Synthesis of porphyrin receptors modified by glycosylated steroids

Article abstract of DOI:10.1135/cccc20041149

5,10,15,20-Tetrakis-[3α-(2,3,4,6-tetra-O-benzyl-β-D- glucopyranosyl)-5β-cholan-24-yl]porphyrin and 5,10,15,20-tetrakis- [3α-(2,3,4,6-tetra-O-benzyl-β-D-galactopyranosyl)-5β-cholan-24- yl]-porphyrin were synthesized by condenzation of the respective steroi

Full text of DOI:10.1135/cccc20041149

Porphyrin Receptors Modified by Glycosylated Steroids
1149
SYNTHESIS OF PORPHYRIN RECEPTORS MODIFIED BY
GLYCOSYLATED STEROIDS+
a
b,c1
Karel ZELENKAa1, Tomáš TRNKAa2, Iva TIŠLEROVÁ , Vladimír KRÁL
,
b,c
b,c2,
Mykhaylo DUKH and Pavel DRAŠAR
*
a
Department of Organic Chemistry, Charles University, Albertov 8, 128 40 Prague 2,
Czech Republic; e-mail: zeli1@post.cz,2 trnka@natur.cuni.cz
1
b
c
Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic,
Flemingovo nám. 2, 166 10 Prague 6, Czech Republic
Department of Chemistry of Natural Compounds, Institute of Chemical Technology, Prague,
1
Technická 5, 166 28 Prague 6, Czech Republic; e-mail: vladimir.kral@vscht.cz,
2
pavel.drasar@vscht.cz
Received Jan uary 19, 2004
Accepted February 16, 2004
Dedicated to Professor Ivan Stibor on the occasion of his 60th birthday.
5,10,15,20-Tetrakis-[3α-(2,3,4,6-tetra-O-ben zyl-β-D-glucopyran osyl)-5β-ch olan -24-yl]porph yrin
an d 5,10,15,20-tetrakis-[3α-(2,3,4,6-tetra-O-ben zyl-β-D-galactopyran osyl)-5β-ch olan -24-yl]-
porph yrin were syn th esized by con den zation of th e respective steroid aldeh ydes an d
pyrrole-1-yl m agn esium brom ide.
Keyw ord s: Porph yrin oids; Porph yrin s; Pyrrols; Steroids; m eso-Substitution ; Receptor m odifi-
cation ; Steroid glycosides; Supram olecular ch em istry.
Th e aim of th e work was to prepare com poun ds con tain in g tailored carbo-
h ydrate, steroid an d porph yrin m oieties. Th e idea was based on th eir fun c-
tion as th ey m igh t sh ow m an y in terestin g properties like ion com plexation ,
m olecular an d ch iral recogn ition , form ation of self-assem blin g system s an d
ion ch an n els followed by un specified biological activities. We aim ed our
work at possible an alytical use of th is n ew type of receptor4,5, wh ich h as
practically im portan t two levels of its lipoph ilicity/h ydroph ilicity con trol.
First, via utilization of differen t bile acids as lin kers (ch olic, lith och olic,
deoxych olic, etc.)6,7 an d secon d, via utilization of carboh ydrates with dif-
+ Presen ted in parts as prelim in ary com m un ication 1–3
.
Collect. Czech. Chem. Commun. (Vol. 69) (2004)
doi:10.1135/cccc20041149

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Zelenka, Trnka, Tišlerová, Král, Dukh, Drašar:
feren t con figuration an d levels of deoxygen ation an d OH groups protec-
tion . As an addition al fun ction , carboh ydrate could an ch or th e lipoph ilic
steroid m oiety (an d vice versa) to th e in terph ase between im m iscible
ph ases or on to a m em bran e, allowin g th e porph yrin to com plex or tran sfer
th e ion ic substrates8,9. An oth er role of steroid–sacch aride structure could be
th e utilization of differen t types of recogn ition 10,11 an d h ydrogen bon din g
durin g m olecular recogn ition 12–14 an d self-assem bly. Th is paper aim s to
open syn th etic path way to th is fam ily of m odified receptors. Th e properties
of th ese com poun ds are bein g studied.
Th e above com poun ds possess special properties an d could play an im -
portan t role in biological system s. It was sh own in a sim ilar study of
ph en an th rolin e receptors15 th at th is expectation was fulfilled in m an y as-
pects. Th e key structural features respon sible for differen t aspects of th e
fun ction ality could be con trolled even by usin g cation com plexation 15. Re-
cen tly, porph yrin an d calix[4]pyrrole structures substituted in meso posi-
tion s by steroid un its were prepared16–21. We presen t th e syn th esis of
porph yrin rin g core substituted with glycosylated steroid lin kers. Th e syn -
th etic target of th is study was th e developm en t of a m ultistep syn th esis of
glycosylated steroid-substituted porph yrin with a protected carboh ydrate
m oiety, as a bulky lipoph ilic system with good ch iral UV ch rom oph ores
aside from a typical Sorret on e.
Strategies for th e syn th esis of lipoph ilic type of sym m etric tetrasubstitu-
ted porph yrin structures were in vestigated (Sch em e 1). Startin g com poun ds
1, 2 an d 3 were prepared accordin g to literature22,23. Glycosylation of 3
with 1 or 2 un der Kön igs–Kn orr con dition s gave com poun ds 4 an d 5 in
good yields. 2,3,4,6-Tetra-O-acetyl-α-D-glucopyran osyl brom ide (1) in aceto-
n itrile gave with m eth yl ester of lith och olic acid (3) un der catalysis with
m ercuric cyan ide β-glucoside 4 in 50% yield; sim ilarly 2,3,4,6-tetra-O-
acetyl-α-D-galactopyran osyl brom ide (2) gave 54% of β-galactoside 5. Th e
acetylated glycoside don ors were ch osen for th e expected h igh er yields of
glycosides.
Deprotection of acetyl groups was ach ieved un der Zem plén con dition s
with sodium m eth oxide in m eth an ol to give com poun ds 6 an d 7 in
70–80% yields. Th e reaction of 6 an d 7 with ben zyl brom ide in toluen e pro-
vided com poun ds 8 an d 9 in 82 an d 43% yields, respectively. Th ese com -
poun ds were reduced with LiAlH4 in dieth yl eth er at room tem perature to
obtain com poun ds 10 an d 11 in 82 an d 89% yields, respectively. Oxidation
of 10 an d 11 with pyridin ium ch loroch rom ate (PCC) in CH2Cl2 gave alde-
h ydes 12 an d 13 in ca. 80% yields. All th e above com poun ds were fully
ch aracterized.
