Photoinitiated hydrothiolation of pyranoid exo-glycals: the d-galacto and d-xylo cases
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G aphical Abs ac
pp. 1e7
Pho oini ia ed hyd o hiola ion o py anoid exo-glycals: he
D
-galac o and
D
-xylo cases
J
anos J
ozse , L
aszl
o Juh
asz, Tünde Zi a Illy
es, Magdolna Cs
a
as, Anik
o Bo b
as, L
aszl
o Soms
ak
*
Highligh s
Pho oini ia ed hiol-ene eac ion o O-ace yla ed exo-glycals.
Syn hesis o
b
-
D
-glycopy anosylme hyl-sulfide ype glycomime ics.
Exclusi e egio- and s e eoselec i i y wi h exo-galac al.
Exclusi e egio- and e y high s e eoselec i i y wi h exo-xylal.
Disaccha ide mimicks o Gly-CH
2
-S-Gly sca olds.
Con en s lis s a ailable a ScienceDi ec
Ca bohyd a e Resea ch
jou nal homepage: www.else ie .com/loca e/ca es
h p://dx.doi.o g/10.1016/j.ca es.2015.05.008
0008-6215/©2015 Published by Else ie L d.
Ca bohyd a e Resea ch xxx (2015) 1
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CAR7009_g abs ■6 June 2015 ■1/1
Please ci e his a icle in p ess as: J
ozse J, e al., Pho oini ia ed hyd o hiola ion o py anoid exo-glycals: he D-galac o and D-xylo cases,
Ca bohyd a e Resea ch (2015), h p://dx.doi.o g/10.1016/j.ca es.2015.05.008
No e
Pho oini ia ed hyd o hiola ion o py anoid exo-glycals: he
D
-galac o
and
D
-xylo cases
Q3
Q2
J
anos J
ozse
a
,L
aszl
oJuh
asz
a
,Tünde Zi a Illy
es
a
,Magdolna Cs
a
as
b
,Anik
oBo b
as
b
,
L
aszl
oSoms
ak
a
,
*
a
Depa men o O ganic Chemis y, PO Box 20, Uni e si y o Deb ecen, H-4010 Deb ecen, Hunga y
b
Depa men o Pha maceu ical Chemis y, PO Box 70, Uni e si y o Deb ecen, H-4010 Deb ecen, Hunga y
a icle in o
A icle his o y:
Recei ed 30 Ap il 2015
Accep ed 22 May 2015
A ailable online xxx
Keywo ds:
Thiol-ene click eac ion
Exo-galac al
Exo-xylal
Disaccha ide mimicks
abs ac
Radical-media ed addi ion eac ions o hiols o O-pe ace yla ed exo-galac al and exo-xylal wi h 2,2-
dime hoxy-2-phenylace ophenone as he pho oini ia o esul ed in high yielding o ma ion o he co -
esponding
b
-
D
-glycopy anosylme hyl-sulfide de i a i es (2,6-anhyd o-1-deoxy-1-S-subs i u ed-1- hio-
aldi ols) wi h exclusi e egio- and e y high s e eoselec i i y, including disaccha ide mimicks wi h Gly-
CH
2
-S-Gly sca olds.
©2015 Published by Else ie L d.
Glycomime ic compounds a e widely used o deciphe ing he
biological oles o ca bohyd a e de i a i es.
1
Glycomime ics
esemble na u al ca bohyd a es in hei s uc u e and/o biological
unc ion and o en se e as lead compounds o d ug design.
2
One
o he mos impo an ea u es o such compounds is he hyd oly ic
s abili y o he bond(s),which eplace he na u al O-glycosidic
linkage(s). A wide ange o such eplacemen s we e sugges ed,
among o he s S-glycosides and C-glycosyl de i a i es wi h a sul u
a om o a me hylene g oup, espec i ely, in he posi ion o he
glycosidic oxygen.
1
In addi ion, in a numbe o examples wo (o
e en mo e) a oms a e inse ed be ween he glycon and aglycon
3
in
he o m o e.g., SeS,
4e8
SeSe,
8e10
SO
2
eN,
11e13
NeC(¼O)eN linking
moie ies.
14e17
Ca bohyd a e de i a i es displaying Gly-CH
2
-S-R sca olds a e
much less ep esen ed among glycomime ics al hough some syn-
he ic me hods, mos ly limi ed o he applica ion o O-pe benzy-
la ed exo-glycals, can be ound in he li e a u e. Thus, exo-glucal
was ans o med in se e al s eps in o a Glc-CH
2
-I de i a i e,
18e20
which was eac ed unde basic condi ions wi h alipha ic and a o-
ma ic hiols including suga de i a i es o gi e he abo e s uc-
u es. Ring openings by nucleophiles o an exo-glucal-de i ed
spi o-epoxide
21
as well as a spi o-episul onium ion
22
esul ed in
ulose de i a i es ea u ing he abo e s uc u e. Radical-media ed
addi ion o AcSH o exo-glycals u nished S-(
b
-
D
-glycosylme hyl)
hioace a es.
23
The hiol-ene addi ion chemis y,
24,25
ei he in ionic o adical-
media ed e sions, has ound se e al applica ions in ca bohyd a e
chemis y o S-glycoconjuga ion, whe ein he suga de i a i e
gene ally plays he ole o he hiol o is unc ionalized by O- o C-
appended unsa u a ed moie ies.
26
Much less wo k has been
de o ed o addi ions o hiols o suga ‘ene’-s in which he double
bond is pa o o di ec ly a ached o he suga ing: hus, addi ions
o suga de i ed enones
27
and some eac ions o endo-
28e30
and
ecen ly also exo-glycals
30e33
as well as de i a i es wi h an exo-
me hylene g oup in he 4- and a 5-posi ion o a u anoside and a
py anoside,
34
espec i ely, and a 3-exome hylene-gluco u -
anose
31,32
ha e been epo ed.
Exo-glycals o e hemsel es o he cons uc ion o Gly-CH
2
-S-R
ype compounds in hiol-ene couplings p o ided ha a su ficien
deg ee o eac i i y as well as o egio- and s e eoselec i i ies can
be achie ed and he eac ion condi ions a e compa ible wi h he
p o ec i e g oups. Base induced anionic addi ions o hiola es can
be expec ed ine ec i e wi h he elec on- ich double bond,
33
and
acid-ca alyzed eac ions o hiols yield S-glycosides due o he
s abili y o he glycosylium ion.
35
Radical-media ed addi ions mus
be highly a ou able due o he elec ophilic na u e o hiyl adi-
cals
25
and a good egioselec i i y may also be o eseen based on he
be e s abiliza ion o he e ia y glycosyl e sus he p ima y gly-
cosylme hyl adical. Al hough adical-media ed hyd o hiola ions
*Co esponding au ho . Tel.: þ36 52512900, þ36 52522348; ax: þ36 52512744.
Q
1
E-mail add ess: [email p o ec ed] (L. Soms
ak).
Con en s lis s a ailable a ScienceDi ec
Ca bohyd a e Resea ch
jou nal homepage: www.else ie .com/loca e/ca es
h p://dx.doi.o g/10.1016/j.ca es.2015.05.008
0008-6215/©2015 Published by Else ie L d.
