Synthesis of 2-amino-2-deoxy-β-D-galactopyranosyl-(1→4)-2-amino- 2-deoxy-β-D-galactopyranosides: Using various 2-deoxy-2-phthalimido-D- galactopyranosyl donors and acceptors

Article abstract of DOI:10.1135/cccc20041914

A systematic study is presented of the efficiency of the most common glycosylation methods using standard 2-deoxy-2-phthalimidogalactopyranosyl donors ethyl 4-O-acetyl-3,6-di-O-benzyl-2-deoxy-2-phthalimido-1-thio-β-D- galactopyranoside (3a), 4-O-Acetyl-3,

Full text of DOI:10.1135/cccc20041914

1914
Veselý, Ledvina, Jindřich, Trnka, Šaman:
SYNTHESIS OF 2-AMINO-2-DEOXY-β-D-GALACTOPYRANOSYL-
(1→4)-2-AMINO-2-DEOXY-β-D-GALACTOPYRANOSIDES:
USING VARIOUS 2-DEOXY-2-PHTHALIMIDO-D-GALACTOPYRANOSYL
DONORS AND ACCEPTORS
3a
Jan VESELÝ1a, Miroslav LEDVINA1b,*, Jindřich JINDŘICH2a, Tomáš TRNKA and
2b
David ŠAMAN
a
Department of Organic Chemistry, Charles University, Albertov 2030, 128 40 Prague 2,
Czech Republic; e-mail: jxvesely@natur.cuni.cz, jindrich@natur.cuni.cz, trnka@natur.cuni.cz
Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic,
Flemingovo nám. 2, 166 10 Prague 6, Czech Republic; e-mail: ledvina@uochb.cas.cz,
saman@uochb.cas.cz
1
2
3
b
1
2
Received Jun e 2, 2004
Accepted July 25, 2004
Dedicated with due respect to Professor Miloslav Černý on the occasion of his 75th birthday in
recognition of his outstanding contributions to carbohydrate chemistry.
A system atic study is presen ted of th e efficien cy of th e m ost com m on glycosylation m eth -
ods usin g stan dard 2-deoxy-2-ph th alim idogalactopyran osyl don ors eth yl 4-O-acetyl-3,6-di-O-
ben zyl-2-deoxy-2-ph th alim ido-1-th io-β-D-galactopyran oside (3a), 4-O-Acetyl-3,6-di-O-ben zyl-
2-deoxy-2-ph th alim ido-β-D-galactopyran osyl brom ide (4), 4-O-acetyl-3,6-di-O-ben zyl-2-
deoxy-2-ph th alim ido-β-D-galactopyran osyl fluoride (5b ), O-(4-O-acetyl-3,6-di-O-ben zyl-2-
deoxy-2-ph th alim ido-β-D-galactopyran osyl) trich loroacetim idate (7) an d eth yl 3,6-di-O-
ben zyl-2-deoxy-2-ph th alim ido-1-th io-β-D-galactopyran oside (8), pen t-4-en yl 3,6-di-O-ben zyl-
an d 3-O-allyl-6-O-ben zyl-2-deoxy-2-ph th alim ido-β-D-galactopyran oside (10a) an d (10b) an d
pen t-4-en yl 3,6-di-O-ben zyl-2-deoxy-2-ph th alim ido-4-O-(trim eth ylsilyl)-β-D-galactopyran -
oside (11) as glycosyl acceptors in th e syn th esis of 2-am in o-2-deoxy-β-D-galactopyran osyl-
(1→4)-2-am in o-2-deoxy-β-D-galactopyran osides 12, 16a an d 17a. It was foun d th at due to a
low reactivity of th e axial OH(4) group of glycosyl acceptors, disacch arides 16b an d 17b
with α(1→4) bon d were also form ed. Th e un expected in term olecular m igration of eth yl-
sufan yl group from th e reducin g en d of glycosyl acceptor 8 th e reducin g en d of th e acti-
vated form of glycosyl don or 4 in th e glycosylation step to give eth ylsulfan yl derivative 3a
was proved. For preparation of th e glycosyl don ors an d glycosyl acceptors with galacto con -
figuration an approach based on epim erization of 4-O-m esyl derivatives of appropriate
syn th on s with gluco con figuration 2a an d 2b was em ployed.
Keyw ord s: Carboh ydrates; Oligosacch arides; Am in osugars; D-Galactosam in e; Ph th alim ide;
Glycosyl don ors; Glycosyl acceptors; Glycosylation s; Peptidoglycan ; Glycoprotein s.
Collect. Czech. Chem. Commun. (Vol. 69) (2004)
doi:10.1135/cccc20041914

2-Amino-2-deoxy-β-D-galactopyranosyl-(1→4)-2-amino-2-deoxy-β-D-galactopyranosides
1915
Th e β(1→4)-lin ked 2-am in o-2-deoxy-D-h exopyran ose m oieties are fre-
quen tly occurrin g structural un its in various biologically im portan t oligo-
sacch arides an d th eir glycocon jugates, wh ich h ave m ultiple biological fun c-
tion s an d activities, such as a play a key role in m olecular recogn ition an d
in teraction s of th e cell–cell, cell–bacteria, an d cell–virus types1–3. In con -
trast to th e large n um ber of works devoted to th e syn th esis of oligosacch a-
rides with β(1→4)-lin ked 2-am in o-2-deoxy-D-glucopyran ose un its, th e syn -
th esis of an alogous oligosacch arides with β(1→4)-lin ked 2-am in o-2-deoxy-
D-galactopyran ose un its h as received on ly little atten tion so far. Th e
β(1→4)-lin ked N-acetylglucosam in e m oieties form e.g. an im portan t struc-
tural polysacch aride ch itin 4, glycan part of peptidoglycan of bacterial cell
walls5,6 as well as th e reducin g en d of glycan residues of N-glycoprotein s3.
A system atic study devoted to th e use of th e m ost com m on glycosylation
m eth ods for th e form ation of 1,2-trans-glycosidic bon d in th e syn th esis of
oligosacch arides with β(1→4)-lin ked 2-am in o-2-deoxy-D-glucopyran ose
un its was reported by Paulsen et al.7 Th e β(1→4)-lin ked N-acetylgalactos-
am in e to 3-O-sialosyl-β-D-galactopyran oside un it con stitutes a core un it of
gan gliosides8,9. Due to th e problem of form ation of β(1→4) glycosidic bon d
between two D-galactosam in e un its on ly on e article related to th is topic de-
scribin g syn th esis of gan glioside lactam s (i.e., stable an alogs of gan glioside
lacton es) was publish ed. Th is syn th esis is based on th e glycosylation of
2-am in o-2-deoxy-3-O-(sialosyl-1′,2′-lactam )-β-D-galactopyran oside subun it
or 2-azido-2-deoxy-3-O-sialosyl-β-D-galactopyran oside subun it as glycosyl
acceptor in position OH(4) with peracetylated 2-deoxy-2-ph th alim ido-
D-galactopyran osyl brom ide as glycosyl don or10. Oligosacch arides con sist-
in g of β(1→4)-lin ked 2-am in o-2-deoxygalactopyran ose un its are a group of
com poun ds h avin g a sign ifican t poten tial from both th e syn th etic an d bio-
logical poin ts of view. Th e 2-am in o-2-deoxy-β-D-galactopyran ose un its
h ave equatorially orien ted glycosidic bon d an d axially orien ted C(4)–O
bon d (i.e., in verted con figuration at both lin kage cen ters in com parison to
th e α-D-glucopyran ose un its, form in g cyclodextrin m olecules) an d so th ey
satisfy th e basic criteria for cyclization 11. Oligosacch arides con sistin g of
β(1→4)-lin ked 2-acetam ido-2-deoxy-D-galactopyran ose un its also seem to
be poten tial m im ics of n atural ligan ds for activated receptor of NK (n atural
killer) cells, takin g in to accoun t th e fact th at th e bin din g activity of
N-acetyl-D-galactosam in e is h igh er th an N-acetyl-D-glucosam in e an d in th e
case of ch itooligom ers th is activity in creases with elon gation of th e
sacch aride ch ain 12. Th e above m en tion ed facts m otivated us to focus our
atten tion on th e problem of syn th esis of oligosacch arides con sistin g
β(1→4)-lin ked 2-acetam ido-2-deoxy-D-galactopyran ose un its.
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

1916
Veselý, Ledvina, Jindřich, Trnka, Šaman:
RESULTS AND DISCUSSIONS
In th e syn th esis of an oligosacch aride con sistin g from β(1→4)-lin ked
2-am in o-2-deoxy-D-galactopyran ose un its we were con fron ted with th e
problem of stereoselective form ation of 1,2-trans-glycosidic bon d between
glycosyl don or an d glycosyl acceptor bearin g a free axially orien ted
OH group in position 4. A large n um ber of procedures for th e syn th esis of
1,2-trans-di- an d oligosacch arides are described. For th e 1,2-trans-glycosidic
lin kin g of 2-am in o-2-deoxyh exopyran oside residue, th e Koen igs–Kn orr,
oxazolin e an d ph th alim ide m eth ods are m ost often used3,13,14. Th e
ph th alim ide m eth od is th e m ost preferred, because 2-deoxy-2-ph th alim ido-
h exopyran oses with h alogen , trich loroacetim idate or alkylsulfan yl group at
C-1 seem to be th e m ost efficien t don ors an d sh ow th e h igh est stereo-
selectivity3,7. Th e axially orien ted OH(4) group on th e galactopyran ose skel-
eton is in gen eral foun d to be th e least reactive15. Th us, we were been
prom pted to m ake a system atic com parative in vestigation of th e m ost
widely used glycosylation m eth ods usin g th e syn th esis of m odel disac-
ch arides.
For th e preparation of appropriate glycosyl don ors an d acceptors of
galacto con figuration , th e approach based on th e in version of con figuration
at C-4 of th e correspon din g syn th on s with gluco con figuration 16–18 was ap-
plied (Sch em e 1). We used th e m esyl group as a leavin g group an d sodium
acetate as a n ucleoph ile, in stead of a com bin ation of trifluorom eth an e-
sulfon yl group with tetrabutylam m on ium or cesium acetate16–18. Th e m ore
stable 4-O-m esyl derivatives 2a an d 2b (in con trast to an alogical 4-O-
trifluorom eth an esulfon yl derivatives) can be isolated an d are useful syn -
th on s for reaction s with oth er n ucleoph iles, wh ich give th e correspon din g
sacch aride un its with galacto con figuration . Eth yl 3,6-di-O-ben zyl-2-deoxy-
4-O-m esyl-2-ph th alim ido-1-th io-β-D-glucopyran oside (2a) an d eth yl 3-O-
allyl-6-O-b en zyl-2-d eo xy-4-O-m esyl-2-p h t h alim id o -1-t h io -β-D-glu co-
pyran oside (2b) were obtain ed by th e reaction of eith er eth yl 3,6-di-O-
ben zyl-2-deoxy-2-ph th alim ido-1-th io-β-D-glucopyran oside19–21 (1a), or eth yl
OBn
OBn
OBn
AcO
RO
O
O
b
O
a
HO
RO
MsO
RO
SEt
SEt
SEt
NPht
NPht
NPht
1a, R= Bn
1b, R=All
2a, R=Bn
2b, R=All
3a, R=Bn
3b, R=All
a) MsCl, pyridine; b) NaOAc, DMSO
Ms = mesyl; Pht = phthaloyl
SCHEME 1
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