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Porphyrin Receptors Modified by Glycosylated Steroids
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SCHEME 1
Reaction of pyrrol-1-yl m agn esium brom ide (for com parison with oth er
ch iral aldeh ydes see24) with aldeh ydes 12 an d 13 (Sch em e 2) form ed por-
ph yrin ogen wh ich was oxidized to porph yrin rin g with DDQ to give 14 an d
15, respectively wh ich were fully ch aracterized. Th e reaction sequen ce used
was selected as th e m ost efficien t after a com parison with altern ative
routes.
Th e fin al ch rom atograph ies on a silica gel colum n in toluen e–dieth yl
eth er an d on preparative TLC plates gave two colored fraction s each . On ly
th e secon d fraction s were fully ch aracterized an d elucidated in both galacto-
an d gluco-series as sin gle defin ed ch em ical en tities 14 an d 15 in th e yields
of 9.5 an d 6.3%, respectively. Th e first fraction s were n ot fully ch aracter-
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Zelenka, Trnka, Tišlerová, Král, Dukh, Drašar:
ized due to in sufficien t am oun ts of experim en tal m aterial; so we den ote
th em just as fraction s in both cases n ot to cause possible m isin terpreta-
tion s. In itial an alyses sh ow both first fraction s are an alogous porph yrin s as
14 an d 15, h owever on e meso position in each h ad sign ifican tly ch an ged.
SCHEME 2
Th e suitabile syn th etic path way for th e n ew type of meso-substituted por-
ph yrin s (14 an d 15) en ables th e study of th is n ew kin d of supram olecules
an d supram olecular syn th on s. Th ese are bein g utilized in electroch em istry4,
m em bran e, super assem bly an d biological studies, i.a. We will em ploy th is
n ew syn th etic path way for th e syn th esis of h exasacch aride an d pen ta-
sacch aride series of th is receptor types with a tailored level of lipoph ilicity.
Th is paper sh ows th e possibility of overcom in g several m eth odological
problem s in th e syn th esis of a n ew com plex type of con jugates an d open s
rath er vast territory of th eir possible exploitation s. Th e auth ors aim ed to
dem on strate th e possibility of com bin in g th e kn own receptor m olecules
with carboh ydrates th at can serve as an ch ors, ch iral selectors, or polarity
m odifiers, depen din g on th eir level an d kin d of protection , as discussed
above.
EXPERIMENTAL
Meltin g poin ts were determ in ed on a Boetius m icro-m eltin g poin t apparatus (Germ an y).
Optical rotation s were m easured on an Autopol III (Rudolph Research An alytical, Flan ders,
U.S.A.) polarim eter at 23 °C, [α]D values are given in 10–1 deg cm 2 g–1 an d con cen tration s in
10–1 g l–1. IR spectra (waven um bers in cm –1) were recorded on a Bruker IFS 88 spectrom eter
in ch loroform solution s (23 °C). 1H NMR an d 13C NMR spectra were recorded on a Varian
Un ity 400 In ova (1H at 400 MHz, 13C at 100 MHz). All NMR spectra were m easured at 25 °C
in CDCl3 usin g TMS as an in tern al stan dard. Ch em ical sh ifts (δ) are given in ppm an d cou-
plin g con stan ts (J) in Hz. Mass spectra were recorded on a VG An alytical ZAB-EQ spectrom e-
ter (FAB) an d Bruker Esquire 3000 (ESI). MALDI-TOF an alyses were carried out with a Biflex IV
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Porphyrin Receptors Modified by Glycosylated Steroids
1153
Bruker Dalton ic m ass spectrom eter, equipped with a UV n itrogen laser (337 n m ) an d a dual
m icroch an n el plate detector. Microan alyses were perform ed on a Perkin –Elm er 2400 Series II
CHNS/O elem en tal an alyzer. Th in layer ch rom atograph y was carried out on an alytical plates
Merck (type 5554, with a layer of Kieselgel 60 F254) or silica gel G (ICN Biom edicals), detec-
tion by UV lam p or by sprayin g with con cen trated sulfuric acid or 3% an isaldeh yde solution
in eth an ol an d sulfuric acid, followed by h eatin g. Preparative th in layer ch rom atograph y
was perform ed on 200 × 200 m m plates (layer th ickn ess 0.4 m m ) of silica gel G (ICN
Biom edicals). For colum n ch rom atograph y, n eutral silica gel SiliTech 32-63, 60A (ICN
Biom edicals) or Silpearl (Kavalier, Czech Republic) was used. An alytical sam ples were dried
un der vacuum over P2O5 at room tem perature. For n eutralization of m eth an olic solution s
after deacetylation s, stron gly acid cation exch an ger Fluka (Dowex 50W×8) in H+ cycle was
used. Fresh ly distilled solven ts were used.
Meth yl 3α-(2,3,4,6-Tetra-O-acetyl-β-D-glucopyran osyloxy)-5β-ch olan -24-oate (4)
To a solution of m eth yl lith och olate (3; 10 g, 25.6 m m ol) an d D-acetobrom oglucose (1; 20 g,
48.6 m m ol) in dry aceton itrile (300 m l), m ercuric cyan ide (12.27 g, 48.6 m m ol) was added
an d th e reaction m ixture was h eated to reflux. Th e reaction course was m on itored by TLC
(h exan e–eth yl acetate, 2.5:1). After 5 h , th e reaction m ixture was allowed to warm to room
tem perature, th e solven t was evaporated, th e residue was dissolved in dich lorom eth an e
(200 m l) an d wash ed with water (3 × 100 m l). Th e organ ic layer was separated, dried over
an h ydrous MgSO4 an d th e solven t was rem oved un der vacuum on a rotary evaporator. Th e
residue was purified by ch rom atograph y on a silica gel colum n (toluen e–eth yl acetate, 9:1).