Ca bohyd a e Resea ch xxx (2015) 1e7
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CAR7009_p oo ■6 June 2015 ■1/7
Please ci e his a icle in p ess as: J
ozse J, e al., Pho oini ia ed hyd o hiola ion o py anoid exo-glycals: he D-galac o and D-xylo cases,
Ca bohyd a e Resea ch (2015), h p://dx.doi.o g/10.1016/j.ca es.2015.05.008
could be pe o med wi h O-benzyla ed subs a es, such p o ec ing
g oups may be labile unde hose condi ions (c . a discussion in
Re . 31). On he o he hand, O-acyl p o ec ion is usually ad an a-
geous and s able in adical-media ed eac ions,
36,37
as i was
demons a ed ecen ly also by hyd o hiola ions o O-pe benzoy-
la ed exo-glucal.
31,32
In his case bo h he egio- and s e eo-
selec i i ies p o ed excellen as he o ma ion o
b
-
D
-
glucopy anosylme hyl-sulfides was obse ed only. As a con inua-
ion o hese s udies, he ein we disclose ou findings wi h he
pho oini ia ed hiol-ene eac ions o O-pe ace yla ed exo-galac al
and exo-xylal.
The O-pe ace yla ed exo-glycals 1and 4we e syn hesized om
he co esponding glycosyl cyanides acco ding o ou p o en
p ocedu e.
38e41
The hiol addi ions we e ca ied ou in oluene a
oom empe a u e by i adia ion a
l
max
365 nm o 15 min in he
p esence o 2,2-dime hoxy-2-phenylace ophenone (DPAP,
0.1 equi ) as he pho oini ia o . The p og ess o he eac ion was
con olled by TLC a e he fi s eac ion pe iod and i adia ion and
addi ion o DPAP we e epea ed i necessa y. The hiols we e
applied in 10- old excess o 2aecand in sligh ly mo e han equi-
mola amoun s o 2de . The esul s a e summa ized in Table 1 o
exo-galac al 1and in Table 2 o exo-xylal 4.
Each ans o ma ion needed wo i adia ion cycles a e ,which
ime o al consump ion o he exo-glycals 1o 4was obse ed. The
b
-
D
-galac osylme hyl-sulfides 3we e isola ed by column ch oma-
og aphy in good o high yields (59e87 %, Table 1). In se e al e-
ac ions o 4 he o ma ion o wo p oduc s 5and 6could be seen. In
each o hese cases compounds 5we e he majo p oduc s (52e75
%) and 6could be isola ed in e y small amoun s (<10%, Table 2).
The s uc u e o he p oduc s was es ablished by NMR me hods.
Fo he
D
-galac ose de i a i es 3 he
4
C
1
con o ma ion o he py -
anoid ing and he equa o ial posi ion o he CH
2
-S-R subs i uen
(co esponding o a
b
-D C-glycosylic configu a ion o he C-2
cen e) was deduced om he p o on spec a. The
D
-xylose de i ed
5exis ed also in a
4
C
1
con o ma ion wi h a
b
-
D
-configu ed C-2 as
e ealed by he la ge h ee-bond coupling cons an s o ~10 Hz
h oughou he spec a o hese compounds. On he o he hand, he
p o on spec a o 6exhibi ed se e al b oad single -like signals,
which we e no well esol ed. This was indica i e o a py anoid ing
in he
1
C
4
con o ma ion (o mo e p obably in a con o ma ional
equilib ium in ol ing he
1
C
4
chai and boa as well as skew-boa
con o ma ions). Howe e , he configu a ion o he C-2 ca bon
could no be es ablished on he basis o he p o on spec a since
bo h axial and equa o ial o ien a ion o subs i uen s o ha cen e
mus esul in small icinal couplings in he gi en con o ma ion.
The e o e, he
1
J
C-2,H-2
coupling cons an s we e de e mined o he
pai 5c and 6c by
1
H decoupled and undecoupled HSQC measu e-
men s.
1
J
C,H
coupling cons an s we e ob ained by measu ing he
dis ance o peaks maxima in F2 (
1
H) dimension om undecoupled
HSQC spec a. The p ac ically equal alues o hese couplings
(Table 3, 148.2 Hz o 5c and 147.4 o 6c) indica ed he axial po-
si ion o H-2 in bo h compounds, he eby e ealing he
a
-D
configu a ion o he C-2 a om in 6c. Va ia ions in he
1
J
C,H
alues o
he o he ca bons may also indica e he con o ma ional equilib ium
o hese de i a i es.
42
Fo he o he xylose de i a i es he
amoun s o he isola ed subs ances did no allow o ca y ou
simila pai wise measu emen s, he e o e, he analogous s uc u e
is made p obable by he simila i ies o he
1
H NMR spec a
Table 1
Addi ion o hiols 2 o exo-galac al 1
a
R Ra io o 1:2Yield
b
o 3(%)
aP 1:10 59
bPh 1:10 62
cBn 1:10 75
d1:1.1 72
e1:1.1 87
1:1.1 81
a
To al con e sion o 1was de ec ed a e wo i adia ions o 15 min.
b
Isola ed yields a e pu ifica ion by column ch oma og aphy.
J. J
ozse e al. / Ca bohyd a e Resea ch xxx (2015) 1e72
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CAR7009_p oo ■6 June 2015 ■2/7
Please ci e his a icle in p ess as: J
ozse J, e al., Pho oini ia ed hyd o hiola ion o py anoid exo-glycals: he D-galac o and D-xylo cases,
Ca bohyd a e Resea ch (2015), h p://dx.doi.o g/10.1016/j.ca es.2015.05.008
(Table 4). The op ical o a ions also co obo a e hese assump ions
a leas o compounds wi h non-suga appendages as de i a i es
6aeca e mo e dex o o a o y han 5aec, espec i ely. The S-
glycosyl moie ies o he disaccha ide like 3de ,5de , and 6de
ga e he expec ed signals in he NMR spec a.
In conclusion, he pho oini ia ed addi ion o hiols o O-pe -
ace yla ed exo-galac al and exo-xylal ga e he expec ed
D
-glyco-
sylme hyl-sulfide ype compounds in good yields wi h exclusi e
egioselec i i y. The
D
-galac ose de i a i es we e o med wi h
comple e
b
-s e eoselec i i y, while in he cases o he
D
-xylose
de i a i es besides he majo
b
-C-glycosylic de i a i es he
a
-
coun e pa s we e also isola ed in small amoun s. This s udy
demons a ed ha he hiol-ene eac ion o exo-glycals wi h a wide
ange o hiols can be ex ended o suga s o he han glucose. These
eac ions o e y high egio- and s e eoselec i i ies may be aluable
ools o he cons uc ion o new ypes o glycomime ic
compounds.
