JPS6341502A - Complex polysaccharide and production thereof - Google Patents

Abstract

PURPOSE:To obtain a novel complex polysaccharide useful as an intermediate for synthesizing glycoprotein of cell cortex or as a reagent for elucidating biological significance and function of the glycoprotein, by reacting specific two compounds in the presence of a glycosylation catalyst. CONSTITUTION:A compound shown by formula I (Ac is acetyl; R is lower alkyl) is reacted with a compound shown by formula II (Bn is benzyl; Phth is phthaloyl) in the presence of a glycosylation catalyst (e.g. TiCl4), SnCl4, molecular sieve 4A, etc.) in a solvent preferably dichloroethane, benzene, etc., -25-60 deg.C, and if necessary, deacetylated, debenzylated, dephthaloylated and acetylated to give a novel compound shown by formula III (R is H or lower alkyl; R<1> is H or acetyl; R<2> is H or benzyl; R<3> is H; R<4> is acetyl or R<3> and F<4> form phthaloyl; Y is H, etc.).

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a novel complex polysaccharide and a method for producing the same.

[Background of the invention]

Glycoproteins on the cell surface exist with sugar chains oriented outward,
It functions as a biological information marker.

Among the sugar chains of glycoproteins, sugar chains that are N-glycoside bonded to protein moieties have the most complex structure, and various branch structures are known to date.

The present inventors have developed a complex type Il! with triple division technique! The hexasaccharide unit of the chain has been successfully synthesized. (Ogawa et al., Carbohydrate Res)
, 93 (1981) CI). The present inventors further conducted research with the aim of synthesizing the 9vM unit structure (1) of a complex type sugar chain having a double division technique as shown in Showa 6 (see Publication No. 151702).

The present inventors further discovered that Asn-37 of calf blood coagulation factor
We conducted research aimed at the total synthesis of the 11-saccharide unit structure (IT) shown in (3), which is similar to I, and which is bonded to Asn-261 of factor (6) and factor (2), leading to the completion of the present invention.

■ Formula 1. In TI, SA represents a sialic acid residue, Ga1l represents a galactose residue, GN represents a glucosamine residue, and M represents a mannose residue.

[Structure of the invention]

The present invention provides a complex polysaccharide represented by the following general formula and a method for producing the same.

In the formula, R is a hydrogen atom or a lower alkyl group, R1 is a hydrogen atom or an acetyl group, R2 is a hydrogen atom or a benzyl group, R3 is a hydrogen atom, R4 is an acetyl group, or R'' and R
4 together represent a phthaloyl group, and Y represents a hydrogen atom or (in the formula, R and R1 are as defined above).

The above compound is a compound represented by the formula (1): (wherein, Ac is an acetyl group and R is a lower alkyl group) and a compound represented by the formula (2): (wherein, Bn is a benzyl group, and Ph th is a phthaloyl group). It can be produced by reacting a compound represented by (representing a group) in the presence of a glycosylation catalyst, and optionally deacetylating, debenzylating, defthaloylating and acetylating.

First, the starting material compound (1) for the method of the present invention can be synthesized as follows.

The compound (101) represented by the following formula (101) is mixed with CH30Na, K2CO2, Na in a solvent such as methanol or ethanol.
, CO2, in the presence of a base catalyst such as triethylamine, -
Deacetylation is performed by reacting at 5°C to 60°C for 30 minutes to 24 hours to obtain compound (102).

Compound (102) was mixed with toluenesulfonic acid (TsOH), Zn in a solvent such as DMF, acetone, and DMF-acetone.
Cj! z, BF3. In the presence of a catalyst such as EtzO, dimethoxypropane is reacted at 0°C to 80°C for 30 minutes to 24 hours to obtain a 4,6-di-O-isopropylidene compound, which is further reacted with pyridine, triethylamine, dimethylaminopyridine, etc. In the presence of a base catalyst, acetic anhydride and 0°C ~
The acetyl form (10
3) is obtained.