Recrystallization from a m ixture of ether–petroleum ether gave 4 (9.3 g, 50%). M.p. 132–133 °C,
[α]D +12 (c 0.5, CHCl3). 1H NMR: 0.63 s, 3 H (H-18); 0.91 d, 3 H (J = 6.4, H-21); 0.91 s, 3 H
(H-19); 2.01 s, 3 H; 2.02 s, 3 H; 2.05 s, 3 H; 2.08 s, 3 H (4 × OAc); 0.86–2.40, 28 H (steroid
fin gerprin t); 3.57 tt, 1 H (ΣJ = 31.6, H-3β); 3.67 s, 3 H (COOCH3); 3.69 ddd, 1 H (J1 = 9.9,
J2 = 5.0, J3 = 2.4, H-5′); 4.11 dd, 1 H (J1 = 12.2, J2 = 2.4, H-6a′); 4.26 dd, 1 H (J1 = 12.2, J2
=
5.2, H-6b′); 4.59 d, 1 H (J = 7.9, H-1′); 4.95 dd, 1 H (J1 = 9.6, J2 = 7.9, H-2′); 5.07 t, 1 H (J =
9.9, H-4′); 5.21 t, 1 H (J = 9.5, H-3′). 13C NMR: 11.98, 18.22, 20.59, 20.63, 20.72 (2C); 20.79,
23.34, 24.13, 26.22, 27.15, 27.18, 28.14, 30.95, 31.02, 34.16, 34.61, 35.12, 35.32, 35.77,
40.05, 40.23, 42.16, 42.67, 51.46, 55.84, 56.24, 62.18, 68.56, 71.56 (2C); 72.86, 80.90, 99.87,
169.33, 169.40, 170.36, 170.70, 174.77. MS (FAB, CHCl3), m/z: 743 (M + Na+), 720 (M+). MS
(ESI, MeOH): 743.7 (M + Na+), 759.5 (M + K+); MS2 (743.7) 683.6, 311.2; MS3 (683.6) 623.4,
581.4, 521.4, 479.3, 427.0, 311.1, 251.1. For C39H60O12 (720.9) calculated: 64.98% C, 8.39% H;
foun d: 64.77% C, 8.17% H.
Meth yl 3α-(β-D-Glucopyran osyloxy)-5β-ch olan -24-oate (6)
To a stirred solution of 4 (9.0 g, 12.5 m m ol) in dry m eth an ol (250 m l), sodium m eth oxide
in m eth an ol (10 m m ol, 10 m l) was added. Th e reaction m ixture was stirred at room tem per-
ature an d m on itored by TLC. After com plete deacetylation (approxim ately 1 h ), Dowex 50
in H+ cycle (2 g) was added to th e m ixture an d th e suspen sion was stirred un til th e reaction
m ixture was n eutral to pH paper. Th e resin was filtered off an d m eth an ol was evaporated.
Th e residue was crystallized from m eth an ol to give com poun d 6 (5 g, 72%). M.p. 192–194 °C,
[α]D +18 (c 0.45, MeOH). 1H NMR (MeOH-d4, 45 °C): 0.65 s, 3 H (H-18); 0.91 d, 3 H (J = 6.8,
H-21); 0.92 s, 3 H (H-19); 0.89–2.40, 28 H (steroid fin gerprin t); 2.55 bs, 1 H (OH); 3.03 bs,
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Zelenka, Trnka, Tišlerová, Král, Dukh, Drašar:
1 H (OH); 3.32–3.62, 6 H (H-2′, H-3′, H-4′, H-5′, 2 × OH); 3.66 s, 3 H (COOCH3); 3.67 tt, 1 H
(ΣJ = 31.8, H-3β); 3.78–3.92, 2 H (H-6a′, H-6b′); 4.42 d, 1 H (J = 7.8, H-1′). 13C NMR (25 °C):
12.03, 18.28, 20.85, 23.38, 24.21, 26.39, 26.95, 27.23, 28.17, 31.00, 31.09, 34.25, 34.72,
35.15, 35.35, 35.83, 40.12, 40.37, 42.22, 42.72, 51.47, 56.00, 56.38, 61.90, 69.86, 73.52,
75.41, 76.39, 79.50, 100.75, 174.74. MS (FAB, MeOH), m/z: 553 (M + H+). MS (ESI, MeOH):
575.6 (M + Na+), 591.4 (M + K+); MS2 (575.6) 557.1, 515.5, 485.4, 455.3, 413.2; MS3 (413.2)
347.8. For C31H52O8 (552.7) calculated: 67.36% C, 9.48% H; foun d: 67.28% C, 9.54% H.
Meth yl 3α-(2,3,4,6-Tetra-O-ben zyl-β-D-glucopyran osyloxy)-5β-ch olan -24-oate (8)
To a solution of com poun d 6 (4.8 g, 8.7 m m ol) in dry toluen e (200 m l), fresh ly powdered
potassium h ydroxide (2.5 g, 44.6 m m ol), ben zyl brom ide (5.3 m l, 44.4 m m ol) an d tetra-
butylam m on ium iodide (3.2 g, 8.7 m m ol) were added. Th e reaction m ixture was refluxed
un der argon an d m on itored by TLC. After 24 h , th e secon d portion of potassium h ydroxide
(0.5 g) was added. Th e reaction wen t to com pletion after 2 days, potassium h ydroxide was
filtered off on a silica gel colum n , th e filtrate was wash ed with water (2 × 75 m l), dried an d
th en evaporated to dryn ess. After ch rom atograph y on a silica gel colum n (toluen e–eth yl
acetate, 29:1), pure com poun d 8 (3.2 g, 40%) was obtain ed by crystallization from eth an ol.
M.p. 102–104 °C, [α]D +22 (c 0.5, CHCl3). 1H NMR: 0.64 s, 3 H (H-18); 0.91 s, 3 H (H-19);
0.92 d, 3 H (J = 6.4, H-21); 0.80–2.45, 28 H (steroid fin gerprin t); 3.43 dd, 1 H (J1 = 9.3, J2
=
7.9, H-2′); 3.46 ddd, 1 H (J1 = 9.8, J2 = 5.2, J3 = 1.7, H-5′); 3.52 dd, 1 H (J1 = 9.8, J2 = 8.6,
H-4′); 3.63 t, 1 H (J = 8.9, H-3′); 3.63 dd, 1 H (J1 = 10.6, J2 = 5.2, H-6a′); 3.68 tt, 1 H (ΣJ =
31.6, H-3β); 3.74 dd, 1 H (J1 = 10.8, J2 = 1.8, H-6b′); 4.50 d, 1 H (J = 7.8, H-1′); 4.54 d, 1 H
(J = 10.8, H-ben zyl); 4.55 d, 1 H (J = 12.4, H-ben zyl); 4.60 d, 1 H (J = 12.2, H-ben zyl); 4.72 d,
1 H (J = 10.8, H-ben zyl); 4.78 d, 1 H (J = 11.0, H-ben zyl); 4.82 d, 1 H (J = 11.0, H-ben zyl);
4.92 d, 1 H (J = 11.0, H-ben zyl); 4.98 d, 1 H (J = 10.8, H-ben zyl); 7.16–7.38, 20 H (H-arom .).