2-Amino-2-deoxy-β-D-galactopyranosyl-(1→4)-2-amino-2-deoxy-β-D-galactopyranosides
1917
3-O-allyl-6-O-ben zyl-2-deoxy-2-ph th alim ido-1-th io-β-D-glucopyran oside18,20
(1b) with m eth an esufon yl ch loride in pyridin e. Mesylates 2a an d 2b upon
treatm ent with anhydrous sodium acetate in dry dim ethyl sulfoxide at 130 °C,
afforded th e key com poun ds eth yl 4-O-acetyl-3,6-di-O-ben zyl-2-deoxy-2-
ph th alim ido-1-th io-β-D-galactopyran oside (3a) an d eth yl 4-O-acetyl-3-O-
allyl-6-O-ben zyl-2-deoxy-2-ph th alim ido-1-th io-β-D-galactopyran oside (3b),
respectively, in very good yields.
Th e attractive feature of th ioglycosides in oligosacch aride syn th esis is
th at th ey can be utilized directly as glycosyl don ors by activation via sul-
fon ium ion or readily con verted in to oth er glycosyl don ors used in m ost
com m on glycosylation m eth ods22 (i.e., glycosyl brom ides, fluorides23
,
glycosyl trich loroacetim idates24 an d pen t-4-en yl (Pen t) glycosides). Th e
β-an om er of glycosyl brom ide 4 was obtain ed by th e reaction of eth yl
th ioglycoside 3a with brom in e in dich lorom eth an e (Sch em e 2). Th e reac-
tion of eth yl th ioglycoside 3a with N-brom osuccin im ide (NBS) an d dieth yl-
am in osulfur trifluoride (DAST) in dich lorom eth an e afforded a m ixture of α-
an d β-glycosyl fluorides 5a an d 5b, in th e 1:15 ratio, wh ich was separated
by ch rom atograph y on a silica gel colum n . Th e β-an om er of trich loro-
acetim idate 7 was prepared from eth yl th ioglycoside 3a by splittin g off th e
eth ylsulfan yl group with N-iodosuccin im ide (NIS) in a water–aceton e m ix-
ture, to yield 6, wh ich was th en con verted to 7 by usin g a m odified litera-
ture25 procedure treatm en t with trich loroaceton itrile in th e presen ce of
1,8-diazabicyclo[5.4.0]un dec-7-en e (DBU) in toluen e. Th e silver perch lorate
prom oted reaction of glycosyl brom ide 4 with pen t-4-en -1-ol in dich loro-
m eth an e afforded pen t-4-en yl glycoside 9a. Th e pen t-4-en yl glycoside 9b
was prepared directly from eth yl th ioglycoside 3b by m eth yl triflate-
prom oted con den zation with pen t-4-en -1-ol in dich lorom eth an e. Eth yl
th ioglycoside 8, pen t-4-en yl glycosides 10a an d 10b an d 4-O-trim eth ylsilyl
derivative 11 were ch osen as glycosyl acceptors for th is com parative study.
Com poun d 11 represen ts glycosyl acceptor suited for glycosylation with
glycosyl fluorides an d silicon -based catalysis26. Com poun ds 8, 10a an d 10b
were prepared by Zem plén deacetylation from 4-O-acetates 3a, 9a an d 9b
respectively. Silyl derivative 11 was obtain ed by reaction of com poun d 10a
with trim eth ylsilyl ch loride an d h exam eth yldisilazan e in a m ixture of
dich orom eth an e an d pyridin e.
Th e results of th e presen ted com parative in vestigation of th e m ost widely
used glycosylation m eth ods usin g above specified glycosyl don ors 3a, 4, 5b
an d 7, an d glycosyl acceptors 8, 10a, 10b an d 11 in th e syn th esis of m odel
disacch arides con tain in g (1→4)-lin ked 2-am in o-2-deoxygalactopyran ose
un its are sum m arized in Table I. Th e silver triflate prom oted glycosylation
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

1918
Veselý, Ledvina, Jindřich, Trnka, Šaman:
OBn
AcO
RO
OBn
AcO
BnO
g
O
O
OPent
Br
NPht
NPht
4
9a, R = Bn
9b, R = All
a
e
f
OBn
HO
RO
O
OBn
AcO
BnO
OBn
OPent
AcO
RO
O
b
c
NPht
O
X
SEt
10a, R = Bn
10b, R = All
NPht
Y
NPht
5a, X = H, Y = F
5b, X = F, Y = H
h
3a, R=Bn
3b, R=All
OBn
O
OBn
TMSO
BnO
AcO
O
OPent
OH
BnO
NPht
11
NPht
d
6
OBn
HO
RO
OBn
AcO
BnO
O
NH
CCl3
O
e
SEt
O
NPht
NPht
8, R=Bn
7
a) Br2, CH2Cl2; b) NBS, DAST in CH2Cl2, -35 °C; c) NIS, H2O and acetone; d) CCl3CN and
DBU in toluene, 0°C and then r.t.; e) MeONa in MeOH; f) pent-4-en-1-ol and MeOTf in CH2Cl2;
g) pent-4-en-1-ol and AgClO4 in CH2Cl2; h) TMSCl and HMDS in CH2Cl2 and pyridine
SCHEME 2
of ethyl thioglycoside 8 with glycosyl brom ide 4 in dichlorom ethane at –45 °C
in th e presen ce of base gave th e expected disacch aride 12 in a very low
yield an d eth yl th ioglycoside 3a was obtain ed as a m ajor product (Sch em e 3).
Th e base, in th e case of little reactive glycosyl acceptors acts as a glyco-
OBn
AcO
SEt
NPht
O
O
a or b
OBn
O
+
3a
4
8
+
BnO
NPht
BnO
12
a) AgOTf, CH2Cl2, -45°C; b) AgClO4, AgCO3, CH2Cl2, r.t.
SCHEME 3
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

2-Amino-2-deoxy-β-D-galactopyranosyl-(1→4)-2-amino-2-deoxy-β-D-galactopyranosides
1919
sylation in h ibitor27,28. Application of th e glycosidation procedure usin g sil-
ver perch lorate in th e presen ce of silver carbon ate9, wh ich acts as a scaven -
ger of h ydrogen brom ide, did n ot lead to sign ifican t in crease in th e produc-
tion of target com poun d 12 an d eth yl glycoside 3a was still a m ajor prod-
uct. Th e form ation of un expected eth yl th ioglycoside 3a can be in terpreted
as a result of low reactivity of axially orien ted OH(4) group of glycosyl ac-
ceptor (Sch em e 4). Due to th is fact th e activated form of glycosyl don or at-
tacks m ain ly sulfur at th e reducin g en d of glycosyl acceptor to give sulfon -
ium ion A. Th e ion decom poses to form eth yl th ioglycoside 3a an d carbo-
cation B, wh ich is stabilized by elim in ation to form glycal C. An an alogous
OBn
OBn
HO
AcO
BnO
O
O
+
glycosyl
promotor
SEt
BnO
Br
+
NPht
NPht
4
8
OBn
OBn
BnO
OBn
AcO
AcO
BnO
OH
HO
BnO
Et
O
O
O
O
OBn
SEt
S
BnO
NPht
NPht
NPht
NPht
3a
B
A
-H+
OBn
HO
BnO
O
C
NPht
SCHEME 4
couplin g of th e correspon din g syn th on s with gluco con figuration followed
the expected course, to afford disaccharide 14 in a very good yield (Schem e 5).
Th e problem of in term olecular m igration of eth ylsulfan yl group was solved
by usin g glycosyl acceptor h avin g pen t-4-en yl group at th e reducin g en d.
BnO
AcO
OBn
OBn
BnO
O
O
O
O
a
AcO
BnO
HO
BnO
+
Br
O
BnO
SEt
SEt
BnO
NPht
NPht
NPht
NPht
13
1a
14
a) AgOTf, CH2Cl2, -45 °C
SCHEME 5
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

1920
Veselý, Ledvina, Jindřich, Trnka, Šaman:
Couplin g of glycosyl brom ide 4 with pen t-4-en yl glycoside 10a (Sch em e 6)
prom oted with silver perch lorate in th e presen ce of silver carbon ate gave a
m ixture of β(1→4)- an d α(1→4)-lin ked disacch arides 16a an d 16b, respec-
tively, in th e 2.7:1 ratio, in a total yield of 78%. Th e use of eth yl th io-
glycoside 3a as glycosyl don or activated with m eth yl triflate, by usin g th e
procedure as reported in th e literature20, led to an in crease in th e yield of
α(1→4)-lin ked disacch aride 16b, but th e overall yield was low. Th e attem pt
R3O
R2O
OBn
OBn
AcO
R1O
O
O
+
OPent
Y
NPht
NPht
3a, R1 = Bn, X = SEt
4, R1 = Bn, X = Br
5b, R1 = Bn, X = F
10a, R2 = Bn, R3 = H
10b, R2 = All, R3 = H
11, R2 = Bn, R3 = TMS
7, R1 = Bn, X = OC(NH)CCl3
OBn
AcO
O
OBn
AcO
R1O
OPent
NPht
OPent
O
O
OBn
PhtN
O
OBn
R2O
O
+
R1O
O
NPht
NPht
R2O
16b, R1 = R2 = Bn
17b, R1 = Bn, R2 = All
16a, R1 = R2 = Bn
17a, R1 = Bn, R2 =All
SCHEME 6
to couple β-glycosyl fluoride 5b with pen ten yl glycoside 10a by usin g tita-
n ium tetrafluoride as glycosyl prom otor29 afforded, beside un reacted start-
in g com poun ds, 24% of disacch aride 16a, 17% of disacch aride 16b an d
15% of α-glycosyl fluoride 5a. Th e sam e couplin g carried out with th e use
of m etallocen e (Cp2ZrCl2/AgClO4) as a catalyst30,31 gave, in addition to
un reacted startin g com poun ds, 36% of disacch aride 16a an d 14% of
disacch aride 16b. Glycosylation usin g glycosyl fluorides as glycosyl don ors
an d silicon -based catalysis26, wh ich em ploys th e em in en t affin ity of silicon
to fluorin e, was un successful. Th e trim eth ylsilyl triflate prom oted reaction
of 5b with 10a yielded a com plex m ixture from wh ich th e target
disacch aride 16a was isolated in a very low yield. Couplin g of glycosyl
trich loroacetim idate 7 with 10a prom oted with boron trifluoride eth erate7
afforded, in addition to un reacted glycosyl acceptor 10a, 30% of
disacch aride 16a an d 11% of disacch aride 16b. A sign ifican t in crease in
stereoselectivity an d efficien cy of th is glycosylation , i.e., form ation of
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