Compound (103) was dissolved in Ac0H1CF 3 COO in methanol, ethanol, or a mixed solvent of these and water.
20 minutes to 2 at 0℃ to 80℃ using H(TFA) etc.
The isopropylidene group is removed by treatment for 4 hours to obtain diol (104).

Diol (104), molecular sieve 4A, Hg
Brz-Hg (CN)z, 8go S OzCF 3
, heg-silicate, 8g2CO3, AgCAO4, etc. in the presence of a glycosylation catalyst, the compound represented by formula (120): is reacted to form a tetrasaccharide compound (105)
(α form) and (106) (β form) are obtained. Suitable solvents include dichloroethane, dichloromethane, toluene, nitromethane, benzene, CH3CN, DMF, etc., and the reaction proceeds satisfactorily at -15°C to 60°C for 30 minutes to 24 hours.

Compound (105) was acetylated by a conventional method to obtain compound (
107) is obtained. This compound (107) was converted into AcOH-H
PdCIlz, PdCI2, (Cb
Hs) :+P RhCA! (Wilkinson complex)
Compound (108) is obtained by treatment at room temperature to 80° C. for 1 hour to 24 hours in the presence of a catalyst such as .

Compound (108) in MeOH-AcOH, MeOH.

10% Pd-C, 5% Pd in a solvent such as MeOHHgO
In the presence of a catalyst such as C, Pd (OH)z, pto2,
After removing the benzyl group by hydrogen catalytic reduction at room temperature to 60°C for 1 to 24 hours, acetylation was performed by a conventional method.
Compound (109) is obtained.

Compound (109), DMF, CHtCt2z,
Melts into CA CHzCHzCA etc., NHzNHz・A
Selective deacetylation is performed by treatment at 20° C. to 80° C. for 5 minutes to 3 hours in the presence of cOH to obtain compound (110).

Compound (110) in CHzCA z , CI CHzC
Izc6, dissolved in toluene, benzene, etc., DBtJ
(diazabicycloundecane), trichloroacetonitrile in the presence of a catalyst such as Na1 (-20°C to 40°C)
By reacting at C for 30 minutes to 6 hours, the starting material (
Get 11.

The other starting material (2) is JP-A-60-51702
It can be synthesized according to the method described in the publication.

Compound (1) and compound (2) thus obtained were reacted in the presence of a glycosylation catalyst, and 7! J! sexual compound (3
) and IIIJi compound (7) are obtained. Glycosylation catalysts include BF, ・Et2o, TMS) reflate,
TiCj! , , 5nC14, molecular sieve 4A
.

Molecular sieve AW-300 etc. can be used. Suitable solvents include dichloroethane, dichloromethane, chloroform, toluene, benzene, nitromethane, etc., and the temperature is suitably between -25°C and 60°C.

Compound (3) or (7) is treated in a solvent such as pyridine, collidine, or piacolin in the presence of a Lil catalyst at a temperature of 60°C to reflux for 1 to 12 hours to hydrolyze the ester, resulting in compound (4), respectively. ) or (8) is obtained.

Next, compound (4) or (8) was added to EtOH, MeOH
in the presence of a catalyst such as hydrazine hydrate, n-butylamine, alkyl amines such as methylamine, etc.
Treatment at °C to reflux temperature for 1 to 24 hours removes phthaloyl and acetyl groups, followed by MeOH, EtO
Acetic anhydride is added in a solvent such as H1 water, and the mixture is treated at 0° C. to room temperature for 1 hour to 24 hours to acetylate the amino group to obtain compound (5) or (9), respectively.

Compound (5) or (9) is prepared by a conventional method, for example, 10
% Pd-C, the Hensyl group is removed by hydrogen catalytic reduction to obtain the target compound (6) or 00), respectively.

An example of the above process is shown in the following schemes 1.2.3 and 4.