1. Expe imen al
1.1. Gene al me hods
Mel ing poin s we e measu ed in open capilla y ubes o on a
Kofle ho -s age and a e unco ec ed. Op ical o a ions we e
de e mined wi h a Pe kineElme 241 pola ime e a oom em-
pe a u e. NMR spec a we e eco ded wi h B uke 360 (360/
90 MHz o
1
H/
13
C), B uke 400 (400/100 MHz o
1
H/
13
C) o B uke
A ance II 500 spec ome e equipped wi h TXI z-g adien p obe-
heads (500/125.77 MHz o
1
H/
13
C) spec ome e . Chemical shi s
a e e e enced o TMS as he in e nal e e ence (
1
H), o o he
Table 3
Selec ed
13
C NMR da a o compounds 5c and 6c
C-2 C-3 C-4 C-5 C-6 C-2 C-3 C-4 C-5 C-6
d
[ppm] 78.7 71.5 73.6 69.1 66.7 74.0 67.3 66.2 66.4 66.1
1
J
C,H
[Hz] 148.2 154.0 161.6 162.5 147.4 149.5 164.0 147.4
Table 2
Addi ion o hiols 2 o exo-xylal 4
a
R Ra io o 4:2Yield
b
(%)
56
aP 1:10 63 4
bPh 1:10 52 8
cBn 1:10 68 5
d1:1.1 69 3
e1:1.1 75 n.d.
c
1:1.1 53 4
a
To al con e sion o 4was de ec ed a e wo i adia ions o 15 min.
b
Isola ed yields a e pu ifica ion by column ch oma og aphy.
c
The o ma ion o 6was no de ec ed.
J. J
ozse e al. / Ca bohyd a e Resea ch xxx (2015) 1e73
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CAR7009_p oo ■6 June 2015 ■3/7
Please ci e his a icle in p ess as: J
ozse J, e al., Pho oini ia ed hyd o hiola ion o py anoid exo-glycals: he D-galac o and D-xylo cases,
Ca bohyd a e Resea ch (2015), h p://dx.doi.o g/10.1016/j.ca es.2015.05.008
esidual sol en signals (
13
C).
1
J
C,H
coupling cons an s we e de e -
mined by measu ing he dis ance o peak maximums in F2 (
1
H)
dimension om undecoupled HSQC spec a. The assignmen s o
he
1
H NMR signals o compounds 3d,3 ,5e and 5 we e pe o med
by hei COSY spec a. Mass spec a we e eco ded wi h a The mo
LTQ XL mass spec ome e (The mo Elec on Co p., San Jose, CA,
USA) ope a ed in a ull scan posi i e ion ESI mode. TLC was pe -
o med on DC-Alu olle Kieselgel 60 F
254
(Me ck). TLC pla es we e
isualized unde UV ligh , and by gen le hea ing. Fo column
ch oma og aphy Kieselgel 60 (Me ck, pa icle size
(0.063e0.200 mm) was applied. Thiols 2aecwe e puchased om
SigmaeAld ich o p epa ed acco ding o li e a u e p ocedu es
(2d,
43
2e,
44
2
45
).
1.2. Gene al p ocedu e o he pho oini ia ed eac ion o exo-glycals
wi h hiols
To a solu ion o he s a ing glycal (1o 4,50e100 mg) in d y
oluene (4 mL/100 mg), a hiol 2(10 equi o 2aec, 1.1 equi o
2de ) and 2,2-dime hoxy-2-phenylace ophenone (DPAP, 0.1 equi )
we e added. The solu ion was i adia ed by a me cu y apo lamp
(
l
max
¼365 nm) a o 15 min. A e addi ion o ano he 0.1 equi
o DPAP i adia ion was con inued and, when he s a ing ma e ial
disappea ed (TLC, eluen 5:1 hexaneeace one), he sol en was
emo ed unde diminished p essu e, hen he esidue was pu ified
using column ch oma og aphy (eluen A 5:1 hexaneeace one;
eluen B 6:1 hexaneeace one; eluen C 2:1 hexane: ace one).
1.2.1. 3,4,5,7-Te a-O-ace yl-2,6-anhyd o-1-deoxy-1-S-p opyl-1-
hio-
D
-glyce o-
L
-manno-hep i ol (3a)
By he gene al p ocedu e, s a ing om 1(100 mg, 0.29 mmol)
o gi e 3a (eluen A) as a colo less oil (72 mg; 59%). R
¼0.42, (eluen
C), [
a
]
D
þ5.0 (c¼0.52, CHCl
3
).
1
H NMR (400 MHz, CDCl
3
)
d
: 5.41 (dd,
1H, J¼1.1, 3.5 Hz, H-5), 5.17 (p , 1H, J¼9.8 Hz, H-3), 5.02 (dd, 1H,
J¼3.5, 9.8 Hz, H-4), 4.13 (dd, 1H, J¼6.5, 11.3 Hz, H-7
A
), 4.07 (dd, 1H,
J¼6.5, 11.3 Hz, He7
B
), 3.90 (ddd, 1H, J¼1.1, 6.5, 6.5 Hz, H-6), 3.60
(ddd, 1H, J¼3.7, 7.2, 9.8 Hz, H-2), 2.69 (dd, 1H, J¼7.2, 14.2 Hz, H-1
A
),
2.65 (dd, 1H, J¼3.7, 14.2 Hz, H-1
B
), 2.53e262 (m, 2H, SeCH
2
), 2.15,
2.05, 2.04, 1.97 (4s, 43H, OAc), 1.66e1.53 (m, 2H, CH
2
), 0.97 ( ,
3H, J¼7.3 Hz, CH
3
).
13
C NMR (101 MHz, CDCl
3
)
d
: 170.41 (CO), 79.95,
74.34, 72.15, 69.16, 67.76 (C-2eC-6), 61.74 (C-7), 35.54, 33.58 (C-1,
CH
2
S), 22.97, 20.98, 20.84, 20.76, 13.56 (CH
3
). C
18
H
28
O
9
S(M
:
420.47 g/mol); MS: [MþH]
þ
¼421.58; [MþK]
þ
¼459.50.
1.2.2. 3,4,5,7-Te a-O-ace yl-2,6-anhyd o-1-deoxy-1-S-phenyl-1-
hio-
D
-glyce o-
L
-manno-hep i ol (3b)
By he gene al p ocedu e, s a ing om 1(100 mg, 0.29 mmol)
o gi e 3b (eluen A) as a yellow oil (82 mg; 62%). R
¼0.37 (eluen C),
[
a
]
D
15.0 (c¼0.53, CHCl
3
).
1
H NMR (400 MHz, CDCl
3
)
d
: 7.39e7.33
(m, 2H, a oma ic), 7.32e7.25 (m, 2H, a oma ic), 7.23e7.17 (m, 1H,
a oma ic), 5.40 (dd, 1H, J¼1.3, 3.5 Hz, H-5), 5.22 (pseudo , 1H,
J¼10.0 Hz, H-3), 5.02 (dd, 1H, J¼3.5, 10.0 Hz, H-4), 4.10 (dd, 1H,
J¼6.8, 11.3 Hz, H-7
A
), 4.04 (dd, 1H, J¼6.8, 11.3 Hz, H-7
B
), 3.87 (ddd,
1H, J¼1.3, 6.8, 6.8 Hz, H-6), 3.62 (ddd, 1H, J¼4.4, 6.7, 10.0 Hz, H-2),
3.08 (dd,1H, J¼4.4,13.6 Hz, H-1
A
), 3.12 (dd, J¼6.7,13.6 Hz,1H, H-1
B
),
2.16, 2.05, 2.04, 1.98 (4s, 43H, OAc).
