0 (2C), 127.8 (2C), 121.6 (2C), 98.6,
73.4, 71.5, 70.6, 69.5, 67.7, 25.5 (2C).
Yield: 0.16 g (65%); colorless viscous liquid.
HRMS (ESI): m/z calcd for C24H25N06Na: 446.1579; found:
446.1593.
1H NMR (CDCl3, 300 MHz): d = 5.92 (d, J = 10.2 Hz, 1 H), 5.83–
5.64 (m, 1 H), 5.31 (d, J = 9.5 Hz, 1 H), 5.23 (s, 1 H), 4.25–3.96 (m,
3 H), 2.14 (s, 6 H).
13C NMR (CDCl3, 75 MHz): d = 170.1, 169.5, 130.7, 125.6, 96.1,
67.1, 65.1, 62.9, 20.8, 20.6.
IR (KBr): 3443, 2923, 2854, 1726, 1455, 1369, 1206, 1121, 997,
749, 651 cm–1.
5c
Viscous liquid; [a]D +154 (c 0.5, CHCl3).
EIMS: m/z = 268.0 [M + Na]+.
1H NMR (CDCl3, 200 MHz): d = 7.85–7.78 (m, 2 H), 7.76–7.69 (m,
2 H), 6.30 (d, J = 10.1 Hz, 1 H), 6.0–5.78 (m, 3 H), 5.53 (s, 1 H),
5.34–5.09 (m, 5 H), 4.39–3.80 (m, 7 H).
IR (KBr): 3550, 3440, 3080, 2934, 2793, 1732, 1455, 1376, 1240,
1150, 1063, 695 cm–1.
1e
13C NMR (CDCl3, 75 MHz): d = 163.2 (2C), 135.6 (2C), 134.5 (2C),
134.0 (2C), 129.3 (2C), 123.3, 121.7, 117.2, 117.0, 99.5, 72.3, 70.6,
70.4, 69.2, 67.8.
To a stirred solution of compound 1d (0.245 g, 1 mmol) in THF
(5 mL) at r.t., was added Et3N (2 mmol) and Boc2O (1 mmol). The
reaction was stirred for 3 h then quenched with H2O (5 mL) and the
aqueous layer was extracted with EtOAc (3 × 10 mL). The com-
bined organic layers were washed with brine (10 mL), dried over
anhydrous Na2SO4, concentrated under reduced pressure and the
crude product was purified by silica gel (60–120) column chroma-
tography (EtOAc–hexane, 20%) to yield 1e.
HRMS (ESI): m/z calcd for C20H21N06Na: 394.1266; found:
394.1261.
IR (KBr): 3442, 3076, 2957, 2861, 1992, 1686, 1607, 1479, 1391,
1146, 1060, 941, 745, 670 cm–1.
6c
Yield: 0.315 g (90%); colorless viscous liquid; [a]D –60.4 (c 1.0,
Viscous liquid; [a]D +139.8 (c 1.95, CHCl3).
1H NMR (CDCl3, 300 MHz): d = 6.05–5.74 (m, 4 H), 5.40–5.03 (m,
5 H), 4.21–3.71 (m, 8 H), 3.71–3.55 (m, 4 H).
13C NMR (CDCl3, 75 MHz): d = 171.0 (2C), 135.6, 134.4, 121.5
(2C), 117.3 (2C), 98.5, 72.4, 70.5, 70.4, 69.1, 67.7, 25.5 (2C).
CHCl3).
1H NMR (CDCl3, 300 MHz): d = 5.90 (d, J = 10.2 Hz, 1 H), 5.85–
5.64 (m, 1 H), 5.45–5.39 (m, 1 H), 4.36 (dd, J = 12.4, 3.4 Hz, 1 H),
4.2 (d, J = 9.5 Hz, 1 H), 4.10–3.95 (m, 2 H), 1.95 (s, 3 H), 1.88 (s,
3 H), 1.45 (s, 9 H).
13C NMR (CDCl3, 75 MHz): d = 171.6, 170.8, 156.6, 134.7, 124.5,
HRMS (ESI): m/z calcd for C16H21N06Na: 346.1266; found:
346.1259.
96.0, 70.6, 63.8, 63.4, 60.3, 28.4, 21.0, 20.9.
EIMS: m/z = 367.0 [M + Na]+.
IR (KBr): 3852, 3744, 3446, 2925, 1733, 1645, 1512, 1461, 1374,
1290, 1127, 966, 924, 703 cm–1.
IR (KBr): 3450, 3090, 2934, 2793, 1734, 1720, 1465, 1376, 1230,
1150, 1060, 703 cm–1.