〉=≠ = Special opening UG3-41502 (13) AcNeuα2
-6Gallβ1-4 G j! cNAcβ8cNe
to α2−6Ga1β 1→4 G j! In cNAcβ schemes 1.2.3 and 4, ← represents a 〇-acetyl group, and - represents a ○ to benzyl group, respectively.

Compounds (102) and (103) obtained by the above steps
), (104), (105), (106), (1
07), (108), (109), (110),
ftl, (3), (4), (5), (6), (7), (
8), (9) and 00) are new compounds.

〔Usefulness〕

The above novel compounds obtained by the present invention are useful as intermediates in the synthesis of cell surface glycoproteins and as reagents in elucidating the biological significance and functions of cell surface glycoproteins. It is.

The present invention will be explained in more detail with reference to Examples below, but these are not intended to limit the scope of the present invention in any way.

In addition, in the following examples and reference examples, unless otherwise specified, the optical rotation [α] is measured at 25°C in CH (1,
I went there.

Reference Example 1 Compound (101) 650mg (0.59mmo7
Dissolve the solution in methanol, add Na OCHs, and stir at room temperature overnight. Neutralize the reaction solution with Amberlyst 15,
Filter and concentrate under reduced pressure. Compound (102) 435
mg (86%).

[Properties of compound (102)] Rf O,31CIC1,a:MeOH3:INMR
(CD30D) 7.53-7.01 m, 15B,
Benzyl x 3゜6.17-5.69 m, LH, -
CH=CH2゜1.93 131+, S, -NCO
CH3° Reference Example 2 Compound (102) 4.0 g (4,67mmo#)
DMF80mj! 5. Dissolve dimethoxypropane in water and stir at 0°C. Omj2TSOH-HzO160m
g and stirred for 4 hours. Triethylamine 1 in the reaction solution
0rr+j! Add and concentrate under reduced pressure. 80% pyridine in the residue
Add mβ acetic anhydride 3 Q m It and stir overnight.

Concentrate the reaction solution and transfer the residue to a silica gel column (400g>
Compound (103) 2;
50 g (50% yield) are obtained.

[Properties of compound (103)] 17f 0.35 1-luene-ethyl acetate 1:3
Elemental analysis Cs5H6eNOz. Calculated value as C, 6
2,08,H,6,54,N,1.32 actual measurement value C,6
1,84,H,6,6L N, 1.41 [α) o
+20.8” C=0.93 CHC13 Reference Example 3 Compound (103) 2.49 g (2.34 mmoj
MeOH-AcOH1: 1 40mj! and stir at 70-75°C for 1 hour and 45 minutes. The reaction solution was concentrated under reduced pressure, and the residue was applied to a silica gel column (SiOz C-300200g C) (C4!2
-MeOH 20:1). Compound (104) 1
．． 48 g (yield 61%) are obtained.

[Properties of compound (104)] Rf Q, 33 CHCes YIeOH9:
Single element analysis C7゜Hs lN Calculated value as OIb
C,? 1.09. H, 6,71, N, 1.15 actual measurement value C, 70,76, H, 6,73, N, 1.13 [α)
n'+20. OoC=1.26
C) I(1゜NMRCDIts 90MHz
ppm 7MS7.48-7.04.35H,m, benzyl group x 76.08-5.54m, LH,-
CH=CH2゜1.66 s 3HNAc Reference Example 4 Activated M, 3.4A, 7.0g and h(CN)zl,
85 g and 1.32 g of HgBrz were added to form the compound (
104) 1.25 g (1.22 mmo/), Compound (120) 622.3 mg 1.22 mmo7
! 20mj of dichloroethane! and stirred at -15°C under an argon atmosphere. The reaction solution was returned to room temperature and stirred for 8 hours.

The reaction solution was cooled again to -15°C, and compound (120) 63
0 mg (as a 7 mA dichloroethane solution) was added, the mixture was allowed to return to room temperature, and then stirred day and night.