13C NMR: 12.00, 18.24, 20.78, 23.37, 24.15, 26.31, 27.14, 27.34, 28.14, 30.95, 30.98, 34.61
(2C); 35.18, 35.30, 35.76, 40.10, 40.33, 42.08, 42.68, 51.42, 55.89, 56.40, 69.19, 73.33,
74.77, 74.83, 74.95, 75.66, 78.00, 80.15, 82.41, 84.77, 102.26, 127.47, 127.55, 127.56 (2C);
127.60, 127.70, 127.86 (2C); 127.95 (2C); 128.17 (2C); 128.25 (2C); 128.31 (4C); 128.33
(2C); 138.06, 138.26, 138.53, 138.58, 174.71. MS (FAB, CHCl3), m/z: 936 (M + Na+), 913
(M+). MS (ESI, MeOH): 935.7 (M + Na+), 951.6 (M + K+); MS2 (935.7) 905.6, 819.1, 563.3,
455.4; MS3 (563.3) 456.1, 413.2, 323.2, 231.1, 173.2. For C59H76O8 (913.2) calculated: 77.6% C,
8.39% H; foun d: 77.52% C, 8.29% H.
3α-(2,3,4,6-Tetra-O-ben zyl-β-D-glucopyran osyloxy)-5β-ch olan -24-ol (10)
To a solution of m eth yl ester 8 (2.9 m g, 3.2 m m ol) in dieth yl eth er (100 m l, dry), lith ium
alum in ium h ydride (245 m g, 6.4 m m ol) was added cautiously. Th e reaction m ixture was
stirred at room tem perature un der argon atm osph ere an d th e reaction was m on itored by
TLC. After 2 h , wh en n o m eth yl ester was detected by TLC, th e excess LiAlH4 was carefully
decom posed by addition of a m ixture of eth yl acetate (3 m l) an d water (1.5 m l). Th e form ed
suspen sion was filtered over Celite an d wash ed with eth yl acetate. Th e filtrate was dried
over an h ydrous MgSO4 an d evaporated to dryn ess. Th e crude product was crystallized from
eth an ol to obtain alcoh ol 10 (2.3 g, 82%). M.p. 73–74 °C, [α]D +22 (c 0.5, CHCl3). 1H NMR:
0.65 s, 3 H (H-18); 0.91 s, 3 H (H-19); 0.93 d, 3 H (J = 6.4, H-21); 0.90–2.00, 28 H (steroid
fin gerprin t); 3.44 dd, 1 H (J1 = 9.2, J2 = 7.9, H-2′); 3.47 ddd, 1 H (J1 = 9.8, J2 = 5.2, J3 = 1.8,
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Porphyrin Receptors Modified by Glycosylated Steroids
1155
H-5′); 3.53 dd, 1 H (J1 = 9.8, J2 = 8.6, H-4′); 3.58–3.72, 5 H (CH2OH, H-6a′, H-3′, H-3β);
3.74 dd, 1 H (J1 = 10.8, J2 = 1.8, H-6b′); 4.51 d, 1 H (J = 7.9, H-1′); 4.54 d, 1 H (J = 10.8,
H-ben zyl); 4.56 d, 1 H (J = 12.4, H-ben zyl); 4.60 d, 1 H (J = 12.2, H-ben zyl); 4.72 d, 1 H (J =
10.8, H-ben zyl); 4.78 d, 1 H (J = 11.0, H-ben zyl); 4.82 d, 1 H (J = 10.8, H-ben zyl); 4.92 d, 1 H
(J = 10.8, H-ben zyl); 4.99 d, 1 H (J = 10.8, H-ben zyl); 7.16–7.37, 20 H (H-arom .). 13C NMR:
12.04, 18.65, 20.84, 23.41, 24.21, 26.38, 27.21, 27.38, 28.30, 29.42, 31.82, 34.67 (2C); 35.25,
35.57, 35.84, 40.19, 40.41, 42.16, 42.71, 56.19, 56.49, 63.62, 69.27, 73.39, 74.82, 74.87,
74.99, 75.69, 78.07, 80.20, 82.47, 84.82, 102.29, 127.50, 127.57, 127.61 (2C); 127.64,
127.74, 127.90 (2C); 127.99 (2C); 128.21 (2C); 128.30 (2C); 128.35 (4C); 128.38 (2C);
138.12, 138.33, 138.60, 138.65. MS (FAB, CHCl3), m/z: 907 (M + Na+), 885 (M + H+) 884
(M+). MS (ESI, MeOH): 907.8 (M + Na+), 923.6 (M + K+); MS2 (907.8) 875.4, 815.5, 667.6,
563.3, 472.3, 353.2, 323.1; MS3 (563.3) 455.2, 413.4, 323.1, 231.1, 203. For C58H76O7 (885.2)
calculated: 78.70% C, 8.65% H; foun d: 77.47% C, 8.56% H.
3α-(2,3,4,6-Tetra-O-ben zyl-β-D-glucopyran osyloxy)-5β-ch olan -24-al (12)
Alcoh ol 10 (2.1 g, 2.4 m m ol) was dissolved in dich lorom eth an e (6 m l, dry) an d pyridin ium
ch loroch rom ate (650 m g, 3 m m ol) was added. Th e m ixture was stirred un der argon an d th e
course of reaction was m on itored by TLC. After 4 h , dieth yl eth er (6 m l) was added. Th e
dark suspen sion was filtered th rough a silica gel colum n (100 g), th e colum n was furth er
wash ed out with a m ixture of dich lorom eth an e–dieth yl eth er (1:1), an d solven ts were evapo-
rated. Ch rom atograph y on a silica gel colum n (toluen e–eth yl acetate, 29:1) followed by crys-
tallization from dieth yl eth er gave crystallin e aldeh yde 12 (1.6 g, 76%) . M.p. 55–57 °C, [α]D
+20.7 (c 0.53, CHCl3). IR (CHCl3): ν(C=O): ≈1722 m ; ν(C–H) + 2β(HCO): visible bottom
ban d: 2726 w; βs(CH2): ≈1409 w, sh ; –OBn : ν(=C–H): 3089 w (20a), 3066 w (2), 3033 (20b);
ν(rin g): 1497 w (19a), 1453 m (19b); βs(CH2): 1362 m ; γs(CH2): 1332 w; arom atic: 1277 w
(13), 1029 m (18a), 913 w (17b), 699 s (4), 613 w (6b), 462 w (6a); νas(COC) + ν(rin g)
tetrah ydropyran : 1150 w, ≈1117 m , sh ; ≈1091 s, sh ; 1067 vs, 1004 m . 1H NMR: 0.65 s, 3 H
(H-18); 0.91 s, 3 H (H-19); 0.92 d, 3 H (J = 6.4, H-21); 0.80–2.50, 28 H (steroid fin gerprin t);
3.43 dd, 1 H (J1 = 9.2, J2 = 7.9, H-2′); 3.47 ddd, 1 H (J1 = 9.9, J2 = 5.2, J3 = 1.7, H-5′); 3.53 dd,
1 H (J1 = 9.8, J2 = 8.5, H-4′); 3.63 t, 1 H (J = 9.0, H-3′); 3.63 dd, 1 H (J1 = 10.7, J2 = 5.0,
H-6a′); 3.68 m , 1 H (H-3β); 3.74 dd, 1 H (J1 = 10.8, J2 = 1.8, H-6b′); 4.51 d, 1 H (J = 7.8,