13
C NMR (101 MHz, CDCl
3
)
d
:
170.55, 170.37, 170.28, 170.01 (4CO), 130.01, 129.05, 126.63 (a o-
ma ic), 77.98, 74.37, 72.08, 69.25, 67.69 (C-2eC-6), 61.53 (C-7),
36.33 (C-1), 20.97, 20.84, 20.74 (CH
3
). C
21
H
26
O
9
S, M
: 454.49 g/mol;
MS: [MþH]
þ
¼455.58; [MþK]
þ
¼493.50.
1.2.3. 3,4,5,7-Te a-O-ace yl-2,6-anhyd o-1-deoxy-1-S-benzyl-1-
hio-
D
-glyce o-
L
-manno-hep i ol (3c)
By he gene al p ocedu e, s a ing om 1(100 mg, 0.29 mmol)
o gi e 3c (eluen A) as a colo less oil (102 mg; 75%). R
¼0.37 (eluen
C), [
a
]
D
10.0 (c¼0.56, CHCl
3
).
1
H NMR (400 MHz, CDCl
3
)
d
:
7.40e7.16 (m, 5H, a oma ic), 5.41 (dd, 1H, J¼1.2, 3.4 Hz, H-5), 5.16
(pseudo ,1H, J¼10.1Hz, H-3), 5.00 (dd, 1H, J¼3.4, 10.1 Hz, H-4), 4.16
Table 4
Selec ed
1
H NMR da a o he
D
-xylose de i ed compounds 5and 6(
d
[ppm],
3
J
H,H
[Hz] o FWHM
a
[Hz])
Compound R H-1
A
H-1
B
H-2 H-3 H-4 H-5 H-6
eq
H-6
ax
5a P 2.67
3.0,14.1
2.58
7.6,14.1
3.55
3.0,7.6,9.4
4.95
9.4
5.18
9.4
4.99
5.7,9.4,10.7
4.14
5.7,11.2
3.29
10.7, 11.2
6a 2.78
7.5, 13.6
2.60
6.3, 13.6
3.84
d
b
4.89
7.0
a
5.07
8.2
a
4.70
7.5
a
4.03
1.7, 13.2
3.86
2.2, 13.2
5b Ph 3.11
3.0, 13.9
2.98
8.0, 13.9
3.56
3.0, 8.0, 9.4
4.97
9.4
5.17
9.4
5.01
5.6,9.4,11.1
4.14
5.6,11.1
3.27
11.1
6b 3.20
7.7,13.7
3.02
7.0,13.7
3.85
d
b
4.93
6.7
a
5.08
7.9
a
4.68
7.2
a
4.02
1.0,13.3
3.83
2.1,13.3
5c Bn 2.53
3.0,14.3
2.44
7.7,14.3
3.49
3.0,7.7,9.4
4.91
9.4
5.14
9.4
4.98
5.5,9.4,10.5
4.14
5.5,11.2
3.26
10.5,11.2
6c 2.72
7.7,13.7
2.52
6.1,13.7
3.66
1.9,6.1,7.7
4.79
6.9
a
5.02
8.0
a
4.65
6.7
a
3.98
13.6
3.75
2.3,13.6
5d (AcO)
4
-
b
-
D
-Gal
p
2.99
2.7,14.1
2.63
7.5,14.1
3.65
2.7,7.5,9.5
4.88
9.5
5.12
9.5
4.93
5.7,9.5,10.5
4.12
5.7,11.2
3.23
10.5,11.2
6d 3.02
8.1,13.5
2.73
5.5,13.5
3.95
d
b
4.87
7.2
a
5.04
d
b
4.70
6.6
a
4.03
1.8,13.3
3.95
2.2,13.3
5 (iP O)
2
-
a
-
D
-Gal
p
-6-yl 2.75
-
b
2.53
8.2,14.3
3.52
2.7,8.2,9.5
4.86
9.5
5.13
9.5
4.92
5.5,9.5,10.5
4.09
5.5,11.2
3.24
10.5,11.2
6 2.85
8.2,13.8
2.66
5.4,13.8
3.93
d
b
4.86
6.7
a
5.06
7.6
a
4.70
6.6
a
4.02
1.6,14.8
3.87
d
a
FWHM: ull wid h a hal -maximum o he signals.
b
O e lapping mul iple s om which he coupling cons an s could no be ex ac ed.
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ozse e al. / Ca bohyd a e Resea ch xxx (2015) 1e74
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CAR7009_p oo ■6 June 2015 ■4/7
Please ci e his a icle in p ess as: J
ozse J, e al., Pho oini ia ed hyd o hiola ion o py anoid exo-glycals: he D-galac o and D-xylo cases,
Ca bohyd a e Resea ch (2015), h p://dx.doi.o g/10.1016/j.ca es.2015.05.008
(dd, 1H, J¼6.7, 11.3 Hz, H-7
A
), 4.10 (dd, 1H, J¼6.7, 11.3 Hz, H-7
B
), 3.89
(ddd, 1H, J¼1.2, 6.7, 6.7 Hz, H-6), 3.80 (s, 2H, SCH
2
), 3.57 (ddd, 1H,
J¼3.6, 7.2, 10.1 Hz, H-2), 2.56, (dd, 1H, J¼7.2,14.4 Hz, H-1
A
), 2.52 (dd,
1H, J¼3.6, 14.4 Hz, H-1
B
), 2.16, 2.05, 1.98, 1.97 (4s, 43H, OAc).
13
C
NMR (101 MHz, CDCl
3
)
d
: 170.56, 170.37, 170.29, 169.82 (CO), 138.18,
129.18, 128.58, 127.19 (a oma ic), 79.64, 74.35, 72.10, 68.98, 67.73
(C-2eC-6), 61.81 (C-7), 37.14, 32.27 (C-1, SCH
2
), 20.87, 20.83, 20.73
(CH
3
). C
22
H
28
O
9
S, M
: 468.52 g/mol; MS: [MþH]
þ
¼469.67;
[MþK]
þ
¼507.58.
1.2.4. 3,4,5,7-Te a-O-ace yl-2,6-anhyd o-1-deoxy-1-S-(2,3,4,5-
e a-O-ace yl-
b
-
D
-galac opy anosyl)-1- hio-
D
-glyce o-
L
-manno-
hep i ol (3d)
By he gene al p ocedu e, s a ing om 1(50 mg, 0.145 mmol)
o gi e 3d (eluen B) as a yellow oil (74 mg; 72%). R
¼0.13 (eluen C),
[
a
]
D
27.1 (c¼0.55, CHCl
3
).