Add 2616 mg of Hg (CN) to the reaction solution at -15°C.

HgBr, 440mg, compound (120) 630
g (as a 4 ml dichloroethane solution). −
After stirring day and night, the mixture is filtered, and the filtrate is washed with distilled water and saturated deuterated water, dried over MgSO3, and concentrated under reduced pressure. The residue was filtered through a silica gel column (Wakogel C-300 300g,
, CH2C7!2-7Seto730: 1) Te purification. Compound (105) (932 mg, yield 51%)
and compound (106) (673 mg, yield 37%
).

[Properties of compound (105) (α form)] Elemental analysis C7
zHzzNzOsz ・Calculated value assuming 2HzO C, 5
6,39,H, 6,05,N, 1.83 actual measurement value C,5
6,21,H, 6,05,N, 1.83NMR400M
Hz CDCj23 7.38-7.17.15H, m, benzyl group x 35.
92-5.82 1H,m, -CH=CH23,82
7,3) I, s, 0CH32,587dd, J=
4.4.12.6 H-3deq, 2.160°2
．． 134.2.079.2.067, 2.053.2.
048°2.037.2.000. 1.89L,
1.831 -COCI(3x [Compound (106)
(Properties of β-form) Elemental analysis C7□Hz z N 20
Calculated value as 3□・H20 C, 57, 06, H, 6,
12, N, 1.85 actual measurement C, 56, 78, H, 6,
24, N, 1.87Rf O, 56CHCj! 3Me
OH9: 1 [α)D'+2.1" C=1.0
2 CH (13NMR400MHz CDC13 7,38-7,19,15H,m, benzyl group x 35.
91-5.81 LH,m, -C)l-cI+23
．． 831,3H,s, 0CHz 2.476 dd, J=12.8.4.9 H-3
deq, 2.156°2.121.2.078.2.
078.2.054.2.034゜2.029.2.0
14.2.007.1.895.1.789 5-CO
Shore b10 Reference example 5 Compound (105) 1.07 g (0,715 mm
o#) with 20 mj of pyridine! , dissolved in 5 ml of acetic anhydride, and stirred at room temperature overnight. Concentrate under reduced pressure and transfer the residue to a silica gel column (Wakogel C300700gCHCn3:
Purify with MeOH30:1). Chemicals (107)
920 mg (91% yield) is obtained.

[Properties of compound (10T)] Rf O,50 (CHCj!z MeOH30:
1) [α) , -11,4° C=0.88
CHCffi:+Elemental analysis C74Hq 4 N 20
s a・1%H20 calculation value C, 56, 73, H, 6
,24,N,1.79 actual measurement value C,56,74,H,6
,OL N, 1.71NMR400MHz CD
Cit 3 7MS7.38-7.17.15m, benzyl group x 35.92-5.83 1FI m-
(!=CHz3.81L 3H,s, OCH3,2,
551dd, J=4.6;12.9 H-3deq 2.191.2.148.2.132.2.076, 2
．． 057°2.047.2.026.1.999.1.
957.1.894゜1.834 -COCHs x
11 Reference Example 6 Compound (107) 353 mg (0,229 mmo
β) was dissolved in AcOHHzO (95:5), 15 mA, 48 mg of palladium chloride and 46 mg of sodium acetate were added, and the mixture was stirred for 12 hours. The reaction solution was concentrated under reduced pressure, the residue was diluted with ethyl acetate, and insoluble matter was filtered through Celite.

The filtrate is washed with water, dehydrated water, and brine, and dried over Mg5Oa. Concentrate under reduced pressure and purify the residue using a silica gel column.

Elution with CHCAa:MeOH 10:1 gave 121 mg (35%) of compound (108).