2-Amino-2-deoxy-β-D-galactopyranosyl-(1→4)-2-amino-2-deoxy-β-D-galactopyranosides
1921
β(1→4)- an d α(1→4)-lin ked disacch arides 16a an d 16b in th e ratio 5:1 an d
60% overall yield, was ach ieved by usin g trim eth ylsilyl triflate as a stron ger
Lewis acid. Th e replacem en t of ben zyl protectin g group in position OH(4)
with less bulky allyl group did n ot h ave an y positive effect. Silver perch lo-
rate in th e presen ce of silver carbon ate prom oted couplin g of glycosyl bro-
m ide 4 with pen ten yl glycoside 10b gave, in addition to un reacted glycosyl
acceptor 10b, 17% of disacch aride 17a an d 11% of disacch aride 17b.
Sum m arizin g th e results (Table I) revealed th at th e stereoselectivity
an d efficien cy of glycosylation of D-galactosam in e in com parison with D-
glucosam in e was lower, due to th e low reactivity of axially orien ted OH(4)
group in a galactopyran ose rin g. Th e m axim um overall yields of β(1→4)-
an d α(1→4)-lin ked disacch arides were obtain ed by silver perch lorate in th e
presen ce silver carbon ate prom oted glycosylation with glycosyl brom ide.
Quite a good stereoselectivity in favor of β(1→4)-lin ked disacch arides was
ach ieved by Sch m idt’s trich loroacetim idate m eth od.
EXPERIMENTAL
Meltin g poin ts were determ in ed on a Kofler block an d are un corrected. Specific rotation s
were m easured on a Perkin –Elm er 141 polarim eter at 22 °C an d are given in deg cm 2 g–1
.
Elem en tal an alyses were perform ed usin g a Perkin –Elm er 2400 II in strum en t. NMR spectra
were recorded on a Bruker Avan ce 500 spectrom eter in th e FT m ode at 500.1 MHz (1H) an d
at 125.8 MHz (13C) in CDCl3 or (CD3)2SO, usin g tetram eth ylsilan e as in tern al stan dard for
1H NMR spectra an d CDCl3 (δ 77.0) or (CD3)2SO (δ 39.7) sign als as stan dards for 13C NMR
spectra. For un am biguous assign m en t of sign als in 13C NMR spectra, 1H- an d 13C-h etero-
correlated 2D NMR spectra were m easured by gHSQC an d gHMBC tech n iques usin g th e
stan dard pulse sequen ces delivered by th e producer of th e spectrom eter. Th e followin g typi-
cal param eters were used: spectral width in both f1 an d f2 dim en sion s 5000 an d 17 000 Hz,
respectively, n um ber of scan s 16, n um ber of in crem en ts in f1 dim en sion 256, recycle delay
1 s, acquisition tim e 0.2 s, 90° pulse for 1H was 12.5 µs, data m atrix for processin g 2048 ×
2048 datapoin ts. For processin g, sh ifted sin ebell weigh tin g fun ction was used. Ch em ical
sh ifts are given in ppm (δ-scale) an d couplin g con stan ts (J) in Hz. Positive-ion FAB m ass
spectra were m easured on a BeqG-geom etry m ass spectrom eter ZAB-EQ (VG An alytical,
Man ch ester, U.K.) usin g an M-Scan FAB gun (Xe, en ergy 8 keV) at an acceleratin g voltage of
8 kV. Sam ples were dissolved in ch loroform or m eth an ol, an d a m ixture of glycerol an d
th ioglycerol or dim eth yl sulfoxide was used as m atrix. Th in -layer ch rom atograph y (TLC) was
perform ed on DC-Alufolien Kieselgel 60 F254 (Merck, Darm stadt, Germ an y) or Silufol UV254
(Kavalier, Votice, Czech Republic) silica gel sh eets. Preparative ch rom atograph y was per-
form ed on a silica gel colum n , particle size 40–60 µm (Fluka, Neu-Ulm , Switzerlan d). An alyt-
ical RP HPLC was perform ed usin g a Waters in strum en t (PDA detector, software Milen n ium
32; Milford, MA, U.S.A.) equipped with a Nova-Pak C18 colum n (150 × 3.9 m m ), particle
size 4 µm . Preparative RP HPLC was perform ed on a colum n (250 × 25 m m ) filled with
LiCh rosorb RP-18, particle size 5 µm (Merck, Darm stadt, Germ an y). Solven ts were evapo-
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

1922
Veselý, Ledvina, Jindřich, Trnka, Šaman:
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

2-Amino-2-deoxy-β-D-galactopyranosyl-(1→4)-2-amino-2-deoxy-β-D-galactopyranosides
1923
rated on a rotary vacuum evaporator at 40 °C. An alytical sam ples were dried at 6.5 Pa an d
25 °C for 8 h .
Eth yl 3,6-Di-O-ben zyl-2-deoxy-4-O-m esyl-2-ph th alim ido-1-th io-β-D-
glucopyran oside (2a) an d Eth yl 3-O-Allyl-6-O-ben zyl-2-deoxy-4-O-m esyl-
2-ph th alim ido-1-th io-β-D-glucopyran oside (2b)
Eth yl 3,6-di-O-ben zyl-2-deoxy-2-ph th alim ido-1-th io-β-D-glucopyran oside19–21 (1a; 53.4 g,
100 m m ol) or eth yl 3-O-allyl-6-O-ben zyl-2-deoxy-2-ph th alim ido-1-th io-β-D-glucopyran os-
ide18,20 (1b; 48.4 g, 100 m m ol) was dried at room tem perature an d 20 Pa for 6 h an d th en
dissolved in pyridin e (600 m l). Mesyl ch loride (50 m l, 646 m m ol) was slowly added un der
stirrin g an d th e m ixture was stirred at room tem perature for 24 h . Progress of th e reaction
was m on itored by TLC in toluen e–eth yl acetate (5:1). Toluen e (3000 m l) was added an d th e
m ixture was wash ed with cool 1 M aqueous HCl (3 × 800 m l), water (3 × 600 m l), dried over
an h ydrous m agn esium sulfate an d evaporated in vacuo.
Compound 2a: Yield 58.7 g (96%) of a solid 2a, ch rom atograph ically h om ogen ous in th e
solven t system m en tion ed above. An an alytical sam ple was prepared by crystallization from
toluen e–petroleum eth er; m .p. 60–62 °C, [α]D +76 (c 0.9, ch loroform ). 1H NMR: see Table II,
13C NMR: see Table V. For C31H33NO8S2 calculated: relative m olecular m ass 611.7,
m on oisotopic m ass 611.2. ESI MS, m/z: 634.0 [M + Na]+. For C31H33NO8S2 (611.7) calculated:
60.87% C, 5.44% H, 2.29% N, 10.48% S; foun d: 60.96% C, 5.56% H, 2.21% N, 10.31% S.
Compound 2b: Yield 53.9 g (96%) of a syrupy com poun d 2b, ch rom atograph ically h om og-
en ous in th e solven t system m en tion ed above. An an alytical sam ple was prepared by ch ro-
m atograph y on a silica gel colum n in toluen e–eth yl acetate (9:1), syrup; [α]D +44 (c 0.5,
ch loroform ). 1H NMR: see Table II, 13C NMR: see Table V. For C27H31NO8S2 calculated: rela-
tive m olecular m ass 561.7, m on oisotopic m ass 561.2. ESI MS, m/z: 584.1 [M + Na]+, 600.1
[M + K]+. For C27H31NO8S2 (561.7) calculated: 57.74% C, 5.56% H, 2.49% N, 11.42% S;
foun d: 57.98% C, 5.71% H, 2.58% N, 11.14% S.
Eth yl 4-O-Acetyl-3,6-di-O-ben zyl-2-deoxy-2-ph th alim ido-1-th io-β-D-
galactopyran oside (3a) an d Eth yl 4-O-Acetyl-3-O-allyl-6-O-ben zyl-
2-deoxy-2-ph th alim ido-1-th io-β-D-galactopyran oside (3b)
Com poun d 2a (15.3 g, 25 m m ol) or com poun d 2b (14.0 g, 25 m m ol) an d fresh ly m elted so-
dium acetate (131 g, 1600 m m ol) were dried in a flask equipped with a reflux con den ser at
room tem perature an d 20 Pa for 4 h an d th en th e apparatus was flush ed with argon (2×).
Dry dim eth yl sulfoxide (1400 m l) was added an d th e reaction m ixture was stirred un der
argon atm osph ere at 130 °C for 24 h . Progress of th e reaction was m on itored on TLC in
toluen e–eth yl acetate (5:1). Th e solven t was evaporated in vacuo at 90 °C an d th e residue
was partition ed between toluen e (1000 m l) an d water (700 m l). Organ ic layer was separated,
wash ed with water (2 × 700 m l), dried over an h ydrous m agn esium sulfate an d evaporated.
Th e residue was ch rom atograph ed on a silica gel colum n (350 g) in toluen e–eth yl acetate (7:1).
Compound 3a: Yield 10.4 g (72%) of a syrupy com poun d 3a; [α]D +65 (c 0.6, ch loroform ),
lit.16 gives [α]D +64 (c 1.0, ch loroform ). 1H NMR: see Table II, 13C NMR: see Table V. For
C
32H33NO7S calculated: relative m olecular m ass 575.7, m on oisotopic m ass 575.2. FAB MS,
m/z: 514 [M – EtSH + H]+. ESI MS, m/z: 598.3 [M + Na]+, 614.1 [M + K]+. For C32H33NO7S
(575.7) calculated: 66.76% C, 5.78% H, 2.43% N, 5.57% S; foun d: 67.04% C, 5.89% H,
2.53% N, 5.49% S.
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

1924
Veselý, Ledvina, Jindřich, Trnka, Šaman:
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

2-Amino-2-deoxy-β-D-galactopyranosyl-(1→4)-2-amino-2-deoxy-β-D-galactopyranosides
1925
Compound 3b: Yield 8.5 g (65%) of a syrupy com poun d 3b; [α]D +33 (c 0.3, ch loroform );
lit.18 gives [α]D +24 (c 0.6, ch loroform ). 1H NMR: see Table II, 13C NMR: see Table V. For
C
28H31NO7S calculated: relative m olecular m ass 525.6, m on oisotopic m ass 525.2. FAB MS,
m/z: 526 [M + H]+, 548 [M + Na]+. For C28H31NO7S (525.6) calculated: 63.98% C, 5.94% H,
2.66% N, 6.10% S; foun d: 64.17% C, 6.07% H, 2.72% N, 6.21% S.
4-O-Acetyl-3,6-di-O-ben zyl-2-deoxy-2-ph th alim ido-α/β-D-galactopyran osyl Brom ide (4)
Com poun d 3a (576 m g, 1 m m ol) was dried in an apparatus equipped with a septum by
co-distillation with dry ben zen e (3 × 10 m l) an d th en at room tem perature an d 20 Pa for
4 h . Th e apparatus was flush ed with argon (2×) an d dry dich lorom eth an e (2 m l) was added
th rough th e septum . After dissolution , th e m ixture was cooled to 0 °C an d 1 M solution of
brom in e in dry dich lorom eth an e (1.1 m l, 1.1 m m ol) was added th rough th e septum . Th e
m ixture was stirred at 0 °C for 1 h . In th e sam e apparatus th e solven ts were evaporated in
vacuo (water pum p) with exclusion of m oisture. Th e residue was co-evaporated with toluen e
(3 × 10 m l) at 20 Pa, an d lyoph ilized from ben zen e. Yield 590 m g (98%) of α/β-an om eric
m ixture (3:4) of com poun d 4; [α]D +77 (c 0.1, ch loroform ). Th e ratio of an om ers was deter-
m in ed by 1H NMR spectra. 1H NMR: see Table II, 13C NMR: see Table V. For C30H28BrNO7
calculated: relative m olecular m ass 594.5, m on oisotopic m ass 593.1. FAB MS, m/z: 594 [M +
H]+. For C30H28BrNO7 (594.5) calculated: 60.61% C, 4.75% H, 13.44% Br, 2.36% N; foun d:
66.89% C, 4.91% H, 13.32% Br, 2.38% N.
4-O-Acetyl-3,6-di-O-ben zyl-2-deoxy-2-ph th alim ido-α-D-galactopyran osyl Fluoride (5a) an d
4-O-Acetyl-3,6-di-O-ben zyl-2-deoxy-2-ph th alim ido-β-D-galactopyran osyl Fluoride (5b)
Com poun d 3a (1.73 g, 3.0 m m ol) was dried at room tem perature an d 20 Pa for 4 h , th en
N-brom osuccin im ide (1.07 g, 6.0 m m ol) was added an d dryin g was con tin ued in an appara-
tus equipped with a septum for an oth er 1 h . Th e apparatus was flush ed with argon (2×) an d
dry dich lorom eth an e (70 m l) was added trough th e septum . After dissolution , th e m ixture
was cooled to –45 °C an d (dieth ylam in o)sulfur trifluoride (DAST) (1 m l, 5.1 m m ol) was
added un der stirrin g th rough th e septum an d th e stirrin g was con tin ued at –35 °C for 6 h .
Saturated aqueous sodium h ydrogen carbon ate (30 m l) was added an d th e m ixture was
stirred at room tem perature for an oth er 1 h . Th e organ ic layer was separated, wash ed with
water (3 × 15 m l), dried over an h ydrous m agn esium sulfate an d evaporated in vacuo. Ch ro-
m atograph y of th e residue on silica gel colum n (80 g) in toluen e–eth yl acetate (20:1) af-
forded 72 m g (5%) of α-an om er 5a an d 1.1 g (69%) of β-an om er 5b.
Compound 5a: Syrup; [α]D +96 (c 0.2, ch loroform ). 1H NMR: see Table II, 13C NMR: see
Table V. For C30H28FNO7 calculated: relative m olecular m ass 533.5, m on oisotopic m ass
533.2. ESI MS, m/z: 514 [M – F]+, 556 [M + Na]+. For C30H28FNO7 (533.5) calculated: 67.53% C,
5.29% H, 3.56% F, 2.63% N; foun d: 67.26% C, 5.55% H, 3.36% F, 2.48% N.
Compound 5b: Solid; [α]D +65 (c 0.1, ch loroform ). 1H NMR: see Table II, 13C NMR: see
Table V. For C30H28FNO7 calculated: relative m olecular m ass 533.5, m on oisotopic m ass
533.2. ESI MS, m/z: 514 [M – F]+, 556 [M + Na]+. For C30H28FNO7 (533.5) calculated: 67.53% C,
5.29% H, 3.56% F, 2.63% N; foun d: 67.48% C, 5.43% H, 3.39% F, 2.54% N.
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