H-1′); 4.54 d, 1 H (J = 10.8, H-ben zyl); 4.56 d, 1 H (J = 12.2, H-ben zyl); 4.60 d, 1 H (J = 12.2,
H-ben zyl); 4.72 d, 1 H (J = 11.0, H-ben zyl); 4.78 d, 1 H (J = 11.0, H-ben zyl); 4.82 d, 1 H (J =
10.8, H-ben zyl); 4.92 d, 1 H (J = 11.0, H-ben zyl); 4.99 d, 1 H (J = 10.8, H-ben zyl); 7.16–7.37,
20 H (H-arom .); 9.77 t, 1 H (J = 2.0, CHO). 13C NMR: 12.05, 18.38, 20.82, 23.40, 24.19,
26.35, 27.18, 27.40, 27.96, 28.24, 34.66 (2C); 35.24, 35.31, 35.82, 40.15, 40.39, 40.92, 42.14,
42.76, 55.99, 56.46, 69.27, 73.39, 74.82, 74.87, 74.99, 75.69, 78.07, 80.21, 82.47, 84.82,
102.32, 127.51, 127.58, 127.61 (2C); 127.64, 127.90 (2C); 127.99 (2C); 128.21 (2C); 128.30
(2C); 128.35 (4C); 128.38 (2C); 138.12, 138.33, 138.61, 138.64, 203.23. MS (FAB, CHCl3),
m/z: 883 (M + H+). MS (ESI, MeOH): 937.5 (M + MeOH + Na+), 905.5 (M + MeOH + K+),
905.5 (M + Na+), 921.3 (M + K+); MS2 (935.5) 905.5; MS3 (905.5) 563.2, 323.2. For C58H74O7
(883.2) calculated: 78.87% C, 8.45% H; foun d: 78.67% C, 8.37% H.
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

1156
Zelenka, Trnka, Tišlerová, Král, Dukh, Drašar:
5,10,15,20-Tetrakis[3α-(2,3,4,6-tetra-O-ben zyl-β-D-glucopyran osyloxy)-5β-ch olan -24-yl]-
porph yrin (14)
Pyrrole (34 m g, 0.5 m m ol) an d dry dieth yl eth er (30 m l) were added to a flask with a sep-
tum an d eth ylm agn esium brom ide (170 µl, 2.93 m ol l–1) was added dropwise un der argon .
Th e reaction m ixture was stirred for 20 m in an d th en th e solven t was evaporated. Th e resi-
due was dissolved in dich lorom eth an e (50 m l, dry) an d aldeh yde 12 (440 m g, 0.5 m m ol)
was added. Th is solution was stirred un der argon an d th e progress of th e reaction was m on i-
tored by TLC (eth yl acetate–h exan e, 2:1). After 3 days, wh en th e m ixture becam e dark, DDQ
(150 m g, 0.65 m m ol) was added, th e suspen sion was stirred for 2 h an d th en acetic acid
(2.5 m l) in water (20 m l) was added. Th e h eterogen eous m ixture was stirred for 15 m in an d
th en th e organ ic layer was separated. It was wash ed with a saturated solution of sodium
h ydrogen carbon ate (50 m l) an d water (2 × 50 m l), th en dried over an h ydrous MgSO4 an d
evaporated to dryn ess. Th e residue was dissolved an d ch rom atograph ed over a silica gel col-
um n (75 g) usin g a m ixture of eth yl acetate–h exan e (2:1), th e fraction con tain in g porph y-
rin s (after sprayin g TLC with acid, porph yrin becam e green ) was taken an d evaporated. Re-
peated ch rom atograph y on a silica gel colum n (50 g) in toluen e–dieth yl eth er (90:3, 2×) an d
on preparative TLC plates gave two colored fraction s.
Secon d fraction con tain ed 45 m g of red-brown am orph ous product 14 (9.5%). [α]D –0.4
(c 0.08, CHCl3). UV (CHCl3): λm ax 419 n m (log ε = 5.09). IR (CHCl3): ν(N–H): 3323 w;
pyrrole: ν(=C–H) 3109 vw; ν(C=C): 1567 w; ν(C=N): 1480 w, sh ; ν(C–H rockin g): 1004 m ,
≈966 m , sh ; –OBn : ν(=C–H): 3089 w (20a), 3066 w (2), 3030 m (20b); ν(rin g): 1606 w (8a),
1587 w (8b), 1497 m (19a), 1453 s (19b); arom atic + oth er ban ds: 1278 w (13), 1029 s (18a),
917
m (17b), 699 s (4), 615 w (6b), 461 w (6a); νs(CH2): 2867 s; βs(CH2): 1362 s
(+ ν(C–N)pyrrole); γs(CH2): 1336 w; νas(COC) + ν(rin g) tetrah ydropyran , arom atic 18b: 1150 s,
≈1117 s; ≈1088 s; 1067 vs; δs(CH3): 1376 m . 1H NMR: –2.61 bs, 2 H (2 × NH-pyrrole); 0.82 s,
12 H (4 × H-18); 0.97 s, 12 H (4 × H-19); 1.59 d, 12 H (J = 6.5, 4 × H-21); 0.80–2.75, 112 H
(4 × steroid fin gerprin t); 3.43 dd, 4 H (J1 = 9.1, J2 = 7.8, 4 × H-2′); 3.46 ddd, 4 H (J1 = 9.8,
J2 = 5.2, J3 = 1.8, 4 × H-5′); 3.51 dd, 4 H (J1 = 9.8, J2 = 8.6, 4 × H-4′); 3.62 dd, 4 H (J1 = 10.8,
J2 = 5.3, 4 × H-6a′); 3.63 t, 4 H (J = 8.7, 4 × H-3′); 3.70 tt, 4 H (ΣJ = 31.6, 4 × H-3β); 3.73 dd,
4 H (J1 = 10.8, J2 = 1.9, 4 × H-6b′); 4.52 d, 4 H (J = 7.6, 4 × H-1′); 4.52 d, 4 H (J = 11.4, 4 ×
H-ben zyl); 4.55 d, 4 H (J = 12.2, 4 × H-ben zyl); 4.59 d, 4 H (J = 12.2, 4 × H-ben zyl); 4.71 d,
4 H (J = 10.8, 4 × H-ben zyl); 4.77 d, 4 H (J = 10.9, 4 × H-ben zyl); 4.80 d, 4 H (J = 11.0, 4 ×
H-ben zyl); 4.91 d, 4 H (J = 11.0, 4 × H-ben zyl); 4.99 d, 4 H (J = 10.9, 4 × H-ben zyl);
7.16–7.36, 80 H (H-arom .); 9.44 bs, 8 H (8 × H-pyrrole). For C248H302N4O24 calculated exact
m ass: 3720.25, m .w.: 3723.06, m/z: 3722.26 (100.0%), 3723.26 (90.6%), 3721.26 (72.7%),
3724.27 (60.0%), 3725.27 (36.6%), 3720.25 (26.7%), 3726.27 (16.8%), 3724.26 (6.1%),
3727.28 (5.5%), 3723.27 (3.3%), 3728.28 (2.4%), 3727.27 (1.8%), 3722.25 (1.1%), 3726.28
(1.0%); foun d MS (MALDI, CHCl3), m/z: 3723.