[Properties of compound (107)] Rf O,35Men)(CHCj!a 1 :
9 elemental analysis CHI HqoNzCL+x ・1'A
Calculated value as HzO C, 55, 86, H, 6, 14
, N, 1.84 actual measurement value C, 55,80, H, 5,99
, N, 1.75 (α) D-19,8° C=0.61
C) (Cβ3NMR400MHz CD CI!
, s 7MS7.38-7.17 15) l, m
, benzyl group x 33.814 3Hs OCH32,
550dd, J=4.4゜12.7 H-3deq 2.196.2.14L 2.124.2.073.2
．． 060°2.051.2. C23,2,012,1,
960,1,894°1.851 -COCH,x 1
1 Reference Example 7 Compound (108) 391mg (0.26mmoj
20mn of methanol, 8cOH2mj! To? Add 200 mg of 10% Pd-C to a vessel and catalytically reduce the mixture under a hydrogen atmosphere day and night. After filtering and concentrating under reduced pressure, the residue was diluted with pyridine 5
ml and 2.5 ml of acetic anhydride, and stirred at room temperature for 3 hours.

Concentrate under reduced pressure and transfer the residue to a silica gel column (Wakogel C-
30,040 g Hexane-ethyl acetate 1:20) to obtain 284 mg of compound (109) (yield: 83
%).

[Properties of compound (109)] [α), -25,4° C=0.86 CH
(J!3Rf O, CHC4 containing 174% methanol
Three element analysis C5eHaoOa7Nz ・1'AHzO
Calculated value as C, 48, 91, H, 5, 87, N, 1
．． 97 actual measurement value C, 48, 98, H, 5, 6B, N
, 1.94 Reference Example 8 Compound (109) 263 mg (0,188 mmo
D M F 3.0 m j! To? Add 18 mg of hydrazinium acetate to the mixture and stir at room temperature for 40 minutes. The reaction solution was diluted with ethyl acetate, washed with water, further washed with saturated saline, and then dried over Mg5O. Concentrate under reduced pressure and purify the residue using silica gel column chromatography.

Silica gel (Wako gel c-30030g) CHCn3
:MeOH24:1, the starting material compound (1
09) 39 mg was recovered. Further elution yielded 215 mg of compound (110) (yield 91%)
I got it.

[Properties of compound (110)] (α) n −31,02° C=1. ICHC
A 3-element analysis C, 6H780,. Calculated value as Nz HtO C, 48, 9B, H, 5, 87, N, 2
．． 03 actual measurement value C, 49, 02, H, 5, 70, N, 1
．． 89Rf O, 43CHCj! :+ :MeOH
9: 1 Reference Example 9 Compound (110) 201 mg (0,148 mmo
Dissolve A) in 3.0 mn of dichloroethane, add 0.3 ml of trichloroacetonitrile, 22.3 μA of DBU
was added and stirred at 0°C for 30 minutes and at room temperature for 1 hour.
Purify with Ac). 188 mg (yield 84.7%) of compound (1) was obtained.

[Properties of compound (1)] [α)n −19,3° (C=1.55 CH
Cjl! 3) Rf O, 20EtOAc Elemental analysis Calculated value as C65H7sO3bNsCfls C, 46, 45, H, 5, 24, N, 2.80 Actual value C, 46, 35, H, 5, 06, N, 2.81 Example 1 Activated Molecular Sheep AW-300 300mg
compound (2189 mg (0,064 mmol))
, Compound (1) 74mg (0,049mmo6)
was dissolved in 7.0 m 12 of dichloroethane and added, and while stirring at -10°C under an argon atmosphere, BF3.pt2 was added.
o6.5μ! (0,052 mmol) was added and stirred for 2 hours.

The reaction solution is filtered through Celite, and the filtrate is washed with deuterated water and distilled water. After drying with MgSO4, it is concentrated under reduced pressure, and the residue is purified with a silica gel column. Compound (3) was eluted with 25:1 roform-methanol (63.7 m
g (yield 47.3%) was obtained.