1
H NMR (400 MHz, CDCl
3
)
d
: 5.40 (dd,
1H, J¼1.1, 3.4 Hz, H-5), 5.38 (dd,1H, J¼1.1, 3.4 Hz, H-4
0
), 5.19 (pseudo
,1H, J¼9.9 Hz, H-2
0
), 5.18 ( ,1H, J¼10.0 Hz, H-3), 5.02 (dd,1H, J¼3.4,
10.0 Hz, H-4), 5.0 (dd, 1H, J¼3.4, 9.9 Hz, H-3
0
), 4.56 (d, 1H, J¼9.9 Hz,
H-1
0
), 4.14 (m, 2H, H-7
AB
), 4.05 (dd, 1H, J¼11.3, 6.8 Hz, H-6
0
A
), 4.03
(dd, 1H, J¼11.3, 6.8 Hz, H-6
0
B
), 3.90 (dd, 1H, J¼1.1, 6.5 Hz, H-6), 3.86
(ddd, 1H, J¼1.1, 6.8, 6.8 Hz, H-5
0
), 3.70 (ddd, J¼1H, 2.9, 7.4, 10.0 Hz,
H-2), 2.98 (dd, 1H, J¼2.9, 14.0 Hz, H-1
A
), 2.74 (dd, J¼7.4, 14.0 Hz, 1H,
H-1
B
), 2.13, 2.12, 2.06, 2.04, 2.01, 2.01, 1.95, 1.94 (8s, 83H, OAc).
13
C NMR (101 MHz, CDCl
3
)
d
: 170.41, 170.37, 170.25, 170.18, 170.04,
169.64 (CO), 83.27, 78.22, 74.53, 74.37, 72.13, 71.92, 68.74, 67.62,
67.32, 67.15(C-2eC-6 and C-1
0
eC-5
0
), 61.34 (C-7), 61.31 (C-6
0
), 30.58
(C-1), 20.85, 20.83, 20.73, 20.69, 20.66, 20.62 (CH
3
). C
29
H
40
O
18
S, M
:
708.68 g/mol; MS: [MþNa]
þ
¼731.83.
1.2.5. 3,4,5,7-Te a-O-ace yl-2,6-anhyd o-1-deoxy-1-S-(2,3,4- i-
O-ace yl-
b
-
D
-xylopy anosyl)-1- hio-
D
-glyce o-
L
-manno-hep i ol
(3e)
By he gene al p ocedu e, s a ing om 1(50 mg, 0.145 mmol)
o gi e 3e (eluen B) as a colo less oil (80 mg; 87%). R
¼0.16 (eluen
C), [
a
]
D
62.0 (c¼0.59, CHCl
3
).
1
H NMR (360 MHz, CDCl
3
)
d
: 5.39
(dd, 1H, J¼1.1, 3.4 Hz, H-5), 5.21 (pseudo , 1H, J¼10.0 Hz, H-3), 5.11
(pseudo ,1H, J¼8.0 Hz, H-3
0
), 5.00 (dd,1H, J¼3.4,10.0 Hz, H-4), 4.92
(pseudo , 1H, J¼8.0 Hz, H-2
0
), 4.94e4.82 (m, 1H, H-4
0
), 4.67 (d, 1H,
J¼8.1 Hz, H-1
0
), 4.21 (dd, 1H, J¼4.8, 11.8 Hz, H-5
0
eq
), 4.11 (dd, 1H,
J¼6.5, 11.2 Hz, H-7
A
), 4.03 (dd, 1H, J¼6.8, 11.2 Hz, H-7
B
), 3.86 (ddd,
J¼1H, 1.1, 6.5, 6.8 Hz, H-6), 3.65 (ddd, 1H, J¼2.9, 6.9, 10.0 Hz, H-2),
3.36 (dd, 1H, J¼8.5, 11.8 Hz, H-5
0
ax
), 2.91 (dd, 1H, J¼2.9, 14.2 Hz, H-
1
A
), 2.70 (dd, 1H, J¼6.9, 14.2 Hz, H-1
B
), 2.14, 2.06, 2.04, 2.03, 2.02,
2.02, 1.95 (7s, 73H, OAc).
13
C NMR (91 MHz, CDCl
3
)
d
: 170.46,
170.38,170.25,169.88,169.73,169.51 (CO), 83.25, 78.35, 74.34, 72.17,
71.67, 69.78, 68.52, 67.60 (C-2eC-6 and C-1
0
eC-4
0
), 65.06 (C-7),
61.45 (C-5
0
), 31.13 (C-1), 20.91, 20.80, 20.70 (CH
3
). C
26
H
36
O
16
S, M
:
636.62 g/mol; MS: [MþNa]
þ
¼659.92.
1.2.6. 3,4,5,7-Te a-O-ace yl-2,6-anhyd o-1-deoxy-1-S-(1,2:3,4,-di-
O-isop opylidene-
b
-
D
-galac opy anose-6-yl)-1- hio-
D
-glyce o-
L
-
manno-hep i ol (3 )
By he gene al p ocedu e, s a ing om 1(100 mg, 0.29 mmol)
o gi e 3 (eluen B) as a colo less oil (145 mg; 81%). R
¼0.30 (eluen
C), [
a
]
D
27.0 (c¼0.51, CHCl
3
).
1
H NMR (360 MHz, CDCl
3
)
d
: 5.48 (d,
1H, J¼5.1 Hz, H-1
0
), 5.36 (dd, 1H, J¼1.2, 3.4 Hz, H-5), 5.07 (pseudo ,
1H, J¼10.0 Hz, H-3), 4.96 (dd, 1H, J¼3.4, 10.1 Hz, H-4), 4.57 (dd, 1H,
J¼2.4, 7.9 Hz, H-3
0
), 4.26 (dd, 1H, J¼2.4, 5.1 Hz, H-2
0
), 4.20 (dd, 1H,
J¼1.9, 7.9 Hz, H-4
0
), 4.1e3.98 (m, 2H, H-7), 3.90e3.85 (m, 1H, H-6),
3.85e3.80 (m, 1H, H-5
0
), 3.60 (ddd, 1H, J¼3.1, 8.1, 10.0 Hz, H-2), 2.83
(dd, 1H, J¼6.2, 13.6 Hz, H-6
A
0
), 2.75 (dd, 1H, J¼7.6, 13.6 Hz, H-6
B
0
),
2.70 (dd,1H, J¼8.1, 14.4 Hz, H-1
A
), 2.63 (dd,1H, J¼3.1,14.4 Hz, H-1
B
),
2.12, 2.09, 2.00, 1.92 (4s, 43H, OAc), 1.51, 1.39, 1.29, 1.28 (4s,
43H, CH
3
).
13
C NMR (91 MHz, CDCl
3
)
d
: 170.51, 170.22, 170.15,
169.84 (CO), 109.26, 108.56 (C), 96.71, 80.02, 74.25, 71.97, 71.80,
70.99, 70.48, 68.98, 67.69, 67.07 (C-2eC-6 and C-1
0
eC-5
0
), 61.72 (C-
7), 32.96 (C-6
0
), 32.40 (C-1), 26.08, 26.01, 24.93, 24.49 (CH
3
), 20.83,
20.72, 20.63 (CH
3
CO). C
27
H
40
O
14
S, M
: 620.66 g/mol; MS:
[MþH
2
O]
þ
¼638.25.
1.2.7. 3,4,5-T i-O-ace yl-2,6-anhyd o-1-deoxy-1-S-p opyl-1- hio-
D
-gulo-hexi ol (5a)
By he gene al p ocedu e, s a ing om 4(100 mg, 0.37 mmol)
o gi e 5a (eluen B) as a colo less oil (80 mg; 63%). R
¼0.47 (eluen
C), [
a
]
D
50
(c¼0.59, CHCl
3
).