Meth yl 3α-(2,3,4,6-Tetra-O-acetyl-β-D-galactopyran osyloxy)-5β-ch olan -24-oate (5)
Com poun d 5 was syn th esized in th e sam e way as 4 from m eth yl lith och olate 3 (10 g, 25.6
m m ol) an d acetobrom ogalactose 2 (20 g, 48.6 m m ol), an d m ercuric cyan ide (12.27 g, 48.6
m m ol). Th e preparation gave th e solid product 5 (10 g, 54%). M.p. 74–76 °C, [α]D +20
(c 0.5, CHCl3). 1H NMR: 0.63 s, 3 H (H-18); 0.91 s, 3 H (H-19); 0.91 d, 3 H (J = 6.4, H-21);
1.98 s, 3 H; 2.04 s, 3 H; 2.06 s, 3 H; 2.15 s, 3 H (4 × OAc); 0.90–2.40, 28 H (steroid fin ger-
prin t); 3.56 tt, 1 H (ΣJ = 31.7, H-3β); 3.67 s, 3 H (COOCH3); 3.89 td, 1 H (J1 = 6.8, J2 = 1.2,
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

Porphyrin Receptors Modified by Glycosylated Steroids
1157
H-5′); 4.11 dd, 1 H (J1 = 11.1, J2 = 7.0, H-6a′); 4.20 dd, 1 H (J1 = 11.3, J2 = 6.6, H-6b′); 4.54 d,
1 H (J = 7.9, H-1′); 5.01 dd, 1 H (J1 = 10.5, J2 = 3.5, H-3′); 5.18 dd, 1 H (J1 = 10.5, J2 = 7.9,
H-2′); 5.38 dd, 1 H (J1 = 3.4, J2 = 1.1, H-4′). 13C NMR: 12.00, 18.24, 20.60, 20.66, 20.68,
20.82 (2C); 23.35, 24.16, 26.25, 27.20, 27.31, 28.15, 30.98, 31.06, 34.34, 34.63, 35.16, 35.35,
35.81, 40.10, 40.25, 42.19, 42.70, 51.46, 55.89, 56.30, 61.35, 67.04, 69.17, 70.48, 71.01,
81.25, 100.66, 169.42, 170.22, 170.33, 170.40, 174.76. MS (FAB, CHCl3), m/z: 720 (M+).
MS (ESI, MeOH): 743.7 (M + Na+), 759.5 (M + K+); MS2 (743.7) 683.6, 581.4, 371.2, 311.2;
MS3 (683.6) 641.5, 623.4, 581.1, 521.1, 413.2, 311.1, 251.1, 227.1. For C39H60O12 (720.9)
calculated: 64.98% C, 8.39% H; foun d: 64.94% C, 8.53% H.
Meth yl 3α-(β-D-Galactopyran osyloxy)-5β-ch olan -24-oate (7)
Com poun d 7 was syn th esized as 6 from protected galactoside 5 (9.5 g, 13.2 m m ol) an d
sodium m eth oxide in m eth an ol (10 m m ol, 10 m l). Th e residue was recrystallized from
m eth an ol to obtain 7 (5.8 g, 79.5%). M.p. 211–213 °C, [α]D +22 (c 0.5, MeOH). 1H NMR
(MeOH-d4, 45 °C): 0.65 s, 3 H (H-18); 0.91 d, 3 H (J = 6.4, H-21); 0.92 s, 3 H (H-19);
0.90–2.40, 28 H (steroid fin gerprin t); 2.40 bs, 1 H (OH); 2.70 bs, 1 H (OH); 3.10 bs, 2 H (2 ×
OH); 3.54 ddd, 1 H (J1 = 6.1, J2 = 4.9, J3 = 1.2, H-5′); 3.58–3.64, 2 H (H-2′, H-3′); 3.66 s, 3 H
(COOCH3); 3.69 tt, 1 H (ΣJ = 31.4, H-3β); 3.86 dd, 1 H (J1 = 11.8, J2 = 5.0, H-6a′); 3.93 dd,
1 H (J1 = 11.7, J2 = 6.0, H-6b′); 4.01 dd, 1 H (J1 = 2.9, J2 = 1.2, H-4′); 4.37 d, 1 H (J = 7.5,
H-1′). 13C NMR (45 °C): 12.06, 18.32, 20.91, 23.36, 24.23, 26.42, 27.10, 27.25, 28.17, 31.09,
31.16, 34.44, 34.78, 35.23, 35.38, 35.93, 40.23, 40.52, 42.30, 42.82, 51.38, 56.12, 56.54,
62.59, 69.50, 71.97, 73.64, 74.34, 79.37, 101.22, 174.67. MS (FAB, MeOH), m/z: 553 (M +
H+). MS (ESI, MeOH): 575.5 (M + Na+), 591.3 (M + K+); MS2 (575.5) 405.8, 355.2, 313.6, 203.
For C31H52O8 (552.7) calculated: 67.36% C, 9.48% H; foun d: 66.65% C, 9.57% H.