1926
Veselý, Ledvina, Jindřich, Trnka, Šaman:
4-O-Acetyl-3,6-di-O-ben zyl-2-deoxy-2-ph th alim ido-β-D-galactopyran ose (6)
Com poun d 3a (1.04 g, 1.8 m m ol) an d N-iodosuccin im ide (930 m g, 4.1 m m ol) were dis-
solved un der stirrin g in a m ixture aceton e–water (4:1, 30 m l) at room tem perature an d stir-
rin g was con tin ued for 12 h . Th e solven ts were evaporated in vacuo an d th e residue was
co-distilled with toluen e (3 × 30 m l) an d th en dissolved in ch loroform (30 m l). Th e solution
was wash ed with 30% aqueous sodium th iosulfate (3 m l), water (2 × 3 m l), dried over an h y-
drous m agn esium sulfate an d evaporated in vacuo, givin g 950 m g (98%) of com poun d 6;
[α]D +66 (c 0.3, ch loroform ). Com poun d 6 with out specification of con figuration on th e
an om eric cen tre is described in th e literature25 as a product of deallylation product of ap-
propriate allyl glycoside; [α]D +83 (c 0.6, ch loroform ). 1H NMR: see Table II, 13C NMR: see
Table V. For C30H29NO8 calculated: relative m olecular m ass 531.5, m on oisotopic m ass 531.5.
FAB MS, m/z: 514 [M – H2O]+, 554 [M + Na]+. For C30H29NO8 (531.5) calculated: 67.79% C,
5.50% H, 2.64% N; foun d: 67.61% C, 5.61% H, 2.49% N.
O-(4-O-Acetyl-3,6-di-O-ben zyl-2-deoxy-2-ph th alim ido-β-D-galactopyran osyl)
Trich loroacetim idate (7)
Com poun d 6 (870 m g, 1.6 m m ol) was dried in an apparatus equipped with a septum at
room tem perature an d 20 Pa for 4 h . Th e apparatus was flush ed with argon (2×) an d dry
toluen e (23 m l) was added th rough th e septum . After dissolution , th e m ixture was cooled to
0 °C, an d trich loroaceton itrile (2 m l, 9.6 m m ol) an d 1 M solution of DBU in toluen e (320 µl,
0.32 m m ol) were added th rough th e septum . Th e stirrin g was th en con tin ued at room tem -
perature for 24 h . Progress of th e reaction was m on itored on TLC in toluen e–eth yl acetate
(1:1). A saturated aqueous am m on ium ch loride (2 m l) was added. Organ ic layer was sepa-
rated, wash ed with water (2 × 10 m l), th en dried over an h ydrous m agn esium sulfate an d
evaporated in vacuo. Ch rom atograph y of th e residue on a silica gel colum n (20 g) in
toluen e–eth yl acetate (20:1) afforded 680 m g (63%) of com poun d 7; [α]D +63 (c 0.2, ch loro-
form ). Com poun d 7 is described in 25 as in com plete ch aracterized in term ediate. 1H NMR: see
Table II, 13C NMR: see Table V. For C32H29Cl3N2O8 calculated: relative m olecular m ass
675.9, m on oisotopic m ass 674.1. FAB MS, m/z: 514 [M – CCl3CNHO]+, 697 [M + H]+. For
C
32H29Cl3N2O8 (675.9) calculated: 56.86% C, 4.32% H, 15.73% Cl, 4.14% N; foun d: 56.73% C,
4.45% H, 15.60% Cl, 4.08% N.
Eth yl 3,6-Di-O-ben zyl-2-deoxy-2-ph th alim ido-1-th io-β-D-galactopyran oside (8)
Com poun d 3a (576 m g, 1 m m ol) was dried in an apparatus equipped with a septum by
co-distillation with dry ben zen e (3 × 5 m l) an d th en at room tem perature an d 20 Pa for 4 h .
Th e apparatus was flush ed with argon (2×), dry m eth an ol (10 m l) an d 1 M MeONa (100 µl,
0.1 m m ol) were added th rough th e septum an d th en th e m ixture was stirred at room tem -
perature for 80 h . Progress of th e reaction was m on itored by TLC in toluen e–eth yl acetate
(5:1). Th e m ixture was n eutralized by addition of Dowex 50 (pyridin ium form ). Th e ion
exch an ger was filtered off, wash ed with m eth an ol (20 m l) an d th e filtrate was evaporated in
vacuo. Ch rom atograph y of th e residue on a silica gel colum n (40 g) in th e above m en tion ed
solven t system gave 460 m g (80%) of a syrupy com poun d 8, wh ich was crystallized from
eth an ol to afford 444 m g (77%) of com poun d 8; m .p. 112–113 °C, [α]D + 58 (c 0.9, ch loro-
form ). 1H NMR: see Table II, 13C NMR: see Table V. For C28H31NO7S calculated: relative m o-
lecular m ass 533.6, m on oisotopic m ass 533.2. FAB MS, m/z: 472 [M – EtSH + H]+, 556 [M +
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

2-Amino-2-deoxy-β-D-galactopyranosyl-(1→4)-2-amino-2-deoxy-β-D-galactopyranosides
1927
Na]+. For C30H31NO6S (533.6) calculated: 67.53% C, 5.85% H, 2.63% N, 6.00% S; foun d:
67.61% C, 5.88% H, 2.61% N, 5.97% S.
Pen t-4-en yl 4-O-Acetyl-3,6-di-O-ben zyl-2-deoxy-2-ph th alim ido-β-D-
galactopyran oside (9a)
A m ixture of silver perch lorate (1.4 g, 6.7 m m ol) an d m olecular sieves 3 Å (3 g) was dried in
an apparatus equipped with a septum at room tem perature an d 20 Pa for 4 h . Th e apparatus
was flush ed with argon (2×) an d dry dich lorom eth an e (30 m l) an d pen t-4-en -1-ol (2 m l,
19.4 m m ol) were added th rough th e septum an d th e m ixture was stirred at room tem pera-
ture for 1 h . Th e m ixture was cooled to –40 °C an d a solution of glycosyl brom ide 4, fresh ly
prepared from 3a (2.4 g, 4 m m ol) an d dry dich lorom eth an e (20 m l), was added th rough th e
septum un der stirrin g durin g 10 m in an d stirrin g was con tin ued at –20 °C for 12 h . A satu-
rated aqueous sodium h ydrogen carbon ate (10 m l) was added at –20 °C an d after warm in g to
room tem perature th e m ixture was diluted with dich lorom eth an e (70 m l) an d filtered
th rough a Celite. Th e filtrate was wash ed with saturated aqueous sodium h ydrogen carbon ate
(30 m l), water (3 × 30 m l), dried over an h ydrous m agn esium sulfate an d evaporated in
vacuo. Ch rom atograph y of th e residue on silica gel colum n (140 g) in toluen e–eth yl acetate
(25:1) gave 2.2 g (90%) of a syrupy com poun d 9a; [α]D +39 (c 0.2, ch loroform ). 1H NMR: see
Table III, 13C NMR: see Table V. For C35H37NO8 calculated: relative m olecular m ass 599.7,
m on oisotopic m ass 599.3. FAB MS, m/z: 600.8 [M + H]+, 622.8 [M + Na]+. For C35H37NO8
(599.7) calculated: 70.10% C, 6.22% H, 2.34% N; foun d: 70.26% C, 6.34% H, 2.26% N.
Pen t-4-en yl 4-O-Acetyl-3-O-allyl-6-O-ben zyl-2-deoxy-2-ph th alim ido-β-D-
galactopyran oside (9b)
Com poun d 3b (1.0 g, 2.0 m m ol) was dried in an apparatus equipped with a septum by co-
distillation with dry ben zen e (3 × 15 m l) an d th en at room tem perature an d 20 Pa for 6 h .
Th e apparatus was flush ed with argon (2×) an d dry dich lorom eth an e (40 m l) was added
th rough th e septum . After dissolution , th e m ixture was cooled to –30 °C an d m eth yl triflate
(0.9 m l, 8.0 m m ol) was added un der stirrin g th rough th e septum . Th e tem perature was al-
lowed to in crease to 0 °C (durin g 15 m in ) an d pen t-4-en -1-ol (2 m l, 19.4 m m ol) was added
th rough th e septum an d stirrin g was th en con tin ued at room tem perature for 6 h . Progress
of th e reaction was m on itored by TLC in toluen e–eth yl acetate (5:1). Pyridin e (2 m l) was
added an d after 1 h stirrin g at room tem perature th e m ixture was diluted with dich loro-
m eth an e (30 m l). Th e solution was wash ed with saturated aqueous sodium h ydrogen -
carbon ate (30 m l), water (2 × 30 m l), dried over an h ydrous m agn esium sulfate an d evapo-
rated in vacuo. Ch rom atograph y of th e residue on silica gel colum n (70 g) in toluen e–eth yl
acetate (20:1) gave 1.0 g (92%) of a syrupy com poun d 9b ; [α]D +4 (c 0.4, ch loroform ).
1H NMR: see Table III, 13C NMR: see Table V. For C31H35NO8 calculated: relative m olecular
m ass 549.6, m on oisotopic m ass 549.2. FAB MS, m/z: 600.8 [M + H]+, 622.8 [M + Na]+. For
C
31H35NO8 (549.6) calculated: 67.74% C, 6.42% H, 2.55% N; foun d: 67.68% C, 6.58% H,
22.49% N.
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