7c
Viscous liquid; [a]D +168.5 (c 2.0, CHCl3).
1f
1H NMR (CDCl3, 200 MHz): d = 7.86–7.68 (m, 4 H), 6.32 (d,
J = 10.3 Hz, 1 H), 5.96 (dt, J = 2.8, 10.3 Hz, 1 H), 5.52 (s, 1 H),
4.34–4.22 (m, 1 H), 4.08 (d, J = 9.5 Hz, 1 H), 3.62–3.34 (m, 8 H).
13C NMR (CDCl3, 75 MHz): d = 163.1 (2C), 134.9 (2C), 134.1 (2C),
129.2 (2C), 123.3, 121.8, 99.5, 75.0, 70.9, 70.2, 59.1, 56.7.
To a stirred solution of compound 1e (0.345 g, 1 mmol) in CH2Cl2
at r.t., was added benzaldehyde (1 mmol). The reaction mixture was
stirred for 24 h then quenched with H2O (5 mL) and the aqueous
layer was extracted with CH2Cl2 (3 × 10 mL). The combined organ-
ic extracts were washed with brine (10 mL), dried over anhydrous
Na2SO4 and concentrated under reduced pressure to obtain the prod-
uct 1f.
HRMS (ESI): m/z calcd for C16H17N06Na: 342.0953; found:
342.0948.
Yield: 0.18 g (60%); colorless solid; mp 134.7–137.0 °C; [a]D
+52.6 (c 1.0, CHCl3).
1H NMR (CDCl3, 300 MHz): d = 8.11 (s, 1 H), 7.65–7.56 (m, 2 H),
7.40–7.29 (m, 3 H), 6.04–5.87 (m, 2 H), 5.76 (s, 1 H), 5.34 (d,
J = 9.8 Hz, 1 H), 4.28–4.05 (m, 3 H), 2.10 (s, 3 H), 1.98 (s, 3 H).
IR (KBr): 3446, 2924, 2853, 1788, 1734, 1462, 1372, 1186, 1123,
1100, 964, 901, 761 cm–1.
8c
Viscous liquid; [a]D +133.6 (c 0.4, CHCl3).
Synthesis 2008, No. 1, 122–126 © Thieme Stuttgart · New York

126
Ch. R. Reddy et al.
PAPER
13C NMR (CDCl3, 75 MHz): d = 170.3, 169.7, 150.6, 134.3, 131.6,
131.5, 130.9, 130.5, 130.2, 128.6, 128.4, 96.2, 67.4, 65.0, 62.6,
20.8, 20.6.
Angerbauer, R. Carbohydr. Res. 1981, 89, 159.
(h) Danishefsky, S. J.; Bilodeau, M. T. Angew. Chem., Int.
Ed. Engl. 1996, 30, 1357. (i) Bussolo, V. D.; Kim, Y.-J.;
Gin, D. Y. J. Am. Chem. Soc. 1998, 120, 13515.
(j) Tolstikov, A. G.; Tolstikov, G. A. Russ. Chem. Rev. 1993,
62, 579.
HRMS (ESI): m/z calcd for C17H19N06Na: 356.0861; found:
356.0876.
IR (KBr): 3432, 3029, 2922, 1450, 1302, 1096, 925, 695 cm–1.
(7) (a) Ferrier, R. J.; Prasad, N. J. Chem. Soc. C 1969, 1, 570.
(b) For a review on the Ferrier rearrangement, see: Ferrier,
R. J. Top. Curr. Chem. 2001, 215, 153. (c) For a review on
glycosidation, see: Toshima, K.; Tatsuta, K. Chem. Rev.
1993, 93, 1503.
1g
To a stirred solution of compound 1f (0.333 g, 1 mmol) in acetone–
H2O (4:1, 10 mL) at r.t., were added 4-methylmorpholine N-oxide
(1.3 mmol) and a catalytic amount of OsO4. The reaction was stirred
for 48 h then quenched with sat. aq sodium sulfite (5 mL) and the
acetone was removed under reduced pressure. The aqueous layer
was extracted with EtOAc (3 × 10 mL) and the combined organic
layers were washed with brine (10 mL), dried over anhydrous
Na2SO4, concentrated under reduced pressure and the crude product
was purified by silica gel (60–120) column chromatography
(EtOAc–hexanes, 80%) to yield the compound 1g.
(8) (a) Takhi, M.; Abdel-Rahman, A. A.-H.; Schmidt, R. R.
