Synthesis of 1,6-anhydro-2,3,4-trideoxy-2,3-epimino- and 1,6-anhydro-2,3,4-trideoxy-3,4-epimino-β-D-hexopyranoses and their NMR and infrared spectra

Article abstract of DOI:10.1135/cccc20041939

A complete series of 2,3,4-trideoxy-2,3-epimino and 2,3,4-trideoxy-3,4- epimino derivatives of 1,6-anhydro-β-D-hexopyranoses were prepared by lithium aluminium hydride reduction of vicinal trans azido tosylates. Unusual formation of the aziridine ring from precursors with the trans-diequatorial arrangement of the reacting groups was observed. NMR and infrared spectra of the aziridines are discussed.

Full text of DOI:10.1135/cccc20041939

Epimino-β-D-hexopyranoses
1939
SYNTHESIS OF 1,6-ANHYDRO-2,3,4-TRIDEOXY-2,3-EPIMINO- AND
1,6-ANHYDRO-2,3,4-TRIDEOXY-3,4-EPIMINO-β-D-HEXOPYRANOSES
AND THEIR NMR AND INFRARED SPECTRA
a,
b
c
Jindřich KARBAN *, Miloš BUDĚŠÍNSKÝ and Jiří KROUTIL
a
Institute of Chemical Process Fundamentals, Academy of Sciences of the Czech Republic,
165 02 Prague 6, Czech Republic; e-mail: karban@icpf.cas.cz
Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic,
166 10 Prague 6, Czech Republic; e-mail: milos.budesinsky@uochb.cas.cz
Department of Organic and Nuclear Chemistry, Charles University,
b
c
128 40 Prague 2, Czech Republic; e-mail: kroutil@natur.cuni.cz
Received Jun e 23, 2004
Accepted Septem ber 10, 2004
Dedicated to Professor Miloslav Černý on the occasion of his 75th birthday.
A com plete series of 2,3,4-trideoxy-2,3-epim in o an d 2,3,4-trideoxy-3,4-epim in o derivatives
of 1,6-an h ydro-β-D-h exopyran oses were prepared by lith ium alum in ium h ydride reduction
of vicin al trans azido tosylates. Un usual form ation of th e aziridin e rin g from precursors with
th e trans-diequatorial arran gem en t of th e reactin g groups was observed. NMR an d in frared
spectra of th e aziridin es are discussed.
Keyw ord s: An h ydrosugars; 1,6-An h ydro-β-D-h exopyran oses; Azides; Aziridin es; NMR spec-
troscopy; In frared spectroscopy; Pyram idal in version ; Carboh ydrates; Am in osugars.
Durin g th e recen t years our in terest in aziridin e derivatives of carbo-
h ydrates1–5 (called also epim in es) as useful ch iral syn th on s led us to th e
syn th esis of th e com plete series of aziridin e derivatives of 1,6-an h ydro-
β-D-h exopyran oses. Th e syn th esis in volved th e reductive cyclization 2,6–8 of
suitable vicin al trans azido tosylates usin g lith ium alum in ium h ydride or
th e Mitsun obu reaction 1,9 of suitable vicin al trans ben zylam in o h ydroxy
derivatives as th e key steps of th e syn th esis. Now we wish to report an ex-
ten sion of th e form er m eth od to th e syn th esis of 1,6-an h ydro-2,3,4-tri-
deoxy-2,3-epim in o- an d 1,6-an h ydro-2,3,4-trideoxy-3,4-epim in o-β-D-h exo-
pyran oses as th e com plete series of four con figuration al isom ers.
Our approach can be ch aracterized as th e tran sform ation of an oxiran e
derivative in to th e aziridin e derivative th rough th e ch an ge of con figuration
on both carbon atom s of th e oxiran e rin g (Sch em e 1).
Collect. Czech. Chem. Commun. (Vol. 69) (2004)
doi:10.1135/cccc20041939

1940
Karban, Buděšínský, Kroutil:
OTs
O
1. NaN3
2. TsCl
LiAlH4
N
H
N3
SCHEME 1
Startin g dian h ydro derivatives 1 an d 2 were prepared accordin g to th e
procedures described in literature10,11. Sin ce procedures reported12 in litera-
ture for th e preparation of dian h ydro derivatives 3 an d 4 are tedious an d af-
ford low yields, we decided to prepare th ese com poun ds by an altern ative
reaction sequen ce from dian h ydro derivative 5. Reduction of com poun d 5
with diboran e gen erated in situ from sodium boroh ydride an d boron tri-
fluoride eth erate afforded tosylate 10a in 57% yield togeth er with 30% of
th e startin g dian h ydride 5 an d 9% of th e dih ydroxy derivative 6. A pro-
lon ged reaction tim e resulted in accum ulation of com poun d 6, wh ich was
form ed m ost likely from tosylate 10a by reductive cleavage of 1,6-an h ydro
bridge at carbon C-1. Wh en excess of boron trifluoride eth erate in 1,2-di-
m eth oxyeth an e was used, com poun d 7, form ed by participation of th e sol-
ven t, was isolated as th e m ain product. In th e n ext step, m esylation of 10a
yielded m esylate 10b . Sulfon ates 10a an d 10b reacted with sodium
m eth an olate to give dian h ydrides 3 an d 4, respectively (Sch em e 2).
O
O
O
O
O
O
O
O
O
O
O
O
1
2
3
4
CH2OH
O
O
O
O
O
OH
OH
O
TsO
TsO
TsO
(i)
OCH2CH2OCH3
6
5
7
O
O
O
O
(iii)
(iii)
(ii)
4
OH
OMs
3
TsO
TsO
10a
(i) NaBH4, BF3·Et2O, 1,2-dimethoxyethane; (ii) MsCl, pyridine; (iii) CH3ONa, CH3OH–CH2Cl2
SCHEME 2
10b
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

Epimino-β-D-hexopyranoses
1941
Dian h ydrides 1 an d 4 reacted regioselectively with sodium azide in
2-m eth oxyeth an ol–water m ixture13 un der th e diaxial splittin g of th e
oxiran e rin g affordin g azides 8a an d 10c, respectively, wh ich were con -
verted to azido tosylates 8b an d 10d (Sch em e 3). In con trast, azidolysis of
dian h ydrides 2 an d 3 un der th e sam e con dition s provided in addition to
products of diaxial splittin g 8c an d 10e, respectively, also products 9a an d
11a, respectively, form ed by “an om alous” diequatorial splittin g of th e
oxiran e rin g. Azides 10e an d 11a were separated by colum n ch rom atogra-
ph y an d con verted to tosylates 10f an d 11b. Azides 8c an d 9a could be sep-
arated by colum n ch rom atograph y after th eir con version to tosylates 8d
O
O
(i)
N3
1
OR
8a, R= H
(ii)
8b, R = Ts
O
O
O
O
(i)
(i)
(i)
OR
RO
+
2
3
4
N3
N3
9a, R= H
8c, R= H
(ii)
(ii)
9b, R = Ts
8d, R = Ts
O
O
O
O
RO
OR
+
N3
N3
11a, R= H
10e, R= H
10f, R = Ts
(ii)
(ii)
11b, R = Ts
O
O
N3
RO
(i) NaN3, NH4Cl,
2-methoxyethanol–water
(ii) TsCl, pyridine
10c, R= H
(ii)
10d, R = Ts
SCHEME 3
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