1928
Veselý, Ledvina, Jindřich, Trnka, Šaman:
TABLE III
1H NMR param eters of com poun ds 9–11a
Param eter
9a
9b
10a
10b
11
δ(H-1)
5.13 d
5.15 d
5.09 d
5.12 d
5.11 d
δ(H-2)
4.39 dd
4.42 dd
4.45 dd
4.47 dd
4.57 dd
δ(H-3)
4.28 dd
4.34 dd
4.26 dd
4.28 dd
4.15 dd
δ(H-4)
5.67 dd
5.57 dd
4.16 d
4.15 bd
4.26 d
δ(H-5)
3.92 ddd
3.59 dd
3.92 ddd
3.57 dd
3.79–3.81 m
3.76–3.78 m
3.87–3.89 m
3.39 dt
3.79 dd
3.71–3.76 m
3.64 m
δ(H-6a)
δ(H-6b)
δ(H-1a′)
δ(H-1b′)
δ(H-2′)
δ(H-3′)
δ(H-4′)
δ(H-5a′)
δ(H-5b′)
3.79 dd
3.64 dd
3.63 dd
3.88 dd
3.71–3.76 m
3.36 ddd
3.79 dt
3.39 ddd
3.81 dt
3.43 ddd
3.84 dt
3.42 ddd
3.82 dt
3.80 dt
1.40–1.60 m
1.75–1.92 m
5.55 ddt
4.69 ddt
4.73 ddt
1.44–1.62 m
1.79–1.93 m
5.57 ddt
4.75 ddt
4.72 ddt
1.40–1.58 m
1.77–1.92 m
5.56 ddt
4.71 ddt
4.74 ddt
1.43–1.60 m
1.80–1.93 m
5.58 ddt
4.73 dq
1.40–1.55 m
1.74–1.87 m
5.54 ddt
4.68 ddt
4.72 ddt
4.75 ddt
J(1,2)
8.5
11.1
3.4
1.2
7.0
5.8
9.5
8.4
11.2
3.3
1.2
6.8
6.0
9.6
8.5
8.5
8.5
J(2,3)
10.9
11.0
3.3
11.1
2.8
J(3,4)
3.3
b
J(4,5)
0.0
0.0
b
b
b
b
J(5,6a)
J(5,6b)
J(6a,6b)
5.8
b
b
8.2
11.8
a
Param eters of pen t-4-en yl residue sign ed H-1′ to H-5′, typical values of couplin g con stan ts
in pen t-4-en yl residue: J1a′,2a′ = 6.3, J1a′,2b′ = 7.1, J1b′,2a′ = J1b′,2b′ = 6.2, J1a′,1b′ = 9.8, J3a′,4′
=
J3b′,4′ = 6.6, J3a′,5a′ = J3a′,5a′ = 1.7, J3a′,5b′ = J3b′,5b′ = 1.4, J4′,5a′ = 17.0, J4′,5b′ = 10.3, J5a′,5b′ = 1.9.
Addition al NMR param eters an d param eters of substituen ts: 9a – arom . H: 6.89–7.87 m ,
OCH2C6H5: 4.26 d (1 H, J = 12.4), 4.50 d (1 H, J = 11.9), 4.60 d (1 H, J = 11.9), 4.60 d (1 H,
J = 12.4), OAc: 2.14 s; 9b – arom . H: 7.28–7.89 m , OCH2C6H5: 4.50 d (1 H, J = 11.9), 4.59 d
(1 H, J = 11.9), OAc: 2.14 s, OCH2CH=CH2: 3.80 ddt (1 H, J = 1.3, 1.3, 6.3, 12.9), 4.06 ddt
(1 H, J = 1.5, 1.5, 5.1, 12.9), 5.56 dddd (J = 5.1, 6.3, 10.4, 17.2), 4.95 ddt (J = 1.3, 1.3, 1.7,
10.4), 5.05 dq (J = 3 × 1.6, 17.2); 10a – arom . H: 6.96–7.92 m , OCH2C6H5: 4.34 d (1 H, J =
12.3), 4.64 d (1 H, J = 12.3), 4.62 s (2 H); 10b – arom . H: 7.26–7.92 m , OCH2C6H5: 4.62 s
(2 H), OCH2CH=CH2: 3.88 ddt (1 H, J = 1.4, 1.4, 5.9, 12.9), 4.07 ddt (1 H, J = 1.4, 1.4, 5.5,
12.9), 5.65 ddt (1 H, J = 5.8, 5.8, 10.4, 17.2), 4.99 dq (1 H, J = 3 × 1.3, 10.4), 5.11 dq (1 H,
J = 3 × 1.5, 17.2); 11 – arom . H: 6.92–7.83 m , OCH2C6H5: 4.23 d (1 H, J = 12.1), 4.56 d (1 H,
b
J = 11.9), 4.59 d (1 H, J = 11.9), 4.64 d (1 H, J = 12.1), OSi(CH3)3: 0.15 s (9 H). Value n ot
determ in ed.
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

2-Amino-2-deoxy-β-D-galactopyranosyl-(1→4)-2-amino-2-deoxy-β-D-galactopyranosides
1929
Pen t-4-en yl 3,6-Di-O-ben zyl-2-deoxy-2-ph th alim ido-β-D-galactopyran oside (10a) an d
Pen t-4-en yl 3-O-Allyl-6-O-ben zyl-2-deoxy-2-ph th alim ido-β-D-galactopyran oside (10b)
Com poun d 9a (1.2 g, 2.0 m m ol) or com poun d 9b (1.1 g, 2 m m ol) was dried in an apparatus
equipped with a septum by co-distillation with dry ben zen e (3 × 10 m l) an d th en at room
tem perature an d 20 Pa for 6 h . Th e apparatus was flush ed with argon (2×) an d dry m eth an ol
(40 m l) an d 0.5 M MeONa in m eth an ol (0.5 m l) were added th rough th e septum . Th e m ix-
ture was stirred at room tem perature for 7 days: Progress of th e reaction was m on itored on
TLC in toluen e–eth yl acetate (5:1). Th e m ixture was n eutralized by addition of Dowex 50
(pyridin ium form ), th e ion exch an ger was filtered off, wash ed with m eth an ol (50 m l) an d
filtrate was evaporated in vacuo. Th e residue was ch rom atograph ed on a silica gel colum n
(100 g) in toluen e–eth yl acetate (10:1)
Compound 10a: Yield 981 m g (88%) of a syrupy com poun d 10a; [α]D +33 (c 0.6, ch loro-
form ). 1H NMR: see Table III, 13C NMR: see Table V. For C33H35NO7 calculated: relative m o-
lecular m ass 557.6, m on oisotopic m ass 557.2. FAB MS, m/z: 558.2 [M + H]+, 580.2 [M + Na]+.
For C33H35NO7 (557.6) calculated: 71.08% C, 6.33% H, 2.51% N; foun d: 71.19% C, 6.41% H,
2.43% N.
Compound 10b: Yield 822 m g (81%) of a syrupy com poun d 10b; [α]D +5 (c 0.4, ch loro-
form ). 1H NMR: see Table III, 13C NMR: see Table V. For C29H33NO7 calculated: relative m o-
lecular m ass 507.6, m on oisotopic m ass 507.2. FAB MS, m/z: 508.2 [M + H]+, 530.7 [M + Na]+.
For C29H33NO7 (507.6) calculated: 68.62% C, 6.55% H, 2.76% N; foun d: 68.49% C, 6.68% H,
2.64% N.
Pen t-4-en yl 3,6-Di-O-ben zyl-2-deoxy-2-ph th alim ido-4-O-(trim eth ylsilyl)-β-D-
galactopyran oside (11)
Com poun d 10a (160 m g, 0.3 m m ol) was dried in an apparatus equipped with a septum by
co-distillation with dry ben zen e (3 × 5 m l) an d th en at room tem perature an d 20 Pa for 4 h .
Th e apparatus was flush ed with argon (2×), an d dry dich lorom eth an e (9 m l) an d dry pyri-
din e (4.5 m l) were added th rough th e septum . After dissolution , 1,1,1,3,3,3-h exam eth yl-
disilazan e (130 µl, 0.6 m m ol) an d ch lorotrim eth ylsilan e (150 µl, 1.2 m m ol) were added un -
der stirrin g th rough th e septum an d stirrin g was con tin ued at room tem perature for 48 h .
Progress of th e reaction was m on itored on TLC in toluen e–eth yl acetate (5:1). Th e reaction
m ixture was evaporated in vacuo an d th e residue was ch rom atograph ed on a silica gel col-
um n (12 g) in toluen e–eth yl acetate (20:1), to give 160 m g (88%) of a syrupy com poun d 11;
[α]D +24 (c 0.02, ch loroform ). 1H NMR: see Table III, 13C NMR: see Table V. For
C
36H43NO7Si calculated: relative m olecular m ass 629.8, m on oisotopic m ass 629.3. ESI MS,
m/z: 652 [M + H]+. For C36H43NO7Si (629.8) calculated: 68.65% C, 6.88% H, 2.22% N;
foun d: 68.41% C, 7.07% H, 2.11% N.
Eth yl 4-O-Acetyl-3,6-di-O-ben zyl-2-deoxy-2-ph th alim ido-β-D-galactopyran osyl-
(1→4)-3,6-di-O-ben zyl-2-deoxy-2-ph th alim ido-1-th io-β-D-galactopyran oside (12)
Method A. A m ixture of com poun d 8 (133 m g, 0.25 m m ol) an d silver trifluorom eth an e-
sulfon ate (90 m g, 0.35 m m ol) was dried in a flask equipped with a septum at room tem pera-
ture an d 20 Pa for 8 h . Th e apparatus was flush ed with argon (2×) an d dry dich lorom eth an e
(0.7 m l) was added th rough th e septum . After dissolution , th e m ixture was cooled to –45 °C,
an d a solution of glycosyl brom ide 4, fresh ly prepared from 3a (216 m g, 0.38 m m ol) an d
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

1930
Veselý, Ledvina, Jindřich, Trnka, Šaman:
dry dich lorom eth an e (0.6 m l), was added un der stirrin g th rough th e septum durin g 1 h . Th e
m ixture was stirred at –45 °C for an oth er 1 h an d at –20 °C for 30 m in . Pyridin e (0.5 m l)
was added at –20 °C an d after warm in g to room tem perature th e m ixture was diluted with
ch loroform (5 m l) an d filtered. Th e filtrate was wash ed with 0.5 M HCl (3 × 2 m l), saturated
aqueous sodium h ydrogen carbon ate (3 × 2 m l) an d water (3 × 2 m l), dried over an h ydrous
m agn esium sulfate an d evaporated in vacuo. Th e residue was separated by HPLC on silica
gel C18 colum n in solven t system water–m eth an ol (lin ear gradien t 50→100%) to give 13 m g
(5%) of a syrupy com poun d 12 an d 72 m g (50%) of a syrupy com poud 3a, wh ich is iden ti-
cal in all respects ([α]D, MS, an d NMR spectra) with th e auth en tic com poun d 3a described
above.
Method B: A m ixture of com poun d 8 (133 m g, 0.25 m m ol), silver carbon ate (276 m g,
1.0 m m ol), silver perch lorate (62 m g, 0.3 m m ol) an d m olecular sieves 4 Å (0.8 g) was dried
in an apparatus equipped with a septum at room tem perature an d 20 Pa for 8 h . Th e appara-
tus was flush ed with argon (2×) an d dry dich lorom eth an e (1.4 m l) was added th rough th e
septum . Th e m ixture was stirred at room tem perature for 1 h an d a solution of glycosyl bro-
m ide 4, fresh ly prepared from 3a (216 m g, 0.38 m m ol) an d dry dich lorom eth an e (0.6 m l),
was added un der stirrin g th rough th e septum durin g 3 h . Stirrin g was con tin ued at room
tem perature for an oth er 10 h an d th en pyridin e (1 m l) was added. Th e reaction m ixture was
worked up by th e sam e procedure as is given in m eth od A to afford 45 m g (17%) of a syrupy
com poun d 12 an d 38 m g (55%) of a syrupy com poun d 3a.
Compound 12: [α]D +18 (c 0.1, ch loroform ). 1H NMR: see Table IV, 13C NMR: see Table VI.
For C60H58N2O13S calculated: relative m olecular m ass 1047.2, m on oisotopic m ass 1046.4.
FAB MS, m/z: 877.4 [M – (OBn an d EtS)]+, 1048.4 [M + H]+, 1069.4 [M + Na]+. For
C
60H58N2O13S (1047.2) calculated: 68.82% C, 5.58% H, 2.68% N, 3.06% S; foun d: 69.07% C,
5.67% H, 2.74% N, 2.91% S.
Eth yl 4-O-Acetyl-3,6-di-O-ben zyl-2-deoxy-2-ph th alim ido-β-D-glucopyran osyl-
(1→4)-3,6-di-O-ben zyl-2-deoxy-2-ph th alim ido-1-th io-β-D-glucopyran oside (14)
Eth yl 4-O-acetyl-3,6-di-O-ben zyl-2-deoxy-2-ph th alim ido-1-th io-β-D-glucopyran oside20 (430 m g,
0.75 m m ol) was dried in an apparatus equipped with a septum at room tem perature an d 20 Pa
for 10 h . Th e apparatus was flush ed with argon (2×) an d dry dich lorom eth an e (1.7 m l) was
added th rough th e septum . After dissolution , th e m ixture was cooled to 0 °C an d 1 M solu-
tion of brom in e in dry dich lorom eth an e (0.8 m l) was added th rough th e septum un der stir-
rin g. Th en th e m ixture was stirred at 0 °C for 1 h an d th en at room tem perature for 1 h . In
th e sam e apparatus th e solven ts were evaporated in vacuo (water pum p) with exclusion of
m oisture. Th e residue was co-evaporated with toluen e (3 × 1.5 m l) at 20 Pa, added th rough
th e septum an d th e residue was dissolved in dry dich lorom eth an e (1 m l). Th e solution of
glycosyl brom ide20 13 was used for th e con den zation with 1a.
A m ixture of eth yl 3,6-di-O-ben zyl-2-deoxy-2-ph th alim ido-1-th io-β-D-glucopyran oside19,20
(1a; 266 m g, 0.5 m m ol) an d silver trifluorom eth an esulfon ate (193 m g, 0.75 m m ol) was dried
in an apparatus equipped with a septum at room tem perature an d 20 Pa for 8 h . Th e appara-
tus was wash ed with argon (2×) an d dry dich lorom eth an e (1 m l) was added th rough th e sep-
tum . After dissolution , th e m ixture was cooled to –45 °C an d a solution of glycosyl brom ide
13 was added th rough th e septum un der stirrin g durin g 1 h . Th en th e m ixture was stirred at
–45 °C for an oth er 1 h an d at –20 °C for 30 m in . Pyridin e (0.5 m l) was added at –20 °C an d
after warm in g to room tem perature th e m ixture was diluted with ch loroform (10 m l) an d
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