Tetrahedron Lett. 2001, 42, 4053. (b) Yadav, J. S.; Reddy,
B. V. S.; Chand, P. K. Tetrahedron Lett. 2001, 42, 4057.
(c) Yadav, J. S.; Reddy, B. V. S.; Raman, J. V.; Niranjan, N.;
Kumar, S. K.; Kunwar, A. C. Tetrahedron Lett. 2002, 43,
2095. (d) Das, K. S.; Reddy, K. A.; Abbineni, C.; Roy, J.;
Rao, K. V. L. N.; Sachwani, R. H.; Iqbal, J. Tetrahedron
Lett. 2003, 44, 4507; and references cited therein.
(9) (a) Chandrasekhar, S.; Reddy, Ch. R.; Chandrashekar, G.
Tetrahedron Lett. 2004, 45, 6481. (b) Yadav, J. S.; Reddy,
B. V. S. Synthesis 2002, 511. (c) Houston, T. A.; Chervin,
S. M.; Koreeda, M. ITE Lett. Batter. New Technol. Med.
2002, 3, 23. (d) Kawabata, H.; Kubo, S.; Hayashi, M.
Carbohydr. Res. 2001, 333, 153; and references cited
therein.
(10) (a) Smitha, G.; Reddy, Ch. S. Synthesis 2004, 834.
(b) Bettadaiah, B. K.; Srinivas, P. Tetrahedron. Lett. 2003,
44, 7257. (c) Shanmugasundaram, B.; Bose, A. K.;
Balasubramanian, K. K. Tetrahedron Lett. 2002, 43, 6795.
(d) Swamy, N. R.; Venkateshwarlu, Y. Synthesis 2002, 598.
(e) Takhi, M.; Abdel-Rahman, A. A.-H.; Schmidt, R. R.
Synlett 2001, 427. (f) Masson, C.; Soto, J.; Bessodes, M.
Synlett 2000, 1281. (g) Yadav, J. S.; Reddy, B. V. S.;
Murthy, C. V. S. R.; Kumar, G. M. Synlett 2000, 1450.
(h) Babu, B. S.; Balasubramanian, K. K. Tetrahedron Lett.
1999, 40, 5777.
Yield: 0.315 g (86%); colorless viscous liquid; [a]D –46.0 (c 1.0,
CHCl3).
1H NMR (CDCl3, 300 MHz): d = 8.15 (s, 1 H), 7.72–7.58 (m, 2 H),
7.37–7.08 (m, 3 H), 5.65 (s, 1 H), 5.08 (t, J = 7.2 Hz, 1 H), 4.32 (dd,
J = 12.40, 3.80 Hz, 1 H), 4.05–4.16 (m, 2 H), 3.85–3.96 (m, 2 H),
2.13 (s, 3 H), 1.95 (s, 3 H).
13C NMR (CDCl3, 75 MHz): d = 171.9, 171.1, 152.0, 131.3, 130.8,
129.0, 127.6, 101.6, 70.6, 70.0, 69.5, 68.7, 62.5, 21.1, 20.9.
MS (EI): m/z = 368.1 [M + H]+, 390.1 [M + Na]+.
IR (KBr): 3542, 3070, 2957, 2863, 1992, 1686, 1607, 1479, 1391,
1146, 1060, 940, 745 cm–1.
Acknowledgment
Y.S.R. and T.P.K. thank CSIR, New Delhi for financial assistance.
(11) (a) Yadav, J. S.; Reddy, B. V. S.; Geetha, V. Synth.
Commun. 2003, 33, 717. (b) Babu, B. S.; Balasubramanian,
K. K. Tetrahedron Lett. 1999, 40, 5777; and references cited
therein.
(12) Rajendra, M.; Srivastava, R. M.; Oliveira, F. J. S.; da Silva,
L. P.; Filho, J. R. F.; Oliveira, S. P.; Lima, V. L. M.
Carbohydr. Res. 2001, 332, 335; in this report the authors
used BF3·OEt2 as a catalyst in benzene and observed the
formation of only the a-anomer.
(13) Reddy, Ch. R.; Kiranmai, N.; Kiran Babu, G. S.; Sarma, D.
G.; Jagadeesh, B.; Chandrasekhar, S. Tetrahedron Lett.
2007, 48, 215.
(14) (a) Miyabe, H.; Yoshida, K.; Yamaguchi, M.; Takemoto, Y.
J. Org. Chem. 2005, 70, 2148. (b) Miyabe, H.; Matsumura,
A.; Moriyama, K.; Takemoto, Y. Org. Lett. 2004, 6, 4631.
(c) Miyabe, H.; Yoshida, K.; Matsumura, A.; Yamaguchi,
M.; Takemoto, Y. Synlett 2003, 567.
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Synthesis 2008, No. 1, 122–126 © Thieme Stuttgart · New York