1942
Karban, Buděšínský, Kroutil:
an d 9b. Th e n on selective stereoch em ical course of th e n ucleoph ilic cleav-
age of dian h ydrides 2 an d 3 was already observed for oth er n ucleoph iles
an d was in terpreted as th e result of an tagon istic in fluen ce of steric an d po-
lar effects12 on th e cleavage. Steric effect favours form ation of diaxial prod-
ucts, wh ile polar effect causes th e cleavage of th e oxiran e rin g at th e carbon
atom , wh ich is located furth er from th e acetal (dian h ydrides 1 an d 2) or
eth er (dian h ydride 3 an d 4) m oiety. In th e case of dian h ydrides 1 an d 4,
both effects are syn ergistic wh ile in th e case of dian h ydrides 2 an d 3 th e ef-
fects are an tagon istic givin g rise to a m ixture of regioisom ers. Dian h ydrides
1 an d 4 with exo-orien ted oxiran e rin g also n eeded a sign ifican tly sh orter
reaction tim e to com plete th e azidolysis th an dian h ydrides 2 an d 3 with
endo-orien ted oxiran e rin g. Th is is in con trast with th e low reactivity of
O-ben zylated 1,6:2,3- an d 1,6:3,4-dian h ydro-β-D-h exopyran oses with exo-
orien ted oxiran e rin g towards azidolysis2. Th e structure of all deoxy deriva-
1
tives 6, 8–11 was proved by H an d 13C NMR spectra. Th e presen ce of tosyl,
m esyl an d in m ost cases also of th e OH group is m an ifested by ch aracteris-
tic sign als in 1H an d 13C NMR spectra (see Tables I–III). Th e presen ce an d
position of th e azido group was detected on ly in directly from th e upfield
position of correspon din g carbon sign al (δ 55–62 ppm ). Th e CH2 group in
tetrah ydropyran rin g provides ch aracteristic upfield 13C an d 1H sign als (at
δ 29–38 an d 1.60–2.40 ppm , respectively). Vicin al proton couplin gs of CH2
proton s to H-1 an d/or H-5 can distin guish between 2- an d 4-deoxy deriva-
tives. Th e all observed vicin al proton couplin gs of tetrah ydropyran rin g
(Table II) suggest th at it adopts 1C4 (D) con form ation in derivatives 8–11
with xylo an d arabino con figuration s.
Reduction of azido tosylates 8b, 8d , 10d , an d 10f with lith ium alu-
m in ium h ydride in tetrah ydrofuran provided aziridin e derivatives 12a, 13a,
14, an d 15, respectively (Sch em e 4). Th e reaction s proceeded at room tem -
10f 11b
8b
(i)
8d 9b
10d
(i)
(i)
(i)
O
O
O
O
O
O
O
O
NR
NH
HN
NR
14
15
12a, R= H
13a, R= H
(ii)
(ii)
12b, R = Ac
13b, R = Ac
(i) LiAlH4, THF; (ii) Ac2O, CH2Cl2
SCHEME 4
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

Epimino-β-D-hexopyranoses
1943
perature givin g m oderate yields in th e ran ge 55–72%. Epim in e 13a was
foun d to slowly decom pose an d th erefore was con verted to stable N-acetyl
derivative 13b for ch aracterization . Epim in e 12a was also con verted to
N-acetate 12b for ch aracterization purposes. Epim in es 14 an d 15 were sta-
ble crystallin e com poun ds.
Azido tosylates 9b an d 11b reacted with lith ium alum in ium h ydride to
aziridin es 13a an d 15, respectively. Reductive cyclization of th ese azido
tosylates in to th e correspon din g epim in es is an un expected result con sider-
in g th e diequatorial arran gem en t of th e participatin g groups on a relatively
rigid bicyclic skeleton . To our kn owledge, th is is th e first reported case of
a th ree-m em bered rin g closure from a diequatorial precursor in th e
1,6-an h ydro-β-D-h exopyran ose series. Th is reaction m ost likely in volves th e
ch an ge of con form ation from 1C4 (D) in to th e en ergetically disadvan ta-
geous B3,O (D) con form ation , in wh ich th e reactin g azido an d tosyloxy
groups assum e trans-diaxial relation sh ip in dispen sable for SN2 in tra-
m olecular substitution (Sch em e 5).
O
O
O
O
LiAlH4
O
O
O
Ts
OTs
N3
NH
13a
N3
B3.O (D)
1C4 (D)
SCHEME 5
Structure of aziridin e derivatives 12–15 was dem on strated by 1H an d
13C NMR spectra. NMR spectra of epim in es 12a, 13a, 14, an d 15 with a free
am in o group sh owed two sets of sign als due to a slow in version at n itrogen
atom (for details, see lit.14). Th e observed ratios of isom ers in CDCl3 were
79:21 (12a), 86:14 (13a), 64:36 (14) an d 88:12 (15). Th e isom er ratio can be
in fluen ced by th e solven t – for 13a in CD3OD we h ave foun d th e ratio 91:9.
Th e structure assign m en t of sign als belon gin g to th e epim in e isom er with
endo- an d exo-orien ted NH h ydrogen is very difficult sin ce n eith er separate
NH sign als n or NH–CH couplin gs are observed. Th e in spection of m odels
in dicates a possible in tram olecular H-bon din g between NH an d oxygen
atom C(6)–O–C(1) in epim in es 12a an d 14 or oxygen atom C(5)–O–C(1) in
aziridin es 13a an d 15. Th e NH region of th e IR spectra in CCl4 sh owed
in deed two ban ds belon gin g to free NH an d in tram olecularly H-bon ded
im in o group for epim in es 12a an d 13a (see Table IV) with h igh er in ten si-
ties of H-bon ded ban ds. In epim in e 15 on ly th e ban d of H-bon ded NH at
3295 cm –1 is clearly detected an d a weak sh oulder on h igh er-frequen cy side
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