2-Amino-2-deoxy-β-D-galactopyranosyl-(1→4)-2-amino-2-deoxy-β-D-galactopyranosides
1931
filtered. Th e filtrate was wash ed with 0.5 M HCl (3 × 3 m l), saturated aqueous sodium
h ydrogen carbon ate (3 × 3 m l), water (3 × 3 m l), dried over an h ydrous m agn esium sulfate
an d evaporated in vacuo. Ch rom atograph y of th e residue on a silica gel colum n (30 g) in
toluen e–eth yl acetate (9:1) gave 320 m g (61%) of solid com poun d 14; [α]D +47 (c 1.3, ch lo-
roform ). 1H NMR: see Table IV, 13C NMR: see Table VI. For C60H58N2O13S calculated: relative
m olecular m ass 1047.2, m on oisotopic m ass 1046.4. FAB MS, m/z: 877.4 [M – (OBn an d
EtS)]+, 1048.4 [M + H]+, 1069.4 [M + Na]+. For C60H58N2O13S (1047.2) calculated: 68.82% C,
5.58% H, 2.68% N; foun d: 69.09% C, 5.64% H, 2.67% N.
Pen t-4-en yl 4-O-Acetyl-3,6-di-O-ben zyl-2-deoxy-2-ph th alim ido-β-D-galactopyran osyl-
(1→4)-3,6-di-O-ben zyl-2-deoxy-2-ph th alim ido-β-D-galactopyran oside (16a) an d
Pen t-4-en yl 4-O-Acetyl-3,6-di-O-ben zyl-2-deoxy-2-ph th alim ido-α-D-galactopyran osyl-
(1→4)-3,6-di-O-ben zyl-2-deoxy-2-ph th alim ido-β-D-galactopyran oside (16b)
Method A: Com poun d 10a (112 m g, 0.2 m m ol) was dried in an apparatus equipped with a
septum by co-distillation with dry ben zen e (3 × 3 m l), added th rough th e septum . Silver car-
bon ate (320 m g, 1.16 m m ol), silver perch lorate (67 m g, 0.32 m m ol) an d m olecular sieves 4 Å
(300 m g) were added an d dryin g was con tin ued at room tem perature an d 20 Pa for an oth er
TABLE IV
1H NMR param eters of com poun ds 12–17ba
Para-
m eter
12
14
16a
16b
16c
17a
17b
δ(H-1)
δ(H-2)
δ(H-3)
δ(H-4)
δ(H-5)
δ(H-6a)
δ(H-6b)
δ(H-1′)
δ(H-2′)
δ(H-3′)
δ(H-4′)
δ(H-5′)
δ(H-6a′)
4.94 dd
4.11 t
5.10 m
4.88 d
4.90 d
4.93 d
5.03 d
5.03 d
4.02 dd
4.02 dd
4.03 dd
3.94 dd
3.64 ddd
3.75 dd
3.88 dd
5.44 d
4.05 dd
4.01 dd
3.97 dd
3.64 ddd
3.74 dd
3.89 dd
5.24 d
4.77 dd
4.08 dd
4.32 dd
3.53 dd
3.02 dd
3.14 dd
5.30 d
4.38 dd
4.15 dd
4.17 dd
3.75 ddd
3.78 dd
3.88 dd
5.81 d
4.08 ddd 4.14–4.19 m 3.98 dd
4.05 dd
3.93 dd
3.60 ddd
3.73 dd
3.90 dd
5.28 d
3.65 ddd 3.34 ddd
3.70 dd
3.84 dd
5.32 d
3.38 dd
3.52 dd
5.33
4.47 dd
4.43 dd
5.67 dd
4.27 dd
4.77 dd
5.15 dd
4.53 dd
4.40 dd
5.66 dd
3.88 ddd
3.49 dd
3.51 dd
3.25 ddd
3.67 dt
4.69 dd
5.95 dd
5.48 dd
4.08 ddd
4.04 dd
4.17 dd
3.28 ddd
3.71 dt
4.49 dd
4.38 dd
5.64 dd
3.86 dt
4.76 dd
5.61 dd
5.88 dd
4.83 ddd
3.30 dd
3.38 dd
3.29 ddd
3.50 dt
4.98 dd
5.58 t
4.45 dd
5.37 ddd
4.26 dd
4.33 dd
3.35 ddd
3.79 dd
3.87 ddd 3.66 ddd
3.49 dd
3.44 dd
δ(H-6b′) 3.51 dd
3.54 dd
3.51 d
δ(H-1a′′)
δ(H-1b′′)
δ(H-2′′)
δ(H-3′′)
δ(H-4′′)
δ(H-5a′′)
δ(H-5b′′)
–
–
–
–
–
–
–
–
–
–
–
–
–
–
3.29 ddd
3.69 dt
1.33–1.51 m 1.37–1.48 m 1.38–1.55 m 1.37–1.55 m
1.60–1.82 m 1.68–1.81 m 1.73–1.82 m 1.76–1.87 m 1.74–1.88 m
5.50 ddt
4.63 ddt
4.68 ddt
5.51 ddt
4.64 ddt
4.69 ddt
5.54 ddt
4.68 ddt
4.71 ddt
5.59 ddt
4.70 ddt
4.76 ddt
5.54 ddt
4.68 dq
4.71 dd
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

1932
Veselý, Ledvina, Jindřich, Trnka, Šaman:
TABLE IV
(Continued)
Para-
m eter
12
14
16a
16b
16c
17a
17b
b
b
b
J(1,2)
10.3
10.3
2.6
1.0
5.5
6.1
9.6
8.1
11.0
3.2
1.1
6.0
7.0
9.2
7.9
11.0
3.4
8.1
10.1
2.8
7.8
11.1
2.4
8.5
11.1
2.9
0.0
8.6
6.1
9.0
3.3
9.8
3.1
0.9
5.6
7.5
9.1
8.6
10.8
2.9
1.3
6.0
5.9
9.8
4.7
7.5
7.9
3.7
7.1
4.5
11.8
J(2,3)
J(3,4)
J(4,5)
9.3
1.0
0.0
1.0
J(5,6a)
J(5,6b)
J(6a,6b)
J(1′,2′)
J(2′,3′)
J(3′,4′)
J(4′,5′)
J(5′,6a′)
J(5′,6b′)
J(6a′,6b′)
4.0
1.3
5.9
6.0
6.1
5.7
5.4
5.5
11.1
8.4
10.1
8.4
10.3
8.4
10.3
8.4
10.8
9.0
11.1
3.4
11.6
3.4
11.0
3.4
9.8
0.9
0.0
0.7
2.5
6.1
6.0
6.5
4.4
7.0
6.4
6.5
b
9.9
9.2
9.8
a
Param eters of pen t-4-en yl residue sign ed H-1′′ to H-5′′, typical values of couplin g con stan ts in
pen t-4-en yl residue: J1a′′,2a′′ = 6.1, J1a′′,2b′′ = 7.3, J1b′′,2a′′ = J1b′′,2b′′ = 6.1, J1a′′,1b′′ = 9.7, J3a′′,4′′ = J3b′′,4′′ = 6.7,
J3a′′,5a′′ = J3a′′,5a′′ = 1.7, J3a′′,5b′′ = J3b′′,5b′′ = 1.2, J4′′,5a′′ = 17.1, J4′′,5b′′ = 10.2, J5a′′,5b′′ = 2.1. Addition al NMR pa-
ram eters an d param eters of substituen ts: 12 – J1,3 = 1.3, arom . H: 6.56–8.10 m , OCH2C6H5: 4.25 d (1 H, J
= 12.5), 4.34 d (1 H, J = 12.7), 4.40 d (1 H, J = 11.8), 4.49 d (1 H, J = 11.8), 4.52 d (1 H, J = 12.7), 4.54 s (2
H), 4.60 d (1 H, J = 12.5), SCH2CH3: 2.45 dq (1 H, J = 3 × 7.4, 12.3), 2.60 dq (1 H, J = 3 × 7.4, 12.3), 1.32 t
(3 H, J = 7.3), OAc: 2.17 s (3 H); 14 – arom . H: 6.80–7.88 m , OCH2C6H5: 4.32 d (1 H, J = 12.1), 4.43 d (1
H, J = 11.8), 4.44 d (1 H, J = 11.9), 4.50 d (1 H, J = 12.3), 4.52 d (1 H, J = 11.8), 4.52 d (1 H, J = 11.9),
4.60 d (1 H, J = 12.1), 4.84 d (1 H, J = 12.3), SCH2CH3: 2.49 dq (1 H, J = 3 × 7.5, 12.5), 2.57 dq (1 H, J = 3
× 7.5, 12.5), 1.09 t (3 H, J = 7.5), OAc: 1.92 s (3 H); 16a – arom . H: 6.52–7.80 m , OCH2C6H5: 3.93 d (1 H,
J = 12.8), 4.13 d (1 H, J = 12.8), 4.27 d (1 H, J = 12.0), 4.42 d (1 H, J = 11.8), 4.50 d (1 H, J = 11.8), 4.54 d
(1 H, J = 11.9), 4.57 d (1 H, J = 11.9), 4.60 d (1 H, J = 12.0), OAc: 1.92 s (3 H); 16b – arom . H: 6.63–7.75
m , OCH2C6H5: 4.02 d (1 H, J = 12.7), 4.36 d (1 H, J = 12.7), 4.59 s (2 H), OAc: 1.87 s (3 H), 2.03 s (3 H),
2.20 s (3 H); 16c – arom . H: 6.85–7.75 m , OCH2C6H5: 4.25 d (1 H, J = 12.5), 4.42 d (1 H, J = 11.8), 4.50 d
(1 H, J = 11.8), 4.55 d (1 H, J = 11.9), 4.57 d (1 H, J = 11.9), 4.58 d (1 H, J = 12.5), OAc: 2.15 s (3 H),
OCH2CH=CH2: 3.47 ddt (1 H, J = 1.2, 1.2, 6.2, 12.8), 3.71 ddt (1 H, J = 1.4, 1.4, 5.8, 12.8), 5.30 ddt (1 H, J
= 6.0, 6.0, 10.3, 17.2), 4.75 dq (1 H, J = 3 × 1.5, 10.3), 4.80 dq (1 H, J = 3 × 1.6, 17.2); 17a – arom . H:
6.88–7.87 m , OCH2C6H5: 4.15 d (1 H, J = 11.8), 4.16 d (1 H, J = 11.9), 4.18 d (1 H, J = 11.7), 4.32 d (1 H, J
= 11.9), 4.40 d (1 H, J = 11.8), 4.59 d (1 H, J = 9.5), 4.71 d (1 H, J = 11.7), 4.87 d (1 H, J = 9.5), OAc: 2.06
s (3 H); 17b – arom . H: 6.56–7.82 m , OCH2C6H5: 4.06 d (1 H, J = 12.3), 4.34 d (1 H, J = 12.3), 4.61 d (1 H,
b
J = 11.8), 4.67 d (1 H, J = 11.8 ), OAc: 2.03 s (3 H), 2.06 s (3 H), 2.16 s (3 H). Value n ot determ in ed.
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