1
H NMR (360 MHz, CDCl
3
)
d
: 5.18 ( ,
1H, J¼9.4 Hz, H-4), 4.99 (ddd, 1H, J¼5.7, 9.4, 10.7 Hz, H-5), 4.95
(pseudo , 1H, J¼9.4 Hz, H-3), 4.14 (dd, 1H, J¼5.7, 11.2 Hz, H-6
eq
),
3.55 (ddd, 1H, J¼3.1, 7.6, 9.4 Hz, H-2), 3.29 (dd, 1H, J¼10.7, 11.2 Hz,
H-6
ax
), 2.67 (dd, 1H, J¼3.1, 14.1 Hz, H-1
A
), 2.58 (dd, 1H, J¼7.6,
14.1 Hz, H-1
B
), 2.45e2.55 (m, 2H, SCH
2
), 2.05, 2.03, 2.03 (3s,
33H, OAc), 1.66e1.51 (m, 2H, CH
2
), 0.98 ( , J¼7.3 Hz, 3H, CH
3
).
13
C
NMR (91 MHz, CDCl
3
)
d
170.41, 169.85, 169.72 (CO), 79.00, 73.74,
71.73, 69.21 (C-2eC-5), 66.79 (C-6), 35.41, 33.57 (C-1, SCH
2
), 22.86
(CH
3
CO), 20.76 (CH
2
), 13.45 (CH
3
). C
15
H
24
O
7
S, M
: 348.41 g/mol;
MS: [MþH]
þ
¼349.58; [MþK]
þ
¼387.58.
1.2.8. 3,4,5-T i-O-ace yl-2,6-anhyd o-1-deoxy-1-S-phenyl-1- hio-
D
-gulo-hexi ol (5b)
By he gene al p ocedu e, s a ing om 4(100 mg, 0.37 mmol)
o gi e 5b (eluen B) as a colo less oil (73 mg; 52%). R
¼0.42 (eluen
C), [
a
]
D
49.0 (c¼0.53, CHCl
3
).
1
H NMR (360 MHz, CDCl
3
)
d
:
7.41e7.16 (m, 5H, a oma ic), 5.17 (pseudo , 1H, J¼9.4 Hz, H-4), 5.01
(ddd, 1H, J¼5.6, 9.4, 11.1 Hz, H-5), 4.97 ( , 1H, J¼9.4 Hz, H-3), 4.14
(dd, 1H, J¼5.6, 11.1 Hz, H-6
eq
), 3.56 (ddd, 1H, J¼3.0, 8.0, 9.4 Hz, H-2),
3.27 (p , 1H, J¼11.1 Hz, H-6
ax
), 3.11 (dd, 1H, J¼3.0, 13.9 Hz, H-1
A
),
2.98 (dd,1H, J¼8.0,13.9 Hz, H-1
B
), 2.03, 2.02, 2.02 (3s, 33H, OAc).
13
C NMR (91 MHz, CDCl
3
)
d
: 170.32, 169.75, 169.67 (CO), 135.91,
129.63, 128.97, 126.46 (a oma ic), 77.47, 73.58, 71.74, 69.05 (C-2eC-
5), 66.76 (C-6), 36.11 (C-1), 20.68 (CH
3
). C
18
H
22
O
7
S, M
: 382.43 g/
mol; MS: [MþH]
þ
¼383.58; [MþK]
þ
¼421.58.
1.2.9. 3,4,5-T i-O-ace yl-2,6-anhyd o-1-deoxy-1-S-benzyl-1- hio-
D
-gulo-hexi ol (5c)
By he gene al p ocedu e, s a ing om 4(100 mg, 0.37 mmol)
o gi e 5c (eluen B) as a colo less oil (99 mg; 68%). R
¼0.38 (eluen
C), [
a
]
D
58.0 (c¼0.52, CHCl
3
).
1
H NMR (360 MHz, CDCl
3
)
d
:
7.35e7.19 (m, 5H, a oma ic), 5.14 ( , 1H, J¼9.4 Hz, H-4), 5.01 (ddd,
1H, J¼5.5, 9.4, 10.5 Hz, H-5), 4.91 ( , 1H, J¼9.5 Hz, H-3), 4.14 (dd, 1H,
J¼5.5, 11.2 Hz, H-6
eq
), 3.74 (d, 1H, J¼13.5 Hz, CH
2A
), 3.71 (d, 1H,
J¼13.5 Hz, CH
2B
) 3.49 (ddd, 1H, J¼3.0, 7.7, 9.4 Hz, H-2), 3.26 (dd, 1H,
J¼10.5, 11.3 Hz, H-6
ax
), 2.53 (dd, 1H, J¼3.0, 14.3 Hz, H-1
A
), 2.44 (dd,
1H, J¼7.7, 14.3 Hz, H-1
B
), 2.03, 2.01, 1.95 (3s, 33H, OAc).
13
C NMR
(91 MHz, CDCl
3
)
d
: 170.41, 169.85, 169.62 (CO), 138.03, 129.11,
128.51,127.11 (a oma ic), 78.84, 73.70, 71.59, 69.19 (C-2eC-5), 66.79
(C-6), 36.94 (C-1), 32.10 (SCH
2
), 20.76 (CH
3
). C
19
H
24
O
7
S, M
:
396.45 g/mol; MS: [MþH]
þ
¼397.58; [MþK]
þ
¼435.58.
1.2.10. 3,4,5-T i-O-ace yl-2,6-anhyd o-1-deoxy-1-S-(2,3,4,5- e a-
O-ace il-
b
-
D
-galac opy anosyl)-1- hio-
D
-gulo-hexi ol (5d)
By he gene al p ocedu e, s a ing om 4(50 mg, 0.185 mmol)
o gi e 5d (eluen B) as a colo less oil (81 mg; 69%). R
¼0.16 (eluen
C), [
a
]
D
47.0 (c¼0.58, CHCl
3
).
1
H NMR (360 MHz, CDCl
3
)
d
: 5.39
(dd, 1H, J¼1.1, 3.3 Hz, H-4
0
), 5.19 ( , 1H, J¼10.0 Hz, H-2
0
), 5.12 ( , 1H,
J¼9.5 Hz, H-4), 5.00 (dd, 1H, J¼3.3, 10.0 Hz, H-3
0
), 4.93 (ddd, 1H,
J¼5.7, 9.5, 10.5 Hz, H-5), 4.88 ( , 1H, J¼9.5 Hz, H-3), 4.51 (d, 1H,
J¼10.0 Hz, H-1
0
), 4.12 (dd, 1H, J¼6.6, 11.2 Hz, H-6
0
A
), 4.10 (dd, 1H,
J¼5.7, 11.2 Hz, H-6
eq
), 4.05 (dd, 1H, J¼6.8, 11.4 Hz, H-6
0
B
), 3.89 (ddd,
1H, J¼1.1, 6.6, 6.8 Hz, H-5
0
), 3.65 (ddd, 1H, J¼2.7, 7.5, 10.0 Hz, H-2),
3.23 (dd, 1H, J¼10.5, 11.2 Hz, H-6
ax
), 2.99 (dd, 1H, J¼2.7, 14.1 Hz, H-
J. J
ozse e al. / Ca bohyd a e Resea ch xxx (2015) 1e75
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CAR7009_p oo ■6 June 2015 ■5/7
Please ci e his a icle in p ess as: J
ozse J, e al., Pho oini ia ed hyd o hiola ion o py anoid exo-glycals: he D-galac o and D-xylo cases,
Ca bohyd a e Resea ch (2015), h p://dx.doi.o g/10.1016/j.ca es.2015.05.008
1
A
), 2.63 (dd, 1H, J¼7.5, 14.1 Hz, H-1
B
), 2.12, 2.04, 2.03, 2.00, 1.99,
1.97, 1.93 (7s, 73H, OAc).