Meth yl 3α-(2,3,4,6-Tetra-O-ben zyl-β-D-galactopyran osyloxy)-5β-ch olan -24-oate (9)
Com poun d 9 was syn th esized as 8 from 7 (5.5 g, 10 m m ol) in toluen e (200 m l, dry), fresh ly
powdered potassium h ydroxide (2.9 g, 52 m m ol), ben zyl brom ide (6.2 m l, 52 m m ol) an d
tetrabutylam m on ium iodide (3.7 g, 10 m m ol). After ch rom atograph y on a silica gel colum n
(toluen e–eth yl acetate, 29:1), pure product 9 (4 g, 43%) was obtain ed as a syrup. [α]D +11.4
(c 0.52, CHCl3). 1H NMR: 0.64 s, 3 H (H-18); 0.89 s, 3 H (H-19); 0.92 d, 3 H (J = 6.4, H-21);
0.85–2.46, 28 H (steroid fin gerprin t); 3.47–3.69, 5 H (H-3′, H-5′, H-6a′, H-6b′, H-3β); 3.66 s,
3 H (COOCH3); 3.80 dd, 1 H (J1 = 9.8, J2 = 7.6, H-2′); 3.86 bd, 1 H (J = 2.4, H-4′); 4.41 d, 1 H
(J = 11.8, H-ben zyl); 4.45 d, 1 H (J = 11.8, H-ben zyl); 4.46 d, 1 H (J = 7.8, H-1′); 4.61 d, 1 H
(J = 11.8, H-ben zyl); 4.70 d, 1 H (J = 11.8, H-ben zyl); 4.75 d, 2 H (J = 11.3, 2 × H-ben zyl);
4.93 d, 1 H (J = 11.6, H-ben zyl); 4.95 d, 1 H (J = 10.8, H-ben zyl); 7.23–7.39, 20 H (H-arom .).
13C NMR: 12.01, 18.26, 20.80, 23.38, 24.17, 26.33, 27.18, 27.27, 28.15, 31.03, 31.27, 34.50,
34.65, 35.28, 35.34, 35.80, 40.15, 40.35, 42.13, 42.71, 51.44, 55.93, 56.43, 69.16, 73.06,
73.40, 73.50, 73.61, 74.38, 75.19, 79.75, 79.92, 82.36, 102.48, 127.43, 127.48 (2C); 127.50
(2C); 127.69, 127.77 (2C); 128.08 (2C); 128.19 (2C); 128.22 (2C); 128.30 (4C); 128.36 (2C);
138.01, 138.61, 138.71, 138.89, 174.76. MS (FAB, CHCl3), m/z: 913 (M+). MS (ESI, MeOH):
935.7 (M + Na+); MS2 (935.7) 805.6, 563.4, 471.4, 324.2; MS3 (563.3) 455.1, 413.1, 323.1. For
C
59H76O8 (913.2) calculated: 77.6% C, 8.39% H; foun d: 77.76% C, 8.43% H.
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

1158
Zelenka, Trnka, Tišlerová, Král, Dukh, Drašar:
3α-(2,3,4,6-Tetra-O-ben zyl-β-D-galactopyran osyloxy)-5β-ch olan -24-ol (11)
Com poun d 11 was syn th esized as 10 from m eth yl ester 9 (3.5 g, 3.8 m m ol) an d lith ium alu-
m in um h ydride (290 m g, 7.6 m m ol). Product 11 (3 g, 89%) was obtain ed as a syrup. [α]D
+14.5 (c 0.55, CHCl3). 1H NMR: 0.64 s, 3 H (H-18); 0.90 s, 3 H (H-19); 0.93 d, 3 H (J = 6.4,
H-21); 0.85–2.00, 28 H (steroid fin gerprin t); 3.47–3.69, 7 H (CH2OH, H-3′, H-5′, H-6a′, H-6b′,
H-3β); 3.80 dd, 1 H (J1 = 9.8, J2 = 7.7, H-2′); 3.86 bd, 1 H (J = 2.5, H-4′); 4.41 d, 1 H (J = 11.8,
H-ben zyl); 4.45 d, 1 H (J = 11.7, H-ben zyl); 4.46 d, 1 H (J = 7.7, H-1′); 4.61 d, 1 H (J = 11.8,
H-ben zyl); 4.70 d, 1 H (J = 11.8, H-ben zyl); 4.75 d, 2 H (J = 10.6, 2 × H-ben zyl); 4.93 d, 1 H
(J = 11.7, H-ben zyl); 4.95 d, 1 H (J = 10.8, H-ben zyl); 7.24–7.39, 20 H (H-arom .). 13C NMR:
12.03, 18.65, 20.82, 23.39, 24.20, 26.36, 27.20, 27.27, 28.30, 29.43, 31.81, 34.52, 34.67,
35.27, 35.57, 35.82, 40.19, 40.38, 42.15, 42.69, 56.18, 56.48, 63.62, 69.17, 73.07, 73.41,
73.51, 73.62, 74.40, 75.21, 79.76, 79.94, 82.37, 102.48, 127.45, 127.50 (4C); 127.71, 127.79
(2C); 128.10 (2C); 128.22 (2C); 128.25 (2C); 128.32 (4C); 128.38 (2C); 138.02, 138.61,
138.71, 138.89. MS (FAB, CHCl3), m/z: 907 (M + Na+), 885 (M + H+). MS (ESI, MeOH): 907.8