2-Amino-2-deoxy-β-D-galactopyranosyl-(1→4)-2-amino-2-deoxy-β-D-galactopyranosides
1933
TABLE V
13C NMR ch em ical sh ifts of com poun ds 2a–11a
Com poun d
C-1
C-2
C-3
C-4
C-5
C-6
2a
81.23
81.23
81.54
81.76
90.40
78.70
106.34
104.96
93.29
94.36
81.02
98.60
98.77
98.37
98.51
98.78
54.88
54.92
51.64
51.70
54.66
56.13
51.71
52.95
54.69
51.86
51.01
53.02
53.06
52.44
52.51
52.45
78.82
78.68
73.58
74.03
71.39
72.92
69.90
72.25
72.81
72.80
75.63
73.05
73.37
75.06
79.12
77.88b
66.05
66.28
65.52
65.64
66.05
65.30
65.90
65.62
65.74
66.00
66.19
65.63
65.84
67.55
77.85
77.91b
76.09
76.20
72.84
77.30
70.71
72.52
72.54
73.33
77.15
72.33
72.44
73.39
73.45
73.87
68.92
68.90
68.01
68.13
67.30
67.47
67.76
67.56
68.11
67.33
69.16
68.04
68.17
69.12
69.19
68.80
2b
3a
3b
4 α-an om er
4 β-an om er
5a
5b
6
7
8
9a
9b
10a
10b
11
75.23
c
a
13C ch em ical sh ifts of arom atic carbon s from protectin g groups are n ot given . Addition al
13C NMR ch em ical sh ifts of substituen ts: 2a – OCH2C6H5: 74.91 t, 73.60 t, SCH2CH3: 24.11
t, 14.94 q, CH3SO2O: 38.63 q; 2b – OCH2C6H5: 73.56 t, SCH2CH3: 24.14 t, 14.95 q,
CH3SO2O: 38.73 q, OCH2CH=CH2: 73.21 t, 133.42 d, 117.81 t; 3a – OCH2C6H5: 73.65 t,
70.96 t, SCH2CH3: 24.30 t, 14.88 q, OAc: 170.44 s, 20.95 q; 3b – OCH2C6H5: 73.63 t,
SCH2CH3: 24.31 t, 14.90 q, OAc: 170.27 s, 20.86 q, OCH2CH=CH2: 70.16 t, 133.91 d, 117.52 t;
4 – α-an om er – OCH2C6H5: 71.06 t, 73.66 t, OAc: 169.95 s, 23.89 q; 4 – β-an om er –
OCH2C6H5: 71.22 t, 73.72 t, OAc: 170.27 s, 23.89 q; 5a – JC-1,F = 228.1, JC-2,F = 25.7, JC-5,F
=
2.2, OCH2C6H5: 73.64 t, 71.24 t, OAc: 170.07 s, 20.80 q; 5b – JC-1,F = 214.3, JC-2,F = 21.5,
JC-3,F = 9.4, JC-5,F = 5.0, OCH2C6H5: 73.74 t, 71.28 t, OAc: 170.22 s, 20.78 q; 6 – OCH2C6H5:
73.70 t, 71.20 t, OAc: 170.40 s, 20.91 q; 7 – OCH2C6H5: 73.54 t, 71.28 t, OAc: 170.34 s,
20.87 q, OC(NH)CCl3: 160.90 s, 93.21 s; 8 – OCH2C6H5: 73.67 t, 71.24 t, SCH2CH3: 23.69 t,
14.87 q; 9a – OCH2CH2CH2CH=CH2: 68.94 t, 28.41 t, 29.75 t, 137.71 d, 114.61 t;
9b – OCH2C6H5: 73.65 t, OAc: 170.31 s, 20.84 q, OCH2CH2CH2CH=CH2: 68.98 t, 28.48 t,
29.78 t, 137.74 d, 114.61 t, OCH2CH=CH2: 70.25 t, 133.98 d, 117.41 t; 10a – OCH2C6H5:
73.68 t, 71.29 t, OCH2CH2CH2CH=CH2: 68.57 t, 28.48 t, 29.81 t, 137.85 d, 114.53 t;
10b – OCH2C6H5: 73.70 t, OCH2CH2CH2CH=CH2: 68.60 t, 28.54 t, 29.83 t, 137.87 d,
114.54 t, OCH2CH=CH2: 70.37 t, 133.88 d, 117.86 t; 11 – OCH2C6H5: 73.70 t, 72.23 t,
OCH2CH2CH2CH=CH2: 68.80 t, 28.45 t, 29.80 t, 137.88 d, 114.49 t, OSi(CH3)3: 0.57 q.
b
c
Altern ative assign m en t of ch em ical sh ifts. Overlapped by solven t sign al.
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

1934
Veselý, Ledvina, Jindřich, Trnka, Šaman:
8 h . Th e apparatus was flush ed with argon (2×) an d dry dich lorom eth an e (5 m l) was added
th rough th e septum . Th e m ixture was stirred at room tem perature for 1 h , an d a solution of
glycosyl brom ide 4, fresh ly prepared from 3a (230 m g, 0.4 m m ol) an d dich lorom eth an e
(4 m l), was added at –15 °C un der stirrin g th rough th e septum durin g 1 h an d th en th e stir-
rin g was con tin ued at room tem perature for an oth er 10 h . Progress of th e reaction was m on -
itored on TLC in toluen e–eth yl acetate (5:1). Pyridin e (1.5 m l) was added an d after 1 h stir-
rin g at room tem perature, th e m ixture was diluted with ch loroform (12 m l) an d filtered
TABLE VI
Ch aracteristic 13C NMR ch em ical sh ifts of com poun ds 12–17ba
Carbon
12
14
16a
16b
16c
17a
17b
1
80.18
50.77
75.92
73.49
77.14
69.44
99.5
52.94
72.72
65.74
71.67
68.00
–
80.77
54.74
78.82
76.03
77.67
69.45
97.09
56.24
76.87
72.73
73.42
68.25
–
98.02
52.13
75.32
74.54
73.58
69.72
99.86
52.80
72.69
65.70
71.57
68.14
67.95
28.37
29.75
137.96
114.34
98.15
52.27
70.25
75.26
73.60
69.77
99.85
51.14
67.81
66.52
75.26
61.38
68.19
28.41
29.76
137.91
114.39
98.24
52.30
75.50
74.54
73.75
69.86
99.64
52.82
72.79
65.81
71.69
68.18
67.93
28.49
29.82
138.03
114.38
98.04
51.87
75.66
69.68
72.72
66.94
97.62
52.65
70.68
66.77
68.19
68.13
67.24
29.69
29.96
138.08
114.48
98.50
52.60
76.18
73.06
73.30
69.38
104.62
60.81
72.74
77.96
69.03
62.57
68.67
28.47
29.79
137.87
114.49
2
3
4
5
6
1′
2′
3′
4′
5′
6′
1′′
2′′
3′′
4′′
5′′
–
–
–
–
–
–
–
–
a
13C ch em ical sh ifts of arom atic carbon s from protectin g groups are n ot given . Addition al
13C NMR ch em ical sh ifts of substituen ts: 12 – OCH2C6H5: 73.59 t, 72.74 t, 71.43 t, 71.03 t,
SCH2CH3: 22.49 t, 14.63 q, OAc: 170.59 s, 21.03 q; 14 – OCH2C6H5: 74.58 t, 73.90 t, 73.55 t,
72.67 t, SCH2CH3: 23.62 t, 14.86 q, OAc: 169.63 s, 20.89 q; 16a – OCH2C6H5: 73.34 t, 71.60 t,
70.93 t, 68.14 t, OAc: 170.58 s, 20.99 q; 16b – OCH2C6H5: 73.47 t, 71.91 t, OAc: 170.39 s,
170.35 s, 169.92 s, 20.74 q, 20.66 q, 20.57 q; 16c – OCH2C6H5: 73.62 t, 73.42 t, 71.00 t,
OAc: 170.56 s, 20.97 q, OCH2CH=CH2: 71.34 t, 134.28 d, 117.63 t; 17a – OCH2C6H5:
73.46 t, 73.11 t, 71.36 t, 71.13 t, OAc: 170.28 s, 21.27 q; 17b – OCH2C6H5: 73.60 t, 71.97 t,
OAc: 170.43 s, 170.39 s, 170.31 s, 20.78 q, 20.69 q, 20.50 q.
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