13
C NMR (91 MHz, CDCl
3
)
d
: 170.27,
170.10, 169.90, 169.71, 169.55 (CO), 83.34, 77.93, 74.43, 73.65, 71.85,
71.35, 68.98, 67.20, 66.66, (C-2eC5 and C-1
0
eC-5
0
) 66.73 (C-6),61.26
(C-6
0
), 30.54 (C-1), 20.68, 20.63, 20.51 (CH
3
). C
26
H
36
O
16
S, M
:
636.62 g/mol; MS: [MþNa]
þ
¼659.92.
1.2.11. 3,4,5-T i-O-ace yl-2,6-anhyd o-1-deoxy-1-S-(2,3,4- i-O-
ace yl-
b
-
D
-xylopy anosyl)-1- hio-
D
-gulo-hexi ol (5e)
By he gene al p ocedu e, s a ing om 4(50 mg, 0.185 mmol)
o gi e 5e (eluen B) as a colo less oil (78 mg; 75%). R
¼0.20 (eluen
C), [
a
]
D
96 (c¼0.52, CHCl
3
).
1
H NMR (360 MHz, CDCl
3
)
d
: 5.14 ( ,
1H, J¼9.4 Hz, H-4), 5.12 ( , 1H, J¼8.4 Hz, H-3
0
), 4.99e4.82 (m, 4H, H-
3, H-5, H-2
0
, H-4
0
), 4.58 (d, 1H, J¼8.4 Hz, H-1
0
), 4.19 (dd, 1H, J¼5.0,
11.7 Hz, H-5
0
eq
), 4.09 (dd, 1H, J¼5.6, 11.2 Hz, H-6
eq
), 3.58 (ddd, 1H,
J¼2.9, 7.0, 9.8 Hz, H-2), 3.34 (dd, 1H, J¼8.8, 11.7 Hz, H-5
0
ax
), 3.24 ( ,
1H, J¼11.2 Hz, H-6
ax
), 2.90 (dd, 1H, J¼2.9, 14.0 Hz, H-1
A
), 2.63 (dd,
J¼7.0, 14.0 Hz, 1H, H-1
B
), 2.05, 2.02, 2.01, 2.01, 1.99, 1.98 (6s, 63H,
OAc).
13
C NMR (91 MHz, CDCl
3
)
d
: 170.43, 169.89, 169.85, 169.70,
169.53 (CO), 83.17, 78.04, 73.79, 71.93, 71.27, 69.64, 69.12, 68.62 (C-
2eC-5 and C-1
0
eC-4
0
), 66.83 (C-6), 65.35 (C-5
0
), 30.85, 20.79 (CH
3
).
C
23
H
32
O
14
S, M
: 564.56 g/mol; MS: [MþNa]
þ
¼588.08.
1.2.12. 3,4,5-T i-O-ace yl-2,6-anhyd o-1-deoxy-1-S-(1,2:3,4,-di-O-
isop opylidene-
b
-
D
-galac opy anose-6-yl)-1- hio-
D
-gulo-hexi ol
(5 )
By he gene al p ocedu e, s a ing om 4(100 mg, 0.38 mmol)
o gi e 5 (eluen B) as a colo less oil (108 mg; 53%). R
¼0.36 (eluen
C), [
a
]
D
71 (c¼0.58, CHCl
3
).
1
H NMR (360 MHz, CDCl
3
)
d
: 5.47 (d,
1H, J¼5.0 Hz, H-1
0
), 5.13 (pseudo , 1H, J¼9.5 Hz, H-4), 4.92 (ddd,1H,
J¼5.5, 9.5, 10.5 Hz, H-5), 4.86 (pseudo , 1H, J¼9.5 Hz, H-3), 1H, 4.57
(dd, J¼2.4, 7.9 Hz, H-4
0
), 4.27 (dd, 1H, J¼2.2, 5.1 Hz, H-2
0
),4.25
(pseudo , 1H, J¼2.2 Hz, H-3
0
) 4.09 (dd, 1H, J¼5.5, 11.2 Hz, H-6
eq
),
3.85 (m, 1H, H-5
0
), 3.52 (ddd, 1H, J¼2.7, 8.2, 9.5 Hz, H-2), 3.24 (dd,
1H, J¼10.5, 11.2 Hz, H-6
ax
), 2.80e2.69 (m, 3H, H-1
A
and 2H-6
0
),
2.57 (dd, 1H, J¼8.2, 14.3 Hz, H-1
B
), 2.00, 1.99, 1.98 (3s, 33H, OAc),
1.50, 1.40, 1.31, 1.28 (4s, 43H, CH
3
).
13
C NMR (91 MHz, CDCl
3
)
d
:
170.38, 169.86, 169.73 (CO), 109.29, 108.65 (C), 96.68, 78.97, 73.74,
71.74, 71.65, 70.95, 70.55, 69.23, 67.72 (C-2eC-5 and C-1
0
eC-5
0
),
66.75 (C-6), 33.96 (C-1), 32.78 (C-6
0
), 26.10, 26.05, 24.96, 24.51,
20.76 (CH
3
). C
24
H
36
O
12
S, M
: 548.60 g/mol; MS:
[MþH
2
O]
þ
¼566.42.
1.2.13. 3,4,5-T i-O-ace yl-2,6-anhyd o-1-deoxy-1-S-p opyl-1- hio-
D
-ido-hexi ol (6a)
By he gene al p ocedu e, s a ing om 4(100 mg, 0.37 mmol)
o gi e 6a (eluen B) as a colo less oil (5 mg; 4%). R
¼0.42 (eluen C),
[
a
]
D
37 (c¼0.25, CHCl
3
).
1
H NMR (360 MHz, CDCl
3
)
d
: 5.08 ( d, 1H,
J¼1.4, 3.3 Hz, H-4), 4.89 (b oad signal, H-3), 4.70 (b oad signal, H-5),
4.03 (dd, 1H, J¼1.7, 13.2 Hz, H-6
eq
), 3.86 (dd, 1H, J¼2.2, 13.2 Hz, H-
6
ax
), 3.82e3.86 (m,1H, H-2), 2.78 (dd,1H, J¼7.5,13.6 Hz, H-1
A
), 2.60
(dd, 1H, J¼6.3, 13.6 Hz, H-1
B
), 2.56e2.48 (m, 2H, SCH
2
), 2.14, 2.13,
2.11 (3s, 33H, OAc), 1.63e1.54 (m, 2H), 0.98 ( , J¼7.3 Hz, 3H).