1944
Karban, Buděšínský, Kroutil:
m ay in dicate a sm all am oun t of free NH form . On th e con trary th e IR spec-
trum of epim in e 14 sh ows on ly broad ban d of free NH at 3321 cm –1. Th is
observation could be explain ed by a larger distan ce N···O (3.05 Å) in com -
parison with th ree previously discussed epim in es (≈2.8 Å). Th eoretical cal-
culation s usin g th e MM+ m eth od resulted in a sligh tly lower en ergy for
endo-NH isom er in all epim in es 12a, 13a, 14, an d 15. From all th e above
discussed in form ation we believe th at prevailin g isom er is th e endo-NH.
Th e addition of a trace am oun t of CD3COOD to th e CDCl3 solution leads
for all epim in es (12a, 13a, 14, an d 15) to th e observation of on ly on e set of
sign als due to proton ation of n itrogen atom . Th e m easurem en t of tem pera-
ture depen den ce of 1H NMR spectrum of aziridin e 12a in DMSO in th e
ran ge 20–100 °C sh owed on ly n arrowin g of sign als of on e isom er but th e
coalescen ce tem perature m ust be m uch h igh er th an 100 °C. Th e N-acetyl-
ation of aziridin es is kn own to decrease a coalescen ce tem perature dram ati-
cally15 as con firm th e NMR spectra of com poun ds 12b an d 13b con tain in g
on ly on e set of sign als in CDCl3 already at room tem perature.
EXPERIMENTAL
Meltin g poin ts were determ in ed on a Kofler block an d are un corrected. Th e optical rotation s
were m easured on an Autopol III (Rudolf Research , Flan ders, NJ) polarim eter at 23 °C an d
are given in 10–1 deg cm 2 g–1. In frared spectra of epim in es 12a, 13a, 14, an d 15 were re-
corded on a PE684 in tetrach lorom eth an e solution at con cen tration s lower th an 4.0 × 10–3
m ol dm –3 to avoid in tram olecular association s. Waven um bers an d relative in ten sities of th e
absorption ban ds of th e im in o group are given in Table IV. NMR spectra were m easured on
FT NMR spectrom eters Varian UNITY-500 an d Bruker AVANCE-500 (1H at 500 MHz, 13C at
125.7 MHz). Ch em ical sh ifts (in ppm , δ-scale) were referen ced to tetram eth ylsilan e as in ter-
n al stan dard; couplin g con stan ts (J) are given in Hz. Structure assign m en t of proton s an d
carbon atom s was ach ieved usin g correlated h om on uclear 2D-COSY an d h eteron uclear 1H,
13C-2D-HMQC spectra. Th e lon g-ran ge couplin gs were iden tified with selective decouplin g
experim en ts in 1D 1H NMR spectra. TLC was carried out on Merck DC Alufolien with
Kiesegel F254 usin g two solven t system s: toluen e–aceton e 5:1 (S1) an d aceton e (S2). TLC
plates were visualized by UV detection at 254 n m an d with an an isaldeh yde solution in
H2SO4. Colum n ch rom atograph y was perform ed on silica gel 60 Merck (70–230 m esh
ASTM). Th e solven ts were evaporated on a vacuum rotary evaporator at 40 °C. An h ydrous
sodium sulfate was used for dryin g solution s. Th e 1H NMR spectral param eters of com -
poun ds 8–15 are given in Tables I an d II, an d th ose of 13C NMR spectra in Table III.
1,6-An h ydro-2-deoxy-4-O-tosyl-β-D-arabino-h exopyran ose (10a) an d
1,2-Dideoxy-4-O-tosyl-β-D-arabino-h exopyran ose (6)
To a suspen sion of 1,6:2,3-dian h ydro-4-O-tosyl-β-D-m an n opyran ose16 (5; 7.765 g, 26.0 m m ol)
an d a fin ely groun d NaBH4 (3.060 g, 80.9 m m ol) in 1,2-dim eth oxyeth an e (90 m l), BF3·OEt2
(10.5 m l, 83.6 m m ol) was added dropwise un der coolin g an d stirrin g. Th e reaction course
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

Epimino-β-D-hexopyranoses
1945
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

1946
Karban, Buděšínský, Kroutil:
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

Epimino-β-D-hexopyranoses
1947
TABLE II
1H NMR couplin g con stan ts of com poun ds 8–15 in CDCl3
Com poun d
1,2ex 1,2en 2ex,2en 2ex,3 2en ,3 3,4ex 3,4en 4ex,4en 4ex,5 4en ,5 5,6en 5,6ex 6en ,6ex
a
8a
–
2.1
1.9
1.2
–
–
–
1.9
1.9
1.9
–
6.0
6.4
5.6
11.5
–
1.8
1.9
1.5
6.6
2.6
2.1
1.7
2.5
1.4
2.6
–
15.1
15.0
15.8
13.8
–
4.2
4.4
4.1
3.6
–
1.8
2.0
1.6
1.9
1.8
*
0.9
0.9
0.9
1.1
0.8
1.1
1.0
1.0
0.8
1.0
0.8
0.8
*
5.2
5.2
5.2
4.8
5.5
5.6
5.8
5.8
5.3
5.7
5.1
5.0
*
7.1
7.2
7.2
7.6
7.9
8.3
7.6
7.9
7.7
7.8
7.8
8.3
*
b
8b
–
–
–
c
8d
–
–
–
d
9b
1.6
1.7
2.2
1.9
2.3
1.6
1.9
1.4
2.0
–
8.8
5.5
6.0
6.1
6.5
5.2
5.8
10.9
10.8
6.1
6.2
–
e
10a
2.2
1.8
1.5
1.4
1.7
1.9
2.1
1.3
–
15.1
15.6
15.3
15.1
15.3
15.6
13.3
13.5
–
1.2
3.0
1.7
2.4
3.2
1.7
6.5
6.8
–
f
10b
–
–
–
g
10c
–
–
–
2.3
2.5
2.7
1.7
–
h
10d
–
–
–
i
10e
–
–
–
j
10f
–
–
–
k
11a
9.0
9.1
5.9
4.9
≤1.5
0.7
6.9
–
–
4.0
4.1
6.8
6.1
5.3
5.2
6.4
–
l
11b
–
–
–
m
12a + AcOD 4.0
<1
15.4
14.7
15.5
15.0
–
<1
n
12b
3.8
–
–
–
–
1.0
6.6
6.7
–
~0
~0
2.1
1.9
2.0
≤0.3
0.7
5.7
6.2
6.2
4.4
4.4
6.8
7.7
7.7
7.4
7.2
o
13a + AcOD
≤1.5
1.3
~1.0
0.6
–
6.0
6.0
0.8
6.3
p
13b
–
–
–
0.7
t
14 + AcOD
3.2
3.2
15.2
15.5
5.0
0.8
–
u
15 +AcOD
5.8
–
1.7
* J-value could n ot be determ in ed.
a
Addition al couplin g con stan ts: J(1,3) = 1.2, J(1,4ex) ≤ 0.3, J(1,4en ) = 1.0, J(1,6ex) = 0.5,
J(1,6en ) ≤ 0.2, J(2en ,4ex) = 0.6, J(2en ,4en ) = 1.1, J(2en ,5) = 0.5, J(3,5) = 1.0, J(4ex,6ex) = 1.6;
b
J(1,3) = 1.2, J(1,4ex) ≤ 0.3, J(1,4en ) = 0.9, J(1,6ex) = 0.4, J(1,6en ) ≤ 0.2, J(2en ,4ex) = 0.5,
c
J(2en ,4en ) = 1.1, J(2en ,5) = 0.6, J(3,5) = 1.0, J(4ex,6ex) = 1.5; J(1,3) = 1.9, J(1,4en ) = 1.0,
d
e
J(1,6ex) = 0.4, J(2en ,4en ) = 1.5, J(3,5) = 1.7, J(4ex,6ex) = 1.6; J(4ex,6ex) = 1.7; J(1,3) = 1.4,
J(1,4en ) = 0.8, J(1,6ex) ≤ 0.3, J(2en ,4en ) = 1.2, J(2en ,5) = 1.2, J(3,5) = 1.6, J(3,OH) = 7.7;
f
g
J(1,3) ≈ 1.0, J(2en ,4en ) = 1.0, J(3,5) ≈ 1.0; J(1,3) = 1.1, J(1,4en ) = 0.8, J(1,6en ) ≤ 0.2,
h
J(1,6ex) ≤ 0.3, J(2ex,4en ) = 0.5, J(2en ,4en ) = 1.2, J(2en ,5) = 0.7, J(3,5) = 1.5; J(1,3) = 0.9,
J(1,4en ) = 0.9, J(1,6ex) = 0.5, J(2ex,4en ) = 0.5, J(2en ,4en ) = 0.9, J(2en ,5) = 0.8; J(1,3) = 1.3,
J(2en ,4ex) = 0.8, J(3,5) = 1.7; J(1,3) = 1.0, J(1,4en ) < 0.3, J(1,6ex) = 0.4, J(2en ,4en ) = 0.8,
J(2en ,5) = 1.0, J(3,5) = 1.5; J(1,6ex) ≈ 0.5, J(2en ,4ex) ≈ 0.6, J(2en ,5) ≈ 0.4, J(2en ,4ex) ≤ 0.5,
i
j
k
l
m
J(2ex,5) ≤ 0.4, J(4,OH) = 3.8; J(2en ,4ex) ≈ 0.4, J(2en ,5) = 0.7, J(4ex,6ex) = 1.2; J(1,3) = 1.1;
n
o
J(1,3) = 0.4, J(1,4en ) = 1.0, J(1,6en ) = 0.6, J(1,6ex) = 0.5, J(4ex,6ex) = 1.1; J(3,5) = 1.5,
p
r
J(4ex,6ex) = 1.5; J(1,4en ) ≈ 0.5, J(3,5) = 1.4, J(4ex,6ex) = 1.3; J(1,3) = 0.8, J(1,6ex) = 0.5,
J(2en ,4ex) = 0.9; J(1,5) ≤ 0.3, J(1,6en ) ≤ 0.5, J(1,6ex) = 0.5, J(3,5) ≈ 0.9; J(1,3) = 1.1,
J(2en ,4ex) = 0.9; J(1,5) = 0.7, J(1,3) = 1.9, J(2ex,4en ) = 0.8, J(2en ,4en ) = 0.6, J(3,5) = 1.1.
s
t
u
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

1948
Karban, Buděšínský, Kroutil:
was m on itored by TLC (S1). Th e coolin g bath was rem oved after 1 h an d stirrin g con tin ued
for addition al 1.5 h . Th e reaction m ixture was carefully m ixed with water, n eutralized with
5% aqueous HCl an d a crystal of com poun d 5 was added to in duce precipitation . Th e pre-
cipitate was filtered off an d dried to afford 2.335 g (30%) of th e startin g dian h ydride 5. Th e
filtrate was extracted with dich lorom eth an e (5×), organ ic layer was dried an d con cen trated
to afford product 10a (3.867 g, 49.5%), m .p. 104–105 °C (eth an ol–h exan e), [α]D –64 (c 0.3,
CHCl3). For C13H16O6S (300.3) calculated: 51.99% C, 5.37% H, 10.68% S; foun d: 52.14% C,
TABLE III
13C NMR ch em ical sh ifts of com poun ds 8–15 in CDCl3
Com poun d
C-1
C-2
C-3
C-4
C-5
C-6
Oth er carbon s
–
8a
8b
101.10
96.95
68.42
74.52
56.66
55.75
29.63
29.73
71.45
74.19
67.17
70.70
OTs: 145.62, 132.88,
130.20(2), 127.98(2), 21.66
OTs: 145.44, 133.32,
130.16(2), 127.77(2), 21.65
8d
99.67
99.80
59.62
80.92
35.18
74.62
56.48
66.72
31.86
34.71
78.50
70.86
72.49
74.33
67.35
68.57
64.99
OTs: 145.37, 133.08,
129.93(2), 128.05(2), 21.66
9b
OTs: 145.27, 133.40,
130.05(2), 127.77(2), 21.67
10a
100.73
OTs: 145.74, 132.74,
130.18(2), 127.96(2), 21.71
10b
10c
10d
10e
10f
11a
11b
98.95
99.72
33.70
30.87
31.34
35.95
33.57
36.81
37.84
73.30
57.37
55.21
67.20
74.33
59.63
56.49
76.17
69.51
77.38
62.14
60.46
71.15
78.18
73.91
75.94
74.24
74.62
73.66
75.19
73.60
6.76
64.90
65.17
65.91
65.56
64.92
65.19
–
OTs: 145.56, 133.18,
130.15(2), 127.86(2), 21.68
99.13
101.10
99.25
–
OTs: 145.41, 133.16,
130.12(2), 127.78(2), 21.67
100.31
100.09
–
OTs: 145.62, 133.47,
129.98(2), 128.11(2), 21.72
12a NH-endo (79%)
12a NH-exo (21%)
12b
98.79
99.03
97.05
98.00
98.16
96.89
97.62
97.36
99.98
98.41
34.29
35.89
39.22
30.93
31.87
35.33
31.12
31.01
31.55
31.90
22.73
24.86
29.11
25.43
25.99
30.88
23.30
25.19
24.07
23.80
29.19
29.45
28.25
30.05
30.40
28.66
32.34
33.53
31.84
32.47
67.37
67.61
67.16
71.63
70.88
71.08
72.49
72.32
69.60
70.24
68.26
68.20
67.55
68.70
68.43
68.90
64.71
64.88
68.06
67.56
–
–
NAc: 180.77, 22.69
13a NH-endo (86%)
13a NH-exo (14%)
13b
–
–
NAc: 181.14, 23.68
14 NH-endo (64%)
14 NH-exo (36%)
15 NH-endo (88%)
15 NH-exo (12%)
–
–
–
–
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

Epimino-β-D-hexopyranoses
1949
5.35% H, 10.47% S. Ch rom atograph y of th e m oth er liquor on silica gel (60 g) in toluen e–
aceton e 10:1 m ixture afforded addition al product 10a (0.589 g, 7.5%). Furth er elution with
toluen e–aceton e 4:1 gave tosylate 6 (0.672 g, 8.5%), m .p. 87–89 °C (eth yl acetate–dieth yl
eth er–h exan e), [α]D +22 (c 0.3, CHCl3). 1H NMR (CDCl3): 1.75 dddd, 1 H, J(2β,1α) = 12.8,
J(2β,1β) = 5.1, J(2β,2α) = 13.5, J(2β,3) = 11.4 (H-2β); 2.47 bs, 3 H (CH3 (OTs)); 2.07 ddt, 1 H,
J(2α,1α) = 2.1, J(2α,1β) = 1.7, J(2α,2β) = 13.5, J(2α,3) = 5.4 (H-2α); 3.26 ddd, 1 H, J(5,4) =
9.6, J(5,6a) = 4.6, J(5,6b) = 2.4 (H-5); 3.43 ddd, 1 H, J(1α,1β) = 11.8, J(1α,2α) = 2.1, J(1α,2β) =
12.8 (H-1α); 3.56 ddd, 1 H, J(6a,5) = 4.6, J(6a,6b) = 12.3, J(6a,OH) = 6.1 (H-6a); 3.71 ddd, 1 H,
J(6b,5) = 2.4, J(6b,6a) = 12.3, J(6b,OH) = 7.6 (H-6b); 3.85 m , 1 H, J(3,2α) = 5.4, J(3,2β) = 11.4,
J(3,OH) = 2.9, J(3,4) = 8.7 (H-3); 3.99 ddd, 1 H, J(1β,1α) = 11.8, J(1β,2α) = 1.7, J(2β,2β) = 5.1
(H-1β); 4.43 dd, 1 H, J(4,3) = 8.7, J(4,5) = 9.6 (H-3); 7.38 m , 2 H an d 7.85 m , 2 H (C6H4
(OTs)). 13C NMR (CDCl3): 21.72 (CH3 (OTs)); 33.93 (C-2); 61.50 (C-6); 65.49 (C-1); 70.71
(C-3); 77.78 (C-5); 80.94 (C-4); 128.03 (2 C); 130.02 (2 C); 132.59 an d 145.69 (C6H4 (OTs)).
For C13H18O6S (302.3) calculated: 51.64% C, 6.00% H, 10.61% S; foun d: 51.66% C, 6.02% H,
10.58% S.
1,6-An h ydro-2-O-(2-m eth oxyeth oxy)-4-O-tosyl-β-D-glucopyran ose (7)
To a suspen sion of 1,6:2,3-dian h ydro-4-O-tosyl-β-D-m an n opyran ose14 (5; 0.538 g, 1.8 m m ol)
an d a fin ely groun d NaBH4 (0.255 g, 6.7 m m ol) in 1,2-dim eth oxyeth an e (9 m l), BF3·OEt2
(2.0 m l, 15.8 m m ol) was added dropwise un der coolin g an d stirrin g an d th e reaction m ixture
was left to stan d at room tem perature overn igh t. It was th en diluted with water, n eutralized
with sodium h ydrogen carbon ate an d extracted with dich lorom eth an e (5×). Th e extract was
con cen trated an d ch rom atograph y on silica gel (30 g) in S1 gave com poun d 7 (0.359 g,
53%), m .p. 84–86 °C (eth yl acetate–dieth yl eth er), [α]D –46 (c 0.3, CHCl3). 1H NMR (CDCl3):
2.45 bs, 3 H (CH3 (OTs)); 3.02 d, 1 H, J(OH,3) = 2.9 (OH-3); 3.18 dd, 1 H, J(2,1) = 0.9, J(2,3) =
4.9 (H-2); 3.36 s, 3 H (OCH3); 3.52 ddd, 1 H, J(gem ) = 10.8, J(vic) = 5.3 an d 3.8; 3.54 ddd, 1 H,
J(gem ) = 10.8, J(vic) = 5.9 an d 3.4; 3.71 ddd, 1 H, J(gem ) = 11.5, J(vic) = 5.9 an d 3.8; 3.80 ddd,
TABLE IV
Ban ds in IR spectra an d geom etry param eter of epim in es 12a, 13a, 14, an d 15 in CCl4
Param eter
12a
13a
14
15
Waven um ber, cm –1 (relative in ten sity, %)
a
Free NH
3324 (24)
3305 (76)
3319 (10)
3294 (90)
3321 (~100)
–
In tram ol.
H-bon ded NH
3295
Geom etry param eter of H-bon d
2.80 3.05
N···O, Åb
2.76
2.80
a
b
Th e accurate position an d in ten sity could n ot be determ in ed; distan ces were obtain ed
from th e en ergetically m in im ized con form ation s calculated by MM+ m eth od (usin g
HYPERCHEM software package).
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

1950
Karban, Buděšínský, Kroutil:
1 H, J(gem ) = 11.5, J(vic) = 5.3 an d 3.4 (O-CH2-CH2-O); 3.67 dd, 1 H, J(6ex,6en ) = 7.8,
J(6ex,5) = 5.3 (H-6ex); 3.82 tt, 1 H, J(3,2) = 4.9, J(3,4) = 5.4, J(3,1) ≈ 0.7, J(3,5) ≈ 1.0 (H-3);
3.87 dd, 1 H, J(6en ,6ex) = 7.8, J(6en ,5) = 1.0; 4.30 dd, 1 H, J(4,3) = 5.4, J(4,5) = 1.2 (H-4);
4.62 dq, 1 H, J(5,6ex) = 5.3, J(5,6en ) = 1.0, J(5,4) = 1.2, J(5,3) ≈ 1.0 (H-5); 5.42 bs, 1 H (H-1);
7.35 m , 2 H an d 7.83 m , 2 H (C6H4 (OTs)). 13C NMR (CDCl3): 21.66 (CH3 (OTs)); 59.00
(OCH3); 66.79 (C-6); 70.36 an d 72.30 (O-CH2-CH2-O); 70.48 (C-3); 75.44 (C-4); 81.96 (C-5);
82.03 (C-2); 101.95 (C-1); 127.95 (2 C); 129.88 (2 C); 133.36 an d 145.14 (C6H4 (OTs)). For
C
16H22O8S (374.4) calculated: 51.33% C, 5.92% H, 8.56% S; foun d: 51.55% C, 5.87% H,
8.55% S.
1,6:3,4-Dian h ydro-2-deoxy-β-D-lyxo-h exopyran ose (3)
To a solution of tosylate 10a (2.427 g, 8.1 m m ol) in dich lorom eth an e (80 m l) a m eth an ol
(16 m l) solution of sodium (0.70 g, 30.4 m m ol) was added dropwise un der stirrin g an d cool-
in g (ice–water) an d th e reaction m ixture was allowed to stan d at room tem perature for 3 h .
It was th en n eutralized with 5% HCl, diluted with con cen trated solution of NaCl an d ex-
tracted with dich lorom eth an e (4×). Th e extract was dried an d con cen trated (un der pressure
> 90 m bar, oth erwise th e product rapidly volatilizes) to afford crude 3 (0.984 g, 95%), wh ich
was used with out furth er purification for azidolysis.
1,6-An h ydro-2-deoxy-3-O-m esyl-4-O-tosyl-β-D-arabino-h exopyran ose (10b)
To a solution of tosylate 10a (0.765 g, 2.55 m m ol) in pyridin e (10 m l), m eth an esulfon yl
ch loride (0.500 m l, 6.27 m m ol) was added un der stirrin g an d coolin g (ice–NaCl–water). Th e
coolin g bath was rem oved after 2 h an d th e reaction m ixture was allowed to stan d at 4 °C
overn igh t. It was th en diluted with water, extracted with dich lorom eth an e, th e extract was
dried, filtered th rough a layer of silica gel an d con cen trated to afford product 10b (0.726 g,
75%), m .p. 129 °C (dec., aceton e–dieth yl eth er), [α]D –61 (c 0.3, CHCl3). For C14H18O8S2
(378.4) calculated: 44.43% C, 4.79% H, 16.94% S; foun d: 44.50% C, 4.83% H, 16.84% S.
1,6:3,4-Dian h ydro-2-deoxy-β-D-ribo-h exopyran ose (4)
Th e reaction was perform ed as described for th e preparation of dian h ydride 3 usin g a solu-
tion of tosylate 10b (1.609 g, 4.25 m m ol) in dich lorom eth an e (70 m l) an d m eth an ol (18 m l)
con tain in g dissolved sodium (0.67 g, 29.1 m m ol). Th e reaction m ixture was allowed to
stan d at room tem perature overn igh t. It was th en processed as described for com poun d 3 to
afford crude 4 (0.548 g, ca. 100%), wh ich con tain ed about 5% of its lyxo-isom er 3 accordin g
to GC-MS an alysis. Crude 4 was used for azidolysis with out futh er purification .
Gen eral Procedure for th e Preparation of Azido Tosylates 8b, 8d , 9b, 10d , 10f, an d 11b
A solution of dian h ydro derivatives 1–4, sodium azide an d am m on ium ch loride in a m ixture
of 2-m eth oxyeth an ol an d water was h eated to 100 °C un til th e startin g com poun d disap-
peared (TLC, S1). Th e reaction m ixture was th en worked up as described below for in divid-
ual com poun ds to afford vicin al h ydroxy azides, wh ich were ch aracterized as azido tosylates.
Tosylation was carried out by m ixin g a solution of tosyl ch loride an d h ydroxyazide in pyri-
din e an d keepin g it at a given tem perature for a given tim e. Th e pyridin e solution was th en
poured on to crush ed ice. If th e azido tosylate precipitated, it was filtered off an d re-
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

Epimino-β-D-hexopyranoses
1951
crystallized. If n ot, it was extracted with dich lorom eth an e, th e dich lorom eth an e solution
was dried, filtered th rough a layer of silica gel, decolorized with ch arcoal, if n ecessary, an d
con cen trated.
1,6-An h ydro-3-azido-3,4-dideoxy-2-O-tosyl-β-D-xylo-h exopyran ose (8b)
Dian h ydride 1 (3.844 g, 30.0 m m ol), sodium azide (5.0 g, 76.9 m m ol), am m on ium ch loride
(5.0 g, 93.5 m m ol), 2-m eth oxyeth an ol (100 m l) an d water (20 m l) were h eated to 100 °C for
11 h . Th e reaction m ixture was th en con cen trated to a th ick suspen sion , diluted with ace-
ton e an d filtered. Th e filtrate was con cen trated to afford syrupy 8a (4.809 g, 94%), [α]D –12
(c 0.5, CHCl3). Tosylation of product 8a (4.754 g, 27.8 m m ol) with tosyl ch loride (13 g,
68.2 m m ol) in pyridin e (60 m l) at 4 °C for 3 days afforded tosylate 8b (8.371 g, 93%), m .p.
99–101 °C (dieth yl eth er), [α]D –46 (c 0.3, CHCl3). For C13H15N3O5S (325.3) calculated:
47.99% C, 4.65% H, 12.92% N, 9.86% S; foun d: 47.97% C, 4.76% H, 12.79% N, 9.61% S.
1,6-An h ydro-2-azido-2,4-dideoxy-3-O-tosyl-β-D-xylo-h exopyran ose (8d ) an d
1,6-An h ydro-3-azido-3,4-dideoxy-2-O-tosyl-β-D-arabino-h exopyran ose (9b)
Dian h ydride 2 (2.30 g, 18.0 m m ol), sodium azide (2.3 g, 35.4 m m ol), am m on ium ch loride
(2.3 g, 43.0 m m ol), 2-m eth oxyeth an ol (40 m l) an d water (10 m l) were h eated to 100 °C for
80 h . After 30 h an d 60 h , sodium azide (0.7 g, 10.8 m m ol) an d am m on ium ch loride (1.0 g,
18.7 m m ol) were added. Th e reaction m ixture was th en con cen trated to dryn ess, th e residue
was codistilled with toluen e (3×) an d extracted with dich lorom eth an e. Th e dich lorom eth an e
solution was filtered th rough a layer of silica gel an d con cen trated to afford a m ixture of
azides 8c an d 9a (2.52 g, 82%) in th e 28:72 ratio accordin g to 1H NMR spectrum (H-1, δ 5.37
an d 5.55 in CDCl3). Tosylation of th e product m ixture (2.55 g, 14.9 m m ol) with tosyl ch lo-
ride (10.5 g, 55.1 m m ol) in pyridin e (60 m l) at 110 °C for 10 h afforded tosylate 9b (2.52 g,
52%), m .p. 97–99 °C (aceton e–dieth yl eth er), [α]D –54 (c 0.5, CHCl3). For C13H15N3O5S
(325.3) calculated: 47.99% C, 4.65% H, 12.92% N, 9.86% S; foun d: 48.12% C, 4.52% H,
13.26% N, 9.77% S. Ch rom atograph y of con cen trated m oth er liquor on silica gel (200 g) in
ligh t petroleum –eth yl acetate 10:3 gave (in th e followin g order):
1. azido tosylate 8d (0.976 g, 20%), m .p. 52–54 °C (dieth yl eth er–ligh t petroleum ), [α]D
+56 (c 0.6, CHCl3). For C13H15N3O5S (325.3) calculated: 47.99% C, 4.65% H, 12.92% N,
9.86% S; foun d: 48.12% C, 4.60% H, 13.16% N, 9.78% S.
2. addition al azido tosylate 9b (0.215 g, 4%).
1,6-An h ydro-3-azido-2,3-dideoxy-4-O-tosyl-β-D-arabino-h exopyran ose (10d )
Dian h ydride 4 (0.548 g, 4.3 m m ol), sodium azide (1.0 g, 15.4 m m ol), am m on ium ch loride
(1.0 g, 18.7 m m ol), 2-m eth oxyeth an ol (20 m l) an d water (5 m l) were h eated to 100 °C for
7 h . Th e reaction m ixture was th en diluted with aceton e, filtered an d th e filtrate con cen -
trated. Ch rom atograph y on silica gel (30 g) in toluen e–aceton e 10:1 afforded syrupy 10c
(0.515 g, 70%), [α]D –139 (c 0.3, CHCl3). Tosylation of th e product 10c (0.482 g, 2.8 m m ol)
with tosyl ch loride (2.30 g, 12.1 m m ol) in pyridin e (25 m l) at room tem perature overn igh t
afforded 10d (0.587 g, 64%), m .p. 74–75 °C (eth yl acetate–dieth yl eth er–h exan e), [α]D –59
(c 0.2, CHCl3). For C13H15N3O5S (325.3) calculated: 47.99% C, 4.65% H, 12.92% N, 9.86% S;
foun d: 47.80% C, 4.77% H, 12.65% N, 9.89% S.
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

1952
Karban, Buděšínský, Kroutil:
1,6-An h ydro-4-azido-2,4-dideoxy-3-O-tosyl-β-D-arabino-h exopyran ose (10f) an d
1,6-An h ydro-3-azido-2,3-dideoxy-4-O-tosyl-β-D-xylo-h exopyran ose (11b)
Dian h ydride 3 (0.937 g, 7.31 m m ol), sodium azide (1.5 g, 23.1 m m ol), am m on ium ch loride
(1.5 g, 28.0 m m ol), 2-m eth oxyeth an ol (30 m l) an d water (7 m l) were h eated to 100 °C for
27 h . Th e reaction m ixture was th en diluted with aceton e, filtered, con cen trated, th e residue
codistilled with toluen e, diluted with dich lorom eth an e, dried, filtered an d con cen trated.
Ch rom atograph y on silica gel (60 g) in toluen e–aceton e 9:1 afforded (in th e followin g or-
der):
1. syrupy xylo derivative 11a (0.288 g, 23%), [α]D –46 (c 0.25, CHCl3). Tosylation of azide
11a (0.262 g, 1.5 m m ol) with tosyl ch loride (3.06 g, 16.05 m m ol) in pyridin e (25 m l) at 80 °C
for 26 h afforded product 11b (0.313 g, 63%), m .p. 59–61 °C (dieth yl eth er–h exan e), [α]D
–52 (c 0.3, CHCl3). For C13H15N3O5S (325.3) calculated: 47.99% C, 4.65% H, 12.92% N,
9.86% S; foun d: 47.83% C, 4.76% H, 12.54% N, 9.87% S.
2. arabino derivative 10e (0.636 g, 51%), m .p. 88–90 °C (aceton e–dieth yl eth er), [α]D –26
(c 0.3, CHCl3). For C6H9N3O3 (171.2) calculated: 42.11% C, 5.30% H, 24.55% N; foun d:
42.09% C, 5.30% H, 24.28% N. Tosylation of azide 10e (0.625 g, 3.65 m m ol) with tosyl
ch loride (3.794 g, 19.9 m m ol) in pyridin e (25 m l) at room tem perature for 4 days afforded
product 10f (0.966 g, 81%), m .p. 110–112 °C (dieth yl eth er), [α]D –76 (c 0.3, CHCl3). For
C
13H15N3O5S (325.3) calculated: 47.99% C, 4.65% H, 12.92% N, 9.86% S; foun d: 47.96% C,
4.66% H, 12.98% N, 9.89% S.
Gen eral Procedure for th e Preparation of Epim in es 12a, 13a, 14, an d 15
To a suspen sion of lith ium alum in ium h ydride in tetrah ydrofuran , a solution of startin g
azido tosylate in tetrah ydrofuran (3–5 m l) was added un der coolin g (ice–NaCl–water, tem -
perature from –15 to –10 °C) an d stirrin g. Th e coolin g bath was rem oved after 2 h an d th e
reaction m ixture was allowed to stan d at room tem perature overn igh t. Th e am oun ts of th e
reactan ts an d th e volum e of tetrah ydrofuran are given for th e in dividual com poun ds. Th e
un reacted lith ium alum in ium h ydride was th en decom posed by addition of m oist dieth yl
eth er; water (1 m l) was added in th e en d to com plete th e decom position . Th e precipitate
was filtered off an d wash ed with eth yl acetate. Com bin ed filtrates were con cen trated an d
ch rom atograph y of th e residue on silica gel in S1 afforded th e products. Epim in es 12a an d
13a were con verted to N-acetyl derivatives 12b an d 13b for ch aracterization purposes.
1,6-An h ydro-2,3,4-trideoxy-2,3-epim in o-β-D-lyxo-h exopyran ose (12a)
Azido tosylate 8b (0.500 g, 1.54 m m ol), lith ium alum in ium h ydride (0.175 g, 4.6 m m ol),
tetrah ydrofuran (18 m l). Ch rom atograph y afforded epim in e 12a (0.136 g, 70%), m .p.
102–110 °C (75 °C sublim ., dieth yl eth er), [α]D –52 (c 0.3, CHCl3). For C6H9NO2 (127.1)
calculated: 56.68% C, 7.14% H, 11.02% N; foun d: 56.85% C, 7.27% H, 10.72% N.
2,3-(N-Acetylepim in o)-1,6-an h ydro-2,3,4-trideoxy-β-D-lyxo-h exopyran ose (12b)
A solution of epim in e 12a (0.100 g, 0.79 m m ol) an d acetic an h ydride (80 µl, 0.85 m m ol) in
dich lorom eth an e (2 m l) was allowed to stan d at room tem perature for 1 h . It was th en con -
cen trated an d codistilled with toluen e (2×) to afford N-acetylepim in e 12b (0.094 g, 71%),
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