(M + Na+), 923.6 (M + K+); MS2 (907.8) 815.6, 563.5; MS3 (563.3) 455.2, 413.2, 365.1, 323.1,
203. For C58H76O7 (885.2) calculated: 78.69% C, 8.65% H; foun d: 78.65% C, 8.57% H.
3α-(2,3,4,6-Tetra-O-ben zyl-β-D-galactopyran osyloxy)-5β-ch olan -24-al (13)
Com poun d 13 was syn th esized as given for 12 from alcoh ol 11 (2.8 g, 3.1 m m ol) an d
pyridin ium ch loroch rom ate (870 m g, 4 m m ol). Ch rom atograph y on a silica gel colum n
(toluen e–eth yl acetate, 29:1) gave syrup aldeh yde 13 (2.2 g, 80%). [α]D +11.2 (c 0.49,
CHCl3). IR (CHCl3): ν(C=O): 1722 m ; ν(C–H) + 2β(HCO): visible on ly bottom ban d of dou-
blet: 2726 w; βs(CH2): ≈1410 w, sh ; –OBn : ν(=C–H): 3089 w (20a), 3066 w (2), 3033 m (20b);
ν(rin g): 1606 vw (8a), 1586 vw (8b), 1497 m (19a), 1454 s (19b); βs(CH2): 1363 s; arom atic:
1288 w (13), 1028 s (18a), 912 w (17b), 699 s (4), 612 w (6b), 465 w (6a); νas(COC) + ν(rin g)
tetrah ydropyran : 1158 m , 1134 m , 1093 vs, 1073 vvs , 1043 s, 1004 m . 1H NMR: 0.64 s, 3 H
(H-18); 0.90 s, 3 H (H-19); 0.92 d, 3 H (J = 6.4, H-21); 0.80–2.50, 28 H (steroid fin gerprin t);
3.45–3.62, 4 H (H-3′, H-5′, H-6a′, H-6b′); 3.64 tt, 1 H (ΣJ = 32.0, H-3β); 3.80 dd, 1 H (J1 = 9.8,
J2 = 7.6, H-2′); 3.86 bd, 1 H (J = 2.6, H-4′); 4.41 d, 1 H (J = 11.8, H-ben zyl); 4.45 d, 1 H (J =
11.7, H-ben zyl); 4.45 d, 1 H (J = 7.8, H-1′); 4.61 d, 1 H (J = 11.6, H-ben zyl); 4.70 d, 1 H (J =
11.8, H-ben zyl); 4.75 d, 2 H (J = 11.6, 2 × H-ben zyl); 4.93 d, 1 H (J = 11.8, H-ben zyl); 4.95 d,
1 H (J = 10.8, H-ben zyl); 7.20–7.40, 20 H (H-arom .); 9.76 t, 1 H (J = 1.8, CHO). 13C NMR:
12.03, 18.37, 20.79, 23.37, 24.17, 26.33, 27.16, 27.28, 27.94, 28.23, 34.50, 34.65, 35.25,
35.29, 35.80, 40.14, 40.35, 40.89, 42.12, 42.73, 55.95, 56.43, 69.17, 73.06, 73.40, 73.50,
73.61, 74.39, 75.19, 79.75, 79.95, 82.36, 102.51, 127.44, 127.50 (4C); 127.70, 127.78 (2C);
128.10 (2C); 128.20 (2C); 128.23 (2C); 128.31 (4C); 128.37 (2C); 138.01, 138.60, 138.71,
138.90, 203.21. MS (FAB, CHCl3), m/z: 883 (M + H+). MS (ESI, MeCN): 905.6 (M + Na+),
921.4 (M + K+); MS2 (905.6) 813.2, 563.3. For C58H74O7 (883.2) calculated: 78.87% C, 8.45% H;
foun d: 78.92% C, 8.67% H.
15,10,15,20-Tetrakis-[3α-(2,3,4,6-tetra-O-ben zyl-β-D-galactopyran osyloxy)-5-ch olan -24-yl]-
porph yrin (15)
Th e porph yrin 15 was syn th esize as 14 from pyrrole (34 m g, 0.5 m m ol), eth ylm agn esium
brom ide (170 µl, 2.93 m ol l–1), aldeh yde 13 (440 m g, 0.5 m m ol) an d DDQ (150 m g, 0.65
m m ol). Th e residue was dissolved an d ch rom atograph ed over a silica gel (75 g) with a m ix-
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

Porphyrin Receptors Modified by Glycosylated Steroids
1159
ture of eth yl acetate–h exan e (2:1), th e fraction con tain in g porph yrin (after sprayin g TLC
with acid, porph yrin becam e green ) was taken an d evaporated. Next purification by ch rom a-
tograph y on a silica gel colum n (50 g) in toluen e–dieth yl eth er (90:3, 2×) an d on preparative
TLC plates gave two colored fraction s.
Secon d fraction con tain ed 30 m g of red-brown am orph ous product 15 (6.3%). [α]D –3
(c 0.05, CHCl3). UV (CHCl3): λm ax 419 n m (log ε = 5.47). IR (CHCl3): ν(N–H): 3323 w;
pyrrole: ν(=C–H) 3109 vw; ν(C=C): 1567 w; ν(C=N): ≈1480 m , sh ; ν(C–H rockin g): 1004 m ,
≈966 w; –OBn : ν(=C–H): 3089 w (20a), 3066 m (2); ν(rin g): 1606 w (8a), 1585 w (8b), 1497 m
(19a), 1454 s (19b); arom atic + oth er ban ds: 1028 s (18b), 917 m (17b), 699 s (4), 613 w
(6b), 464 w (6a); νs(CH2): 2866 s; βs(CH2): 1363 s (+ ν(C–N)pyrrole); νas(COC) + ν(rin g)
tetrah ydropyran , arom atic 18b: 1163 s, 1135 s; 1093 vs; 1074 vs, 1043 vs; δs(CH3): 1376 m .
1H NMR: –2.61 bs, 2 H (2 × NH-pyrrole); 0.82 s, 12 H (4 × H-18); 0.95 s, 12 H (4 × H-19);
1.60 d, 12 H (J = 6.5, 4 × H-21); 0.80–2.70, 112 H (4 × steroid fin gerprin t); 3.48–3.60, 16 H
(4 × (H-3′, H-5′, H-6a′, H-6b′)); 3.67 tt, 4 H (ΣJ = 32.0, 4 × H-3β); 3.79 dd, 4 H (J1 = 9.7, J2
=
7.7, 4 × H-2′); 3.85 dd, 4 H (J1 = 3.0, J2 = 0.9, 4 × H-4′); 4.40 d, 4 H (J = 11.8, 4 × H-ben zyl);
4.44 d, 4 H (J = 11.7, 4 × H-ben zyl); 4.47 d, 4 H (J = 7.7, 4 × H-1′); 4.59 d, 4 H (J = 11.8, 4 ×
H-ben zyl); 4.67 d, 4 H (J = 11.9, 4 × H-ben zyl); 4.74 d, 8 H (J = 11.6, 8 × H-ben zyl); 4.91 d,
4 H (J = 11.7, 4 × H-ben zyl); 4.96 d, 4 H (J = 10.7, 4 × H-ben zyl); 7.18–7.38, 80 H (H-arom .);
9.45 bs, 8 H (8 × H-pyrrole). For C248H302N4O24 calculated exact m ass: 3720.25, m .w.:
3723.06, m/z: 3722.26 (100.0%), 3723.26 (90.6%), 3721.26 (72.7%), 3724.27 (60.0%),
3725.27 (36.6%), 3720.25 (26,7%), 3726.27 (16.8%), 3724.26 (6.1%), 3727.28 (5.5%),
3723.27 (3.3%), 3728.28 (2.4%), 3727.27 (1,8%), 3722.25 (1.1%), 3726.28 (1.0%); foun d MS
(MALDI, CHCl3), m/z: 3723.
This work was supported by the Ministry of Education, Youth and Sports of the Czech Republic,
projects No. 1131 00001 (T. Trnka), No. 2233 00006 (P. Drašar), OCD 31 (M. Dukh), grant No.
FRVS 2796 (K. Zelenka), and it was a part of project Z4 055 905 (V. Král).
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