1.2.14. 3,4,5-T i-O-ace yl-2,6-anhyd o-1-deoxy-1-S-phenyl-1- hio-
D
-ido-hexi ol (6b)
By he gene al p ocedu e, s a ing om 4(100 mg, 0.37 mmol)
o gi e 6b (eluen B) as a colo less oil (11 mg; 8%). R
¼0.38 (eluen
C), [
a
]
D
47 (c¼0.53, CHCl
3
).
1
H NMR (360 MHz, CDCl
3
)
d
: 7.46e7.06
(m, 5H, a oma ic), 5.08 ( d, 1H, J¼1.3, 3.1 Hz, H-4), 4.93 (b oad
signal, 1H, H-3), 4.97 (ddd, 1H, J¼1.0, 2.1, 3.3 Hz, H-5), 4.04 (dd, 1H,
J¼1.0, 13.3 Hz, H-6
eq
), 3.83 (dd, 1H, J¼2.1, 13.3 Hz, H-6
ax
), 3.82e3.88
(m, 1H, H-2), 3.20 (dd, 1H, J¼7.7, 13.7 Hz, H-1
A
), 3.02 (dd, 1H, J¼7.0,
13.7 Hz, H-1
B
), 2.11, 2.09, 2.08 (3s, 33H, OAc).
1.2.15. 3,4,5-T i-O-ace yl-2,6-anhyd o-1-deoxy-1-S-benzyl-1- hio-
D
-ido-hexi ol (6c)
By he gene al p ocedu e, s a ing om 4(100 mg, 0.37 mmol)
o gi e 6c (eluen B) as a colo less oil (8 mg; 5%). R
¼0.35 (eluen C),
[
a
]
D
50 (c¼0.40, CHCl
3
).
1
H NMR (500 MHz, CDCl
3
)
d
: 7.34e7.22
(m, 5H, a oma ic), 5.02 (b oad signal, 1H, H-4), 4.79 (b oad signal,
1H, H-3), 4.65 (b oad signal,1H, H-5), 4.97 (d,1H, J¼13.6,11.2 Hz, H-
6
eq
), 3.75 (dd, 1H, J¼2.3,13.6 Hz, H-6
ax
), 3.74 (s, 2H, CH
2
), 3.66 (ddd,
1H, J¼1.9, 6.1, 7.7 Hz, H-2), 2.71 (dd, 1H, J¼7.7, 13.7 Hz, H-1
A
), 2.52
(dd, 1H, J¼6.1, 13.7 Hz, H-1
B
), 2.11, 2.09, 2.07 (3s, 33H, OAc).
13
C
NMR (125.77 MHz, CDCl
3
)
d
: 169.87, 168.59 (CO), 138.34, 129.04,
128.71, 127.31 (a oma ic), 74.17, 67.44, 66.67, 66.72 (C-2eC-5), 66.28
(C-6), 37.35 (C-1), 31.73 (SCH
2
), 21.16, 21.0, 20.86 (CH
3
).
1.2.16. 3,4,5-T i-O-ace yl-2,6-anhyd o-1-deoxy-1-S-(2,3,4,5- e a-
O-ace il-
b
-
D
-galac opy anosyl)-1- hio-
D
-ido-hexi ol (6d)
By he gene al p ocedu e, s a ing om 4(100 mg, 0.37 mmol)
o gi e 6d (eluen B) as a colo less oil (3.5 mg; 3%). R
¼0.15 (eluen
C), [
a
]
D
45 (c¼0.175, CHCl
3
).
1
H NMR (360 MHz, CDCl
3
)
d
: 5.44 (dd,
1H, J¼1.0, 3.3 Hz, H-4
0
), 5.22 ( , 1H, J¼10.0 Hz, H-2
0
), 5.04 (b oad
signal, 1H, H-4), 5.04 (dd, 1H, J¼3.3, 10.0 Hz, H-3
0
), 4.87 (b oad
signal, 1H, H-3), 4.70 (b oad signal, 1H, H-5), 4.55 (d, 1H, J¼9.9 Hz,
H-1
0
), 4.09e4.16 (m, 2H, H-6
0
AB
), 4.03 (dd, 1H, J¼1.8, 13.3 Hz, H-6
eq
),
3.95 ( d, 1H, J¼1.1, 6.6 Hz, H-5
0
), 3.91e3.97 (m, 1H, H-2), 3.86 (dd,
1H, J¼2.2, 13.3 Hz, H-6
ax
), 3.01 (dd, 1H, J¼8.1, 13.5 Hz, H-1
A
), 2.72
(dd, 1H, J¼5.5, 13.5 Hz, H-1
B
), 2.17, 2.16, 2.15, 2.14, 2.12, 2.06, 2.05
(7s, 73H, OAc).
1.2.17. 3,4,5-T i-O-ace yl-2,6-anhyd o-1-deoxy-1-S-(1,2:3,4,-di-O-
isop opylidene-
b
-
D
-galac opy anose-6-yl)-1- hio-
D
-ido-hexi ol (6 )
By he gene al p ocedu e, s a ing om 4(100 mg, 0.37 mmol)
o gi e 6 (eluen B) as a colo less oil (7 mg; 3.5%). R
¼0.33 (eluen
C), [
a
]
D
40 (c¼0.35, CHCl
3
).
1
H NMR (360 MHz, CDCl
3
)
d
: 5.52 (d,
1H, J¼5.0 Hz, H-1
0
), 5.06 (b oad signal, 1H, H-4), 4.86 (b oad signal,
1H, H-3), 4.70 (b oad signal, 1H, H-5), 4.61 (dd, J¼2.3, 7.9 Hz, H-4
0
),
4.33e4.27 (m, 2H, H-3
0
, H-2
0
), 4.02 (dd, 1H, J¼1.6, 14.8 Hz, H-6
eq
),
3.86e3.95 (m, 1H, H-2), 3.90e3.84 (m, 2H, H-5
0
, H-6
ax
), 2.85 (dd,
1H, J¼8.2, 13.8 Hz, H-1
A
) 2.82e2.69 (m, 2H, H-6
0
), 2.66 (dd, 1H,
J¼5.4, 13.8 Hz, H-1
B
), 2.13, 2.12, 2.11 (3s, 33H, OAc), 1.54, 1.44,
1.34, 1.33 (4s, 43H, CH
3
).
Acknowledgmen s
This wo k was suppo ed by he Hunga ian Scien ific Resea ch
Fund (G an s: OTKA 109208 and 109450) and he BAROSS
REG_EA_09-1-2009-0028 (LCMS_TAN) p ojec . D . A. Kiss-Szikszai
is hanked o eco ding he mass spec a.
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CAR7009_p oo ■6 June 2015 ■6/7
Please ci e his a icle in p ess as: J
ozse J, e al., Pho oini ia ed hyd o hiola ion o py anoid exo-glycals: he D-galac o and D-xylo cases,
Ca bohyd a e Resea ch (2015), h p://dx.doi.o g/10.1016/j.ca es.2015.05.008
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CAR7009_p oo ■6 June 2015 ■7/7
Please ci e his a icle in p ess as: J
ozse J, e al., Pho oini ia ed hyd o hiola ion o py anoid exo-glycals: he D-galac o and D-xylo cases,
Ca bohyd a e Resea ch (2015), h p://dx.doi.o g/10.1016/j.ca es.2015.05.008