[Properties of compound (3)] Rf O,62CHCj! a:MeOH9:1
[α)n −12,2° (C・0.97 CH
C13) Elemental analysis Cl39HIS6053N4 ・
Calculated value as 5H20 C, 59, 18, H, 5, 93
, N, 1.99 actual measurement value C, 59, 17, H, 5, 62
, N, 2.33 with the same solvent? By discharging Rf
A fraction of O,54 (CHCn 3: CH30H) was separated (15 mg). This fraction was purified by thin layer chromatography (CCL:acetone 1:1) to yield 1.4 mg (0.7%) of compound 17).
I got it.

[Properties of compound (7)] Rf O, 12 ccz, : Acetone 1:1 Example 2 Activated molecular sieve AW-300 500 mg
compound (3119mg (0,0069mmoA),
Compound (1113.5mg (0,009mmon)
was dissolved in 2.5 m of dichloroethane II and added, and while stirring at -10°C under an argon atmosphere, BF3/Et2 was added.
01 μl (0,0081 mmoA) was added dropwise and stirred for 1.5 hours. Compound (IN 3.5 mg (0,009
mmoj2), and BFs・Et201. lj7!
(Add 0,0081 mmojl repeatedly and stir at -10°C to -20°C for 2 hours. The reaction solution is filtered through Celite, and the filtrate is washed with deuterated water and distilled water.
Dry with gSO4. Concentrate under reduced pressure and purify the residue using a silica gel column.

Crude yield: 43 mg, liquid chromatograph GPL22
0 column (CHC7!z) to obtain compound (7
1B, Omg was obtained. (Recovery of compound (3) 9.3 m
(yield 55% including g).

[Properties of compound (7)] Rf O,12 (CC1,:acetone, 1:1) [α
)n −7,81° C=0.4 CHll
.

Elemental analysis C,,,H23□N b Oe e・H20
Calculated value as C, 57, 32, H, 5, 77, N, 2
．． 06 actual measurement value C, 57, 03, H, 5, 75, N, 1
．． 96 Example 3 Compound f316. Omg, 2.20X10-3mmo
j! ,, Li1 (dried under reduced pressure at 180° for 2 hours) 5 mg to pyridine 0,1 m 7! and heat under reflux for 4 hours. The reaction solution was diluted with ethyl acetate and washed with dilute hydrochloric acid and saturated brine. Dry over anhydrous magnesium sulfate, and apply the residue to a silica gel (Wakogel C-3001g) column containing 12% MeOH! , to obtain a compound (414.9 mg (yield: 82%)).

[Properties of compound (4)] (α) o −20,0° (MeOHXC=0.
27) RfO, 1712%MeOH/CHCj2
3 Example 4 Compound (414.9 mg (1,84X 10-' m
mol) was dissolved in 2 mJ of EtOHo, 10 μA of hydrazine hydrate was added, and the mixture was heated under reflux for 10 hours. On TLC (
HPTLCnBuOH=EtOH=Hzo4:
2:2 Rfo, 56) After confirming that the I spot is formed, the solvent is dried under reduced pressure. Residue in MeO
Dissolve the solution in 1 mI2 of Ho, add 05 μl of Acz under ice-cooling and stirring, and stir for 90 minutes. The reaction solution was condensed under reduced pressure, and the residue was washed with Sephadex LH-20' (0.8X 10cm M
eOH) to obtain 4.0 mg of the defthaloyl product.

4.0 mg of dephthaloyl compound was added to MeOH-H, O17:3
Dissolve the solution to 0.2 mm, add 3 mg of 10% Pd-C, and perform catalytic reduction. The reaction solution is filtered, and the mother liquor is concentrated under reduced pressure.

Sephadex G 25 (0.8 x 10 cmH)
z O). Compound f611.4mg (54
%).

[Properties of compound (6)] Rf O,18(nBuOH:EtOH: HzO4
: 2 : 2) [α]. +7.7° (H2C, C=
0.07) NMR400MHz DzO60°, inner product H
OD5.175 J=2.4 H-1aα, 4.
906 H-1d.