Epimino-β-D-hexopyranoses
1953
m .p. 82–83 °C (dieth yl eth er), [α]D –26 (c 0.24, CHCl3). For C8H11NO3 (169.2) calculated:
56.80% C, 6.56% H, 8.28% N; foun d: 56.86% C, 6.75% H, 8.24% N.
1,6-An h ydro-2,3,4-trideoxy-2,3-epim in o-β-D-ribo-h exopyran ose (13a)
A. From azido tosylate 8d . Azido tosylate 8d (0.430 g, 1.32 m m ol), lith ium alum in ium
h ydride (0.252 g, 6.64 m m ol), tetrah ydrofuran (20 m l). Ch rom atograph y afforded epim in e
13a (0.132 g, 79%) as h ygroscopic crystallin e substan ce, wh ich slowly m elted in air an d
becam e con tam in ated with traces of decom position products after storin g in a refrigerator.
B. From azido tosylate 9b. Azido tosylate 9b (0.700 g, 2.15 m m ol), lith ium alum in ium
h ydride (0.410, 10.8 m m ol), tetrah ydrofuran (38 m l). Ch rom atograph y afforded epim in e
13a (0.172 g, 63%) iden tical with th e product prepared un der A.
2,3-(N-Acetylepim in o)-1,6-an h ydro-2,3,4-trideoxy-β-D-ribo-h exopyran ose (13b)
It was prepared as described for com poun d 12b from epim in e 13a (0.125 g, 0.98 m m ol) an d
acetic an h ydride (99 µl, 1.05 m m ol). Th e work-up afforded N-acetylepim in e 13b (0.035 g,
48%), m .p. 70–72 °C (dieth yl eth er), [α]D +7 (c 0.5, CHCl3). For C8H11NO3 (169.2) calcu-
lated: 56.80% C, 6.56% H, 8.28% N; foun d: 56.79% C, 6.56% H, 7.95% N.
1,6-An h ydro-2,3,4-trideoxy-3,4-epim in o-β-D-lyxo-h exopyran ose (14)
Azido tosylate 10d (0.300 g, 0.92 m m ol), lith ium alum in ium h ydride (0.111 g, 2.92 m m ol),
tetrah ydrofuran (12 m l). Ch rom atograph y afforded epim in e 14 (0.136 g, 70%), m .p. 90–102 °C
(60 °C sublim ., dieth yl eth er), [α]D –119 (c 0.2, CHCl3). For C6H9NO2 (127.1) calculated:
56.68% C, 7.14% H, 11.02% N; foun d: 56.61% C, 7.33% H, 10.78% N.
1,6-An h ydro-2,3,4-trideoxy-3,4-epim in o-β-D-ribo-h exopyran ose (15)
A. From azido tosylate 10f. Azido tosylate 10f (0.500 g, 1.54 m m ol), lith ium alum in ium
h ydride (0.175 g, 4.6 m m ol), tetrah ydrofuran (18 m l). Ch rom atograph y afforded epim in e 15
(0.107 g, 55%), m .p. 73–76 °C (65 °C sublim ., dieth yl eth er), [α]D –122 (c 0.25, CHCl3). For
C6H9NO2 (127.1) calculated: 56.68% C, 7.14% H, 11.02% N; foun d: 56.38% C, 7.34% H,
10.70% N.
B. From azido tosylate 11b. Azido tosylate 11b (0.310 g, 0.95 m m ol), lith ium alum in ium
h ydride (0.109 g, 2.9 m m ol), tetrah ydrofuran (11 m l). Ch rom atograph y afforded epim in e 15
(0.070 g, 58%), m .p. 74–76 °C (65 °C sublim ., dieth yl eth er), iden tical with th e product pre-
pared un der A.
REFERENCES
1. Kroutil J., Trnka T., Buděšínský M., Černý M.: Collect. Czech. Chem. Commun. 1998, 63,
813.
2. Karban J., Buděšínský M., Černý M., Trnka T.: Collect. Czech. Chem. Commun. 2001, 66,
799.
3. Kroutil J., Trnka T., Buděšínský M., Černý M.: Eur. J. Org. Chem. 2002, 2449.
4. Kroutil J., Karban J., Trnka T., Buděšínský M., Černý M.: Collect. Czech. Chem. Commun.
2002, 67, 1805.
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1954
Karban, Buděšínský, Kroutil:
5. Kroutil J., Karban J., Buděšínský M.: Carbohydr. Res. 2003, 338, 2825.
6. Guthrie R. D., Liebmann J. A.: J. Chem. Soc., Perkin Trans. 1 1974, 650.
7. Cleophax J., Géro S. D., Hildesheim J., Sepulchre A.-M., Guthrie R. D., Smith C. W.:
J. Chem. Soc. 1970, 1385.
8. Saeki H., Ohki E.: Chem. Pharm. Bull. 1968, 16, 2471.
9. Minamoto K., Azuma K., Tanaka T., Iwasaki H., Eguchi S., Kadoya S., Moroi R.: J. Chem.
Soc., Perkin Trans. 1 1988, 2955.
10. Trnka T., Buděšínský M., Černý M.: Carbohydr. Res. 1994, 259, 131.
11. Pecka J., Černý M.: Collect. Czech. Chem. Commun. 1973, 38, 132.
12. Halbych J., Trnka T., Černý M.: Collect. Czech. Chem. Commun. 1973, 38, 2151.
13. Černý M., Elbert T., Pacák J.: Collect. Czech. Chem. Commun. 1974, 39, 1752.
14. Booth H.: Prog. Nucl. Magn. Reson. Spectrosc. 1965, 5, 187.
15. Anet F. A. L., Osyany J. M.: J. Am. Chem. Soc. 1967, 89, 352.
16. Černý M., Pacák J., Staněk J.: Collect. Czech. Chem. Commun. 1965, 30, 1151.
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