2-Amino-2-deoxy-β-D-galactopyranosyl-(1→4)-2-amino-2-deoxy-β-D-galactopyranosides
1935
th rough Celite. Th e filtrate was evaporated. Th e residue was separated by ch rom atograph y
on a silica gel colum n (15 g) in toluen e–eth yl acetate (10:1) to give 122 m g (57%,) of a syr-
upy com poun d 16a an d 45 m g (21%) of a syrupy com poun d 16b.
Method B: Com poun ds 3a (234 m g, 0.4 m m ol) an d 10a (112 m g, 0.2 m m ol) were dried in
an apparatus equipped with a septum by co-distillation with dry ben zen e (3 × 3 m l), added
th rough th e septum . Crush ed m olecular sieves 4 Å (300 m g) were added an d dryin g was
con tin ued at room tem perature an d 20 Pa for 8 h . Th e apparatus was flush ed with argon
(2×) an d dry dich lorom eth an e (4 m l) was added th rough th e septum . After dissolution ,
m eth yl triflate (60 µl, 0.53 m m ol) was added un der stirrin g at room tem perature th rough
th e septum an d th e stirrin g was con tin ued at th e sam e tem perature for 2 days. Progress of
th e reaction was m on itored as described in m eth od A. Th e m ixture was taken between ch lo-
roform (20 m l) an d saturated aqueous sodium h ydrogen carbon ate (10 m l) an d organ ic layer
was separated, wash ed with water (2 × 5 m l), dried over an h ydrous m agn esium sulfate an d
evaporated in vacuo. Th e residue was separated by a colum n ch rom atograph y as described
in m eth od A, to give 90 m g (42%) of a syrupy com poun d 16a, 45 m g (21%) of a syrupy
com poun d 16b an d 25 m g (22%) of startin g com poun d 10a.
Method C: Com poun d 10a (112 m g, 0.2 m m ol) was dried in an apparatus equipped with a
septum by co-distillation with dry ben zen e (3 × 3 m l). Com poun d 5b (213 m g, 0.4 m m ol)
was added an d dryin g was con tin ued at room tem perature an d 20 Pa for an oth er 8 h . Th e
apparatus was flush ed with argon (2×) an d th e m ixture was dissolved in dry dieth yl eth er
(6 m l) added th rough th e septum . Th e obtain ed solution was added th rough th e septum to
a stirred m ixture of titan ium (IV) fluoride (87 m g, 0.7 m m ol) an d m olecular sieves 3 Å (1.5 g)
un der argon in an apparatus equipped with th e septum at 0 °C. Th e stirrin g was th en con -
tin ued at room tem perature for 18 h . Progress of th e reaction was m on itored as described in
m eth od A. Th e reaction m ixture was worked up by th e sam e procedure as is given in proce-
dure A, to afford 51 m g (24%) of a syrupy com poun d 16a, 36 m g (17%) of a syrupy com -
poun d 16b, 31 m g (15%) of a syrupy com poun d 5a, 23 m g (21%) of startin g com poun d 10a
an d 74 m g (35%) of startin g com poun d 5b.
Method D: Com poun d 10a (112 m g, 0.2 m m ol) was dried in an apparatus equipped with a
septum by co-distillation with dry ben zen e (3 × 3 m l), added th rough th e septum . Com -
poun d 5b (120 m g, 0.22 m m ol) was added an d th e dryin g was con tin ued at room tem pera-
ture an d 20 Pa for an oth er 8 h . Th e apparatus was flush ed with argon (2×) an d th e m ixture
was dissolved in dry dich lorom eth an e (4 m l) added th rough th e septum . Th e obtain ed solu-
tion was added th rough th e septum to a stirred m ixture of bis(cyclopen tadien yl)zircon ium
dich loride (350 m g, 1.2 m m ol), silver perch lorate (250 m g, 1.2 m m ol) an d crush ed m olecu-
lar sieves 4 Å (200 m g) in dry dich lorom eth an e (4 m l) un der argon an d at –20 °C in a appa-
ratus equipped with a septum . Th e m ixture was stirred at –20 °C for 2 h , an d th en ch loro-
form (20 m l) an d saturated aqueous sodium h ydrogen carbon ate (6 m l) were added. After
warm in g to room tem perature th e m ixture was filtered an d organ ic layer was separated,
wash ed with water (2 × 10 m l), dried over an h ydrous m agn esium sulfate an d evaporated in
vacuo. Th e residue was separated by a colum n ch rom atograph y as described in m eth od A,
to give 77 m g (36%) of a syrupy com poun d 16a, 30 m g (14%) of a syrupy com poun d 16b,
40 m g (36%) of startin g com poun d 10a an d 15 m g (13%) of startin g com poun d 5b.
Method E: Com poun ds 11 (126 m g, 0.2 m m ol) an d 5b (213 m g, 0.4 m m ol) were dried in
an apparatus equipped with a septum by co-distillation with dry ben zen e (3 × 3 m l). Th e ap-
paratus was flush ed with argon (2×) an d dry aceton itrile (6 m l) was added th rough th e sep-
tum . After dissolution , th e m ixture was cooled to –45 °C an d trim eth ylsilyl trifluoro-
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

1936
Veselý, Ledvina, Jindřich, Trnka, Šaman:
m eth an esulfon ate (10 µl, 0.05 m m ol) was added un der stirrin g th rough th e septum . Th e
m ixture was stirred at –20 °C for 2 h an d th an at room tem perature for 3 days. Progress of
th e reaction was m on itored as described in m eth od A. Th e m ixture was filtered th rough
Celite, taken between toluen e (30 m l) an d saturated aqueous sodium h ydrogen carbon ate
(10 m l), an d organ ic layer was separated, wash ed with water (2 × 10 m l), dried over an h y-
drous m agn esium sulfate an d evaporated in vacuo. From th e com plex reaction m ixture
24 m g (11%) of a syrupy com poun d 16a was isolated by a colum n ch rom atograph y as de-
scribed in m eth od A, followed by HPLC separation on a silica gel colum n (5 µm ) in h ex-
an e–eth yl acetate (3:1).
Method F: Com poun ds 7 (270 m g, 0.4 m m ol) an d 10a (112 m g, 0.2 m m ol) were dried in
an apparatus equipped with a septum by co-distillation with dry ben zen e (3 × 3 m l), added
th rough th e septum . Crush ed m olecular sieves 4 Å (300 m g) were added an d dryin g was
con tin ued at room tem perature an d 20 Pa for 8 h . Th e apparatus was flush ed with argon
(2×) an d dry dich lorom eth an e (5 m l) was added th rough th e septum . After dissolution , th e
m ixture was cooled to –45 °C an d 1 M solution of boron trifluoride eth erate in dich loro-
m eth an e (100 µl, 0.1 m m ol) was added th rough th e septum un der stirrin g. Th en th e m ix-
ture was stirred at room tem perature for 3 days. Progress of th e reaction was m on itored as
described in m eth od A. Th e m ixture was taken between ch loroform (20 m l) an d saturated
aqueous sodium h ydrogen carbon ate (10 m l), an d organ ic layer was separated, wash ed with
water (2 × 5 m l), dried over an h ydrous m agn esium sulfate an d evaporated in vacuo. Th e res-
idue was separated by a colum n ch rom atograph y as described in m eth od A, to give 64 m g
(30%) of a syrupy com poun d 16a, 24 m g (11%) of a syrupy com poun d 16b an d 54 m g
(48%) of startin g com poun d 10a.
Method G: Com poun ds 7 (270 m g, 0.4 m m ol) an d 10a (112 m g, 0.2 m m ol) were dried in
an apparatus equipped with a septum by co-distillation with dry ben zen e (3 × 3 m l), added
th rough th e septum . Crush ed m olecular sieves 4 Å (300 m g) were added an d dryin g was
con tin ued at room tem perature an d 20 Pa for 8 h . Th e apparatus was flush ed with argon
(2×) an d dry dich lorom eth an e (5 m l) was added th rough th e septum . After dissolution , th e
m ixture was cooled to –45 °C an d trim eth ylsilyl trifluorom eth an esulfon ate (80 µl,
0.4 m m ol) was added un der stirrin g th rough th e septum . Th e m ixture was stirred at th e
sam e tem perature for 12 h an d th en at room tem perature for 3 days. Progress of th e reaction
was m on itored as described in m eth od A. Th e m ixture was filtered th rough Celite, partion ed
between ch loroform (20 m l) an d saturated aqueous sodium h ydrogen carbon ate (10 m l), an d
organ ic layer was separated, wash ed with water (2 × 5 m l), dried over an h ydrous m agn esium
sulfate an d evaporated in vacuo. Th e residue was separated by a colum n ch rom atograph y as
described in m eth od A, to give 105 m g (49%) of a syrupy com poun d 16a an d 24 m g (11%)
of a syrupy com poun d 16b.
Compound 16a: [α]D +13 (c 0.2, ch loroform ). 1H NMR: see Table IV, 13C NMR: see Table VI.
For C63H62N2O14 calculated: relative m olecular m ass 1071.2, m on oisotopic m ass 1070.4.
ESI MS, m/z: 1093.8 [M + Na]+. For C63H62N2O14 (1071.2) calculated: 70.64% C, 5.83% H,
2.62% N; foun d: 70.28% C, 6.02% H, 2.51% N.
Compound 16b: [α]D +46 (c 0.7, ch loroform ). 1H NMR: see Table IV, 13C NMR: see Table VI.
For C63H62N2O14 calculated: relative m olecular m ass 1071.2, m on oisotopic m ass 1070.4.
ESI MS, m/z: 1093.5 [M + Na]+. For C63H62N2O14 (1071.2) calculated: 70.64% C, 5.83% H,
2.62% N; foun d: 70.32% C, 5.91% H, 2.49% N.
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

2-Amino-2-deoxy-β-D-galactopyranosyl-(1→4)-2-amino-2-deoxy-β-D-galactopyranosides
1937
Pen t-4-en yl 4-O-Acetyl-3,6-di-O-ben zyl-2-deoxy-2-ph th alim ido-β-D-galactopyran osyl-
(1→4)-3-O-allyl-6-O-ben zyl-2-deoxy-2-ph th alim ido-β-D-galactopyran oside (17a) an d
Pen t-4-en yl 4-O-Acetyl-3,6-di-O-ben zyl-2-deoxy-2-ph th alim ido-α-D-galactopyran osyl-
(1→4)-3-O-allyl-6-O-ben zyl-2-deoxy-2-ph th alim ido-β-D-galactopyran oside (17b)
Com poun d 10b (102 m g, 0.2 m m ol) was dried in an apparatus equipped with a septum by
co-distillation with dry ben zen e (3 × 3 m l), added th rough th e septum . Silver carbon ate
(276 m g, 1 m m ol), silver perch lorate (48 m g, 0.23 m m ol) an d m olecular sieves 4 Å (300 m g)
were added an d dryin g was con tin ued at room tem perature an d 20 Pa for an oth er 8 h . Th e
apparatus was flush ed with argon (2×) an d dry dich lorom eth an e (3 m l) was added th rough
th e septum . Th e m ixture was stirred at room tem perature for 1 h an d a solution of glycosyl
brom ide 4, fresh ly prepared from 3a (173 m g, 0.3 m m ol), in dry dich lorom eth an e (3 m l)
was added un der stirrin g th rough th e septum durin g 1 h an d th e stirrin g was con tin ued
at room tem perature for an oth er 10 h . Progress of th e reaction was m on itored on TLC in
toluen e–eth yl acetate (5:1). Pyridin e (1.5 m l) was added an d after 1 h stirrin g at room tem -
perature, th e m ixture was diluted with ch loroform (12 m l) an d filtered th rough Celite. Th e
filtrate was evaporated. Ch rom atograph y of th e residue on a silica gel colum n (15 g) in
oluen e–eth yl acetate (10:1) followed by HPLC separation on a silica gel colum n (5 µm ) in
h exan e–eth yl acetate (4:1) afforded 35 m g (17%) of a syrupy com poun d 17a an d 22 m g
(11%) of a syrupy com poun d 17b an d 42 m g (43%) of startin g com poun d 10b.
Compound 17a: [α]D –39 (c 0.2, ch loroform ). 1H NMR: see Table IV, 13C NMR: see Table VI.
For C59H60N2O14 calculated: relative m olecular m ass 1021.1, m on oisotopic m ass 1020.4.
ESI MS, m/z: 1043.3 [M + Na]+. For C59H60N2O14 (1021.1) calculated: 69.40% C, 5.92% H,
2.74% N; foun d: 69.28% C, 6.10% H, 2.66% N.
Compound 17b: [α]D +128 (c 0.2, ch loroform ). 1H NMR: see Table IV, 13C NMR: see Table VI.
For C59H60N2O14 calculated: relative m olecular m ass 1021.1, m on oisotopic m ass 1020.4.
ESI MS, m/z: 1043.5 [M + Na]+. For C59H60N2O14 (1021.1) calculated: 69.40% C, 5.92% H,
2.74% N; foun d: 69.33% C, 6.16% H, 2.62% N.
This work was supported by the Grant Agency of the Czech Republic (grant No. 203/00/0071), by
the Ministry of Education, Youth and Sports (grant No. 1131 00001) and Research Project Z4/055/905,
by the Grant Agency of the Charles University (grant No. 244/2003).
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