4.726 H-1c, 4.685 J=8.
OH-1aβ.

4.600 H-1b, H-1e, 2.663.
J=4.4.12.2H-3geg, 2.011.
2.019.2.039.2.057NHAc,
1.667 J=12.5 H-3gax.

Example 5 Compound (7112mg (2,95X 10-3mmo
5 mg of Lil (dried at 180°C for 2 hours under reduced pressure) and 0.5 m of pyridine. and heat under reflux for 8 hours.

The reaction solution was diluted with chloroform, washed with dilute hydrochloric acid and saturated brine, and dried over MgSO4. Concentrate under reduced pressure and purify the residue with a silica gel column (c-3001g chloroform containing 20% MeOH). Compound (817.0mg (
yield of 59%).

[Properties of compound (8)] [α) n −10,5° (CHsOH9C=0
．． 35) Rf O,05 (20χMeOH-containing CHC
J3) Example 6' Compound (817 mg1.733 X 10-'' mmo
Il to EtOHQ, 2m jl! Dissolved in N HzN
Add H2.Hz○ 20p14 and heat under reflux for 3 hours.

RfO,32nBuOH:EtOH: H2C4:
2: Concentrate under reduced pressure and dissolve the residue in MeOHO, 1mff
Add 10μ2 of Aczo and stir for 2 hours under water cooling.

RfO,39nBuOH:EtOH: H2C4:
2: Concentrate under reduced pressure, dissolve the residue in methanol,
Sephadex LH201, 2cm x 18cm (Purify with methanol. Dissolve the concentrated residue in 0.5 mA methanol, add 10 μR of 0.5N-NaOCH, and stir at room temperature for 3 hours. The reaction solution is purified using Amberlyst 15.
After neutralizing with water, filter and dry under reduced pressure. Compound (913,
Get 2 mg. (α) I, -7,06° (CH30
HC=0.16) Compound (9) 3.2 mg at HzOI
mf, add 3 mg of 10% Pd-C, and perform catalytic reduction at room temperature for 2 days. Filtration, concentration under reduced pressure, and purification of the residue using Sephadex G-25 yielded compound QOI: 1. I got Omg.

Yield 26% (from compound (8)) [Properties of compound αω] (α) D −4,6° (H20C=0.05)N
MR400MH2D20 60”, inner product t-BuOD
5.185 H-1aα, J=2.2.5.128
H-1e.

4.925 H-1d, 4.753 H-1c,
4.695 H-1aαJ=7.4. 4.662
m H-1b Hlh H-1g.

Claims (2)

[Claims] (1) A complex polysaccharide represented by the general formula below. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R is a hydrogen atom or a lower alkyl group, R^1 is a hydrogen atom or an acetyl group, R^2 is a hydrogen atom or a benzyl group, R^3 is a hydrogen atom, R^ 4 is an acetyl group, or R^3 and R^4 jointly represent a phthaloyl group, and Y is a hydrogen atom or ▲A numerical formula, a chemical formula, a table, etc.▼ (In the formula, R and R^1 are as defined above. ). (2) Formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Ac represents an acetyl group, R represents a lower alkyl group.) and the formula: ▲There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, Bn is a benzyl group and Phth is a phthaloyl group.) A compound represented by the following formula is reacted in the presence of a glycosylation catalyst, and if necessary, deacetylation, debenzylation, dephthaloylation, and acetylation are performed. A method for producing a complex polysaccharide represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R is a hydrogen atom or a lower alkyl group, R^1 is a hydrogen atom or an acetyl group, R^2 is a hydrogen atom or a benzyl group, R^3 is a hydrogen atom, R^ 4 is an acetyl group, or R^3 and R^4 jointly represent a phthaloyl group, and Y is a hydrogen atom or ▲A numerical formula, a chemical formula, a table, etc.▼ (In the formula, R and R^1 are as defined above. ).