JPH03188094A - Xyloglucan oligosaccharide - Google Patents

Abstract

NEW MATERIAL:A xyloglucan oligosaccharide expressed by formula I (Xyl is xyloglucan; Glc is glucose). USE:Used as disinfecting agent of plant without environmental pollution. PREPARATION:For instance, hydroxyl group of a compound expressed by formula II is acetylated and protected, then 1-position is brominated, thus 1-position is returned to hydroxyl group through allyl ether group and made to thioglycoside to obtain a compound expressed by formula III. On the other hand, disaccharide expressed by formula IV is used as a raw material and 1-position of said disaccharide is brominated, then made to benzyloxymodification, thus 6-position and 1'-position are tritylated excepting protecting group of other hydroxyl group and residual hydroxyl group is made to benzyloxy-modification to obtain a compound expressed by formula V having hydroxyl groups at 6-position and 1'-position excepting trityl group. Next, resultant compound is reacted with thioglycoside expressed by formula III and protecting group is removed to afford the aimed compound expressed by formula I.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to zyloglucan oligosaccharides.

(Prior Art) It has been reported by McDougall et al. (G, J, McDongalland S. ,
C, Fry, Plants, 175, 412T
416 (1988)), York et al.
A, G, Darvill+and P, A1bashe
im+Plants Ph si Lee, 75,295-
297 (1984)).

(4) Zyloglucan oligosaccharide Fu represented by the following formula
c α1→2 Galβ1−+2Xy1crl−”6
Gfcβ1→4Gj! However, until now, there has been no example of chemically synthesizing this zyloglucan oligosaccharide, and the only method was to collect, separate, and extract it from natural plants.

(Problems to be Solved by the Invention) Therefore, the present invention provides a synthetic intermediate for synthesizing this zyloglucan oligosaccharide.

This synthetic oligosaccharide is expected to be useful as a non-polluting plant protection agent.

(Means for Solving the Problems) The present inventor has realized that by the reaction shown in the scheme below,
The objective zyloglucan oligosaccharide was synthesized and the present invention was completed.

That is, the present invention provides (1) zyloglucan oligosaccharide (2
) Zyloglucan oligosaccharide Xyl represented by the following formula
a 1-'p6 Glc β1-+ 4 Glc(
3) Zyloglucan oligosaccharide (4) represented by the following formula
Zyloglucan oligosaccharide Fuc α represented by the following formula
1-+ 2 Gal β1-+2Xy4 αl→6Gf
It provides cβl→4Gfc.

An example of a synthesis scheme for zyloglucan oligosaccharides via the synthetic intermediates of the present invention is shown below (in the formula, vesico- represents an acetyl group, ph- represents a phenyl group, Br+ represents a benzyl group, H is an acetoxy group, ← is a benzyloxy group, T
r is a trityl group, MP is a methoxyphenyl group, TM
SOTf stands for trimethylsilyl triflate).

The following scheme shows one example of synthesis and is not intended to limit the scope of the present invention in any way.

75% β1→4G1c β1→4Gj! c 8a In the above reaction scheme, reaction conditions for reagents preferably used are described below.

A: Catalyst, etc. B: Solvent C: Reaction temperature D2 hours■2→
Conversion to 3 A: 'I1gBrz, lIgcH, Ag0TfB dichloroethane dichloromethane, chloroform, toluene, benzene C: O''CkRT -20''C~0°C-1?
T~40'CD: 3.5 hours 2 hours~all night■
Conversion from 3 to 4 A: MeONa B: MeOII C: IIT D=1 hour ■ Conversion from 4 to 5 C: RT D: 3 hours ■ Conversion from 5 to 6 C: 80°C EtONa, NaOH tO11 0 °C to 60 °C 30 minutes to overnight 0 °C to 40 °C 1 hour to overnight 60 °C to 100 °C D = 1 hour 1 hour to 3 hours ■ Conversion from 6 to 7 B Nidichloromethane dichloroethane, Lum, Toluene, chlorophobenzene C: 0"C→RT/-20℃ D: 3 hours/20 minutes ■9→10 conversion A: ■gBrz, Hg(CN)z 20℃→l?T/-80℃ ~O℃ 2 hours ~ 5 hours 710 minutes ~ 1 hour gOTf C: 60 "CD = 45 minutes ■ Conversion from 10 to 11 A: MeONa B: MeOH C: RT D = 30 minutes ~ all night ■ From 11 to 12 Conversion C: 60 °C D = 16 hours (overnight) ■ Conversion from 13 to 14 to R7 80 °C 30 minutes to 2 hours EtONa, NaOH εtOFl, MeOH-T) IF O °C ~ reflux 40 °C ~ 80 ° C 8 hours to all night 8, B 90% Ac0H C: 60 C D: 2 days [phase] Conversion from 11 to 15 D: 12 hours ■ Conversion from 16 to 17 C: 60 ℃ D: 10 hours @ 7 + 14 → Conversion to 19 p-) Luenesulfonic acid aqueous solution RTA+reflux 5 hours to 1 week 6 hours to all night RTNreflux 5 hours to 1 week B: CH, N01 Cj! C1hCHtCI! , CHzCl z.

C) ICQ　s+Ether, TolueneC:RT D=4 hours ■Conversion from 19 to 20 RT~40゛C 4 hours to all night D = 14 hours (all night) Conversion from o20 to 21 C: RT D: 24 hours (all night) ■Conversion from 22 to 23 A: DBU ■Conversion from 23+18 to 24 A: BF,・OEt.

B: CHtCj2t C knee 20°C 10 hours to 1 day R7-60°C 10 hours ~ ICO.

MSOTf CI GHzC)lzc l, CHCl 3゜CC
l41 Toluene -78℃~-20℃ ■Conversion A from 7+25 to 26a: CuBrt/HgBrz/n-BuJBrCuB
NBr or MeOTf to rz/8gOTf/n-Bu B: HxNOt CH1Cf□Cffi ctttcnic i! ,.

CHClfftEther, TolueneC: °C~40℃ ■23 +28a → 26a conversion to Heiji BFs　-ot:tz MSOTf C knee 20°C [Phase] Conversion from 26a to 27a A I) MeONa 78°C ~ 0°C aOH Conversion from O2 to 30 C:reflux D: 30 minutes to 10 hours (E) Conversion from 30 to 31 C:reflux ■) ＾： C: D: 2)C: MeONa RT 2 hours 0°C-+RT RTNreflux RTNreflux EtONa, Na0H 0°C ~ 40°C 1 hour to all night 0°C ~ 40°C D: 5 hours 2) Eight: 0°C-RT C: 1 hour 1 hour to all night O'C~40''C 30 minutes to all night Conversion from 37 to 38 1) A, B 90°CAcOHaq C: 90 C D=5 hours 2) C: RT D: All night Conversion from 40 to 41 HCl2-T)IF aq.

60℃~reflux 2 hours~overnight R7-60℃ 10 hours~1 week C: RT D: 2 hours 0℃-RT 1 hour~10 hours 41+33→42 conversion A: Bh ・0Etz TMSOTfC knee 2
0°C 0: 10 minutes - 78°C - 0°C 5 minutes - 1 hour D: 1 hour 30 minutes - all night.

Conversion from 0 31 to 32 B: cict+zcn□CI! .

C knee 20°C CHzCj2 z, CHCj23 78°C to -20°C 0 Conversion from 32 to 33 A: MeONa EtONa, Na0H C: RT D: 3 hours 0°C = reflux 1 hour to all night 0 34 to 35 Conversion of C: 60 °C D: 1.5 hours 40 °C ~ reflux 1 hour ~ 10 hours Conversion to O35 → 36 1)^: MeONa C: RT EtONa, Na0H 0 °C ~ 40 °C 42 → 43 Conversion to: MeONa EtONa, Na0
HB: MeOll EtOll Other alcohol frequency C: 60 C10'C-refluxD:
2 hours 1 hour to all night (i) 44 + 43 → 45a Conversion C: 0°
C-+RT O°C~40°C D=2 hours
Conversion A from 45a to 46 for 2 hours to all night 1) Rh (PPhz)zcl/DABcO
(Ir(COD)(PMePhz)t) PF&2)
HgC1z, Hg0 1IC50℃-+
reflux RTNrefluxQ
Conversion from 46 to 49 A l) MeONa EtO
Conversion to Nao 49-50a, b A: Ac, 0 cC1 O C: RT D: Conversion from 51 to 52 all night 0°C to 50°C 5 hours to 1 week C: RT D: Time 52 to 53 Conversion of 0°C to RT 1 hour to 10 hours to 1 week C knee 20°C D: 30 minutes 78°C to O''C 10 minutes to 1 hour (Effect of the invention) Synthesis using the intermediate of the present invention The zyloglucan oligosaccharide used in this study has the effect of inhibiting the growth of plant cells caused by auxin, and can be used as a plant protection agent.

Further, by using the synthetic intermediate of the present invention, useful zyloglucan oligosaccharides can be produced in high yield.

(Example) The method for producing the compound of the present invention will be described below as an example. The compound number in the examples is the compound number in the above scheme.

Example 1 2 -m-→3 Bromide (2) (10 g, 34 mmol) was dissolved in 20 ml of dichloroethane, and allyl alcohol (12 ml, 170 mmol) and mercuric bromide (
6,2g, 17mmol) mercuric cyanide (4,
3g, 17+uaol) was added. After stirring at room temperature for 3.5 hours, the reaction solution was washed with saturated deuterated water and water, and dried over magnesium sulfate. After evaporation of the solvent, the residue was recrystallized from methanol. 3.4 g (37%) 500 MHz NMR (CDCl: +) δ 5.85
3 (dddd, IH, Allyl),
5.2B0゜5.198 (2dq, 2H, allyl), 5.162 (t, 18J 8.77 Hz
+ H-3), 4.948 (dd, 1B, J
6.478.74 Hz, H-2), 4.950
(dt, IH, H-4).

4.543 (d, LH, J 6.47 Hz, H
-1), 4.293°4.07H2dd, 2H,H
-5), 4.130 (dd, IH, H-5)3.
041 (dd, LH, H-3), 2.061.2
．． 050.2.041° (3s, 9H, 3Ac) [α] o -61,5° (c 1.00 CHC
fs ) R, 0, 52 (2:1) cO to Rueso
Et) mp, 103-104°C Elemental analysis calculation value (Calc, for) C, 4 ■zoo
s: C, 53, 16; H, 6, 37χ Actual value (Found) C, 52, 93; ■,
6.37χ Example 2 3 -1yu 4 Triacetate (3) (10.0g, 31.6
msol) in methanol (90d) to 0.1 M
Sodium methoxide (10d) was added and stirred at room temperature for 1 hour. Amberlyst 1
5.4 g (90%) of hygroscopic crystals were obtained by recrystallization from methanol-ether.

[α] = −61,4(c 1.81 HzO)R
Fo, 45 (5:I CHCfz-MeOH) Elemental analysis calculated value C, 11,, O,: C, 50, 52; H, 7, 42χ Actual value: C, 50, 30, H, 7, 46 χ Example 3 4 --1 → 5 Compound 4 (3.90 g, 20.5 mmol) was converted into D
Dissolved in MF (40d). Add 60% sodium hydride (3.9 g, 98 mmol) under water cooling and stirring,
Next, benzyl bromide (11xtl, 92a+mol)
was dripped.

After stirring at room temperature for 3 hours, methanol was added and stirred for 30 minutes. The solvent was distilled off under reduced pressure, and the residue was dissolved in chloroform, washed with water, and dried over magnesium sulfate.

Flash column chromatography (silica gel 90
0 g, purified with toluene-ethyl acetate (90:1) and recrystallized from ethyl acetate-hexane to obtain 5. 7.47g (79%) 500 MH2'HNMR (C
DCl z) 67.359~7.245 (15H1
3C&H3), 5.939 (m.

IH, allyl), 5.327 (dq, Ill
, Allyl).

5.197 (dq, IH, allyl) + 4.390
(d, IH.

, y 7.44.8-1), 4.355 (dat,
IH, Allyl).

4.120 (ddt, IH, allyl), 3.92
2 (dd, IHJ 5.02 11.49 H-5
) 3.613 (dt, IH, 15, 1B, 8
．． 73 8-4), 3.568(t, IH, J
8.74 H-3), 3.395 (dd,
IH, J 7.77°8.74 H-2), 3
．． 196 (dd, ill, J 10.0
3. 11.65t5) [α] n + 8.4” (c 1.00 C1
1C2,) R, 0,60 (10: 1) Rueso A
c0Et)1, 52-53 °C Elemental analysis calculation value CzJ, I□O1: C,? 5.63 ; )l, 7.00χ Actual value:
C, 75,55, H, 7,01χ Example 4 5 - 1 6 Allyl glycoside 5 (6,0g, 13nuwol
) in 95% acetic acid aqueous solution (120d), palladium chloride (3.2 g, 18 n+mol) and sodium acetate (4.3 g).

52a+mol) was added and heated at 80°C for 1 hour. Insoluble matter was filtered off, and the solvent was distilled off under reduced pressure. The residue was dissolved in chloroform, washed with saturated deuterated water and water, and then dried with magnesium sulfate and subjected to flash column chromatography (
After purification with 500 g of silica gel and toluene-ethyl acetate (9:1), the compound 64 was recrystallized from ethyl acetate-hexane.
．． 1 g (75%) was obtained.

[α] o +15.2@(c 1.00 CHC/
! i) RF O, 48 (3: 1) Lueso Ac
0Et) Elemental analysis calculation value CzbHzllOs :C,
74,26; It, 6.71χ Actual value: C,
74,14; H,6,73χ Example 5 H Compound 6 (5,00g, 11.9n+mol) was dissolved in dichloromethane (50d) and trichloroacetonitrile (12lIi, 59+*mol) was added under water cooling.
, 1,8-diazabicyclo(5,4,0)-7-undecene (DBU) (350 uj2, 24 mmol) was added. After stirring at room temperature for 3 hours, the reaction solution was passed through silica gel.

The solvent was distilled off, and the residue was azeotroped with toluene and then dissolved in 50% dichloroethane. Cool to −20°C and add tributyltin methyl sulfide (Bu+SnSMe) (6.0 g, 18
1III01) Then trifluoroborane, ethyl ether (2,2d, 18+u+ol) was added. After stirring at the same temperature for 20 minutes, saturated sodium chloride water and saturated potassium fluoride aqueous solution were added, and the mixture was stirred at room temperature for 1 hour. Insoluble materials were removed by filtration, and the organic layer was diluted with chloroform and washed with saturated deuterated water and water. After drying magnesium sulfate, use flash column chromatography (700 g of silica gel, 2
0:1) toluene and ethyl acetate. Ethyl acetate
Recrystallization from hexane yielded 74.5 g (86%) of thioglycoside with α:β=526.

500 Mllz' HNMR (CDCi 3)α:
67.193 (d, J 5.18 Hz, H-1
), 3.889(t, J 11.00 tlz,
H-5), 3.784 (t, 9.0011-3)
, 3.733 (dd, J 5.1B, 9.38
Hz), 3.539 (ddd, J 5.50.8
．． 42.10.681 (z), 2.032 (st 5
GHz) β: 64.319 (d, J 9.38 Hz, H
-1), 4.025 (dd, J 4.69, 11.
4914-5), 2.201 (S, 5C113)I
~-”1/R,0,60 (α”) 0.55 (β) (10:
1) Lueso Ac0Et) Elemental analysis calculation value CzJz. 04S: C, 71,97i H, 6,71; S, 7.12
% actual value: C, 72, 23; II, 6.73
S, 7.25% Example 6 Promide (9) (55.0g, 78.6mmo
1) was dissolved in dichloroethane (350d) and benzyl alcohol (150d) was added. In addition, mercuric bromide (1
8.5g, 51mmol), mercuric cyanide (
13g.

51 mmol) was added and heated at 60°C for 45 minutes. After cooling, it was diluted with chloroform, washed with saturated deuterated water and water, and dried over magnesium sulfate. The residue concentrated under reduced pressure was recrystallized from ethyl acetate-hexane to give 1040.7 g (7
1%).

400MHz 'HNMR (CDCfs) 5.141 5.060 (dd.

18, J 18, J (t, 28. J 9.38 H-3a,
If-3b).

(t, LH, J 9.64Hz H-4b),
4.974IH, 7,43,9,64Hz H-2a)
, 4.918 (dd.

7.94.9.18Hz H-2b), 4.548
(dd.

1.96. 11.96 Hz H-6a), 4.
508 (d.

18, J 8.02tlz, H-1b),
4.503 (d, IH.

J 7.8211z, H-1a), 4.372
(dd, LH.

J 4.40. 12.45Hz, H-6b),
4.106 (dd, IH.

J 4.4B, 11.96. H-6' a),
4,077 (dd, IH.

J 1.80. 12.45Hz, H-6' b)
3.796(t, IIl, J 9.52.9.
28Hz, H-4a).

3.656 (ddd, IH, J 1.80.4
．． 40.9.76Hz.

1(-56), 3.567(ddd, IL J
1.96.4.48°10.0IHz H-5a) [α]D -35,3° (c 1.00 CHCj
! x) R, 0, 46 (1: 1) Lueso Ac0
Ht) Rinp, 188-191 °C Elemental analysis calculated value Cs5HazO+m: C, 54, 54
; H, 5,83χ Actual value: C, 54,35; Il, 5.81χ Example 7 It was dissolved in M sodium methoxide methanol solution and stirred at room temperature for 10 hours. It was neutralized with Amberlyst-15, filtered off, and recrystallized from methanol to yield 1131.0 g (
81.4%).

500 MHz 'HNMR (Dto, 60℃) δ
4.923.4.762 (2d, 211 J 11
．． 65J 7.77, H-1a and b) [α]o -38,2° (c 1.00 MeOH
) RF O, 50 (2: I CHCf s9MeO
H) mp, 193.5-194.5 °C Elemental analysis calculation value C+dbsOz: C, 52,77; H,
6,53χ Actual value: Trityl chloride (31 g, 110 s) dissolved in C, 52,60, H, 6,56'& Example 8 (200 d)
sol) was added and heated at 60°C for 16 hours. The residue obtained by distilling off the solvent under reduced pressure was subjected to flash column chromatography (
Silica gel 1) cg, 1:2) toluene-ethyl acetate 1
% triethylamine) to obtain 31.4 g (74%) of the trityl compound (12) of Example 9.

500 Mllz'HNMR (CDCj2+) 4.4
42 (d, IH, J 7.45 Hz, H-1a
or 1l-1b).

4.149 (d, ill, J 7.77 Hz,
H-1a or 1b) [α] , -26,1°
(c 1.00 CI(If!z)R,0,31(1:
2) Luesor Ac0E t) Elemental analysis calculation value C5
JsbO++ ・'AHzO:C, 73,93; H
,6,20% Actual value: C,73,62; 11.6.10% compound 12 (10.0 g, 10.9 mmol) in D
60% sodium hydride (3.5 g, 8.7 + u+ol) was added to the solution under water cooling, and then hensyl bromide (9.7 d, 82 n+mol) was added dropwise. After returning to room temperature and stirring for 2 hours, methanol was added to decompose excess benzyl bromide and sodium hydride. The solvent was distilled off under reduced pressure, and the residue was dissolved in ethyl acetate and washed with water.

After drying magnesium sulfate, it was purified by flash column chromatography (1 kg of silica gel, 9:1 hexane-ethyl acetate 1% triethylamine) to obtain 12.6 g of I3 (
85%) was obtained.

400 MHz 'H-NMR (CDCl3)64.
496 (d, IHJ 7.93 Hz, H-1)
.

4.361 (d, IHJ 7.63Hz, H-1
) [α] a −16,9° (c 1.00. CH
Cfz)R,0,56()Luene) Elemental analysis calculated value C5JsbO++:C,80,7
9; H, 6,34χ Actual value: C, 80,50i H, 6,38χ Example 10 Dissolved in acid and heated at 60° for 2 days. After evaporating the solvent under reduced pressure, the residue was dissolved in chloroform, washed with water, and dried over magnesium sulfate. After purification by flash column chromatography (850 g of silica gel, 2:1 toluene-ethyl acetate), recrystallization from ethyl acetate-hexane yielded 145.
Obtained 0g (80%).

500 MHz 'H-NMR (CDCI2s) 3.8
49 (t, IH, J 9.39 Hz, l
l-4b).

3.661 (t, to, J 9.07 H
z, H-3b).

3.549 (t, IH, J 9.25. H
-3a).

3.442 (t, 211. H-2a,
1i-4b).

3.370 (dd, LH, J 7.93.9
．． 22) 1z, H-2b) [α] o -38,
3” (c 1.00.C)lcj!z)RF O,
62 (1: 1) Lueso AcOEt) mp, 1
49-150 °C Elemental analysis calculated value C54H580□: C,73,45
; H, 6, 62χ Actual value: C,? 3.26 i H,6,57χ Example 11 4.544 (d, IH, J 7.76 Hz,
)l-1a).

4.523 (d, LH, J 7.77 Hz,
H-1b).

Benzaldehyde dimethyl acecool (16rttl, 104m+mol) p − dissolved in (150d)
) Luenesulfonic acid l hydrate 1.3 g (6.9m5
ol) was added.

After stirring at 60°C for 12 hours, the mixture was neutralized with triethylamine. The solvent was concentrated under reduced pressure, and the precipitated crystals were collected by filtration and washed with water.

27.5g (76%) of 15 recrystallized from methanol
Obtained.

[α]o −50,9° (c 1.00. DM
F ) Rr O, 64 (10: 1 (JICf
s Meoll)mp, 191-193°
C Elemental analysis calculated value CzillsJ□・H2O: C, 57
,98; H,6,36χ Actual value: C,57,94,)I, 5.97χ Example 12 15-m-→ 16 Compound 15 (25.4g, 48.8mm+ol)
was dissolved in 250ml of DMF, and while cooling with water, 60% sodium hydride (11.7g, 59n+a+ol) was added thereto, and then benzyl bromide (35d, 59mmol) was added dropwise. After returning to room temperature and stirring for 3 hours, methanol was added to decompose excess sodium hydride and benzyl bromide. The solvent was distilled off under reduced pressure, and the residue was dissolved in ethyl acetate and washed with water. After drying with magnesium sulfate, it was recrystallized from ethyl acetate to obtain 29.2 g (61.6%) of 16.

400 MHz 'H-NMR (CDCl s) 4.5
31 (d, 18. J 7.6311z, H-1
).

4.480 (d, IH, J 7.63 fiz
, H-1) 4.186 (dd, IH, J 5.
04.10.53Hz, H-6b) 4.001 (
t, 9.16Hz, L4a) 3.547 (d
d, LH, J 8.63. 10.56Hz,
H-6b) 3.681 (dd, IH, J 9.
46. 1.521+2. lt-6a) 3.151
(+a, IH, H-5) [α] o -6,
7' (c 1.00. (l(Cj!+)R,0,
54 (10: 11-LuesorAc0Et)mp,
158-161 °C Elemental analysis calculated value CHI) 141011 ・HzO:C,
74,07i H,6,52χ Actual value: C,73,80; 11.6.27 X
Example 13 Compound 16 (27.0 g + 27.2 mmol) was dissolved in 90% acetic acid 2701d and heated at 80°C for 10 hours.

The solvent was distilled off under reduced pressure, and the residue was dissolved in chloroform, washed with saturated deuterated water and water, and dried over magnesium sulfate. Recrystallized from ethyl acetate-hexane to give 1722.6 g (92%
) was obtained.

400MH2NMR (CDCl2z) 64.491
(d, IHJ 7.35. H-1), 3.946
(t.

LH, J 9.19Hz), 3.812 (dd, I
ll, J 4.0B.

10.90Hz), 3.627(dd, IH,3,
16, 11, 82H2).

3.538 (t, IH, J 8.50Hz), 3.
492 (t, 18°J 7.64flz) [(r] o -6,3' (c 1.00 CHC
j! +)R,0,49(1:l)c to Rouesso
OEt)mp, 125-126°C Elemental analysis calculated value C5aHiaO++: C,73,45
; H, 6,622 Actual value: C, 73, 19; ■, 1.7 mmol), triphenylphosphine (445■, 1.7 m+*ol), diethyl azodicarboxylate (265μ2.1.7 mm+
ol) was added. After heating at 60°C for 2 hours, the mixture was diluted with chloroform and washed with 1M aqueous sodium hydroxide solution and water. After drying with magnesium sulfate, it was purified by flash column chromatography (5:1) with ethyl acetate and recrystallized from ethyl acetate-hexane.

840■ (75%) 400MHz' HNMR (CDCl 3) 64.5
26 (d, IH, J 7.2811z, H-1
) 4.485 (d, IH, J 7.6311z,
H-1) 4.040 (t SIH, J 8.85H
z, H-4a) 4.016 (dd, IH, J 3
．． 66.9.76flz, ll-6b) 3.959 (
dd, 18SJ 4.58.10.07Hz, H
-6b) 3.864 (dd, Ill, J3
．． 1? , 10.11 Old 6a).

3.760 (s, LHlOCTo).

3.584 (t, IH, J 8.85, H-3
a).

3.498 (t 7.63.9.15, t2a) [α
] -15,6° (c 1.00, CHCl3)
R,0,38(5: 11-LuesoAcOEt)mp
, 124.5@-126°C Elemental analysis Calculated value CblHb40□・'/, HzOi C,73,73i H,6,54% Actual value C,73,61; H,6,54%Example 15 7 + 14 Add donor 7 (2,00 g, 4.40 m5o) to a brown 3-day flask containing dried molecular sieves 4A.
l), acceptor 14 (980■, 1.11++vo
l) , cupric bromide (1.2 g, 5.3 + II mol
), mercuric bromide (1.9 g, 5.3 mmol
), tetra n-butylammonium bromide (1.7 g,
5.3 o+mol) was added thereto, nitromethane was added under an argon atmosphere, and the mixture was stirred at room temperature for 4 hours. After diluting with chloroform and removing insoluble materials by filtration, the mixture was washed with a saturated aqueous sodium hydrogen carbonate solution and water.

After drying over magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by flash column chromatography (250 g of silica gel, 5:1) to ethyl acetate, and then 500 g of silica gel, 15:1) to ethyl acetate (15:1). , compound 191170 (62%)
I got it.

400M1lz'HNMR δ4.462 (d, IH, J 7.63Hz,
ll-1).

4.053 (t, 1B, J 9.30Hz).

Elemental analysis Calculated value C1゜6HI+0013 ;c,
75.42 ; H, 6,57% Actual value C, 75,44; II, 6.60% Example 16 22.5 MHz "CNMR δc 102.562 .102.454 .97.2
01.97.036 [α) +41. O@ (cl,
65, CHCl3) RF O,40 (5: 1) LuesoAc0tit) Compound 19 (836■, 0.49
Dissolve 5 mmof) in 1:1 THF-methanol (10 d), add 200 μm of palladium on carbon, and dissolve under hydrogen atmosphere for 1 hour.
Stirred for 4 hours. Filter through Celite, remove the solvent under reduced pressure, and
0 (290μ, 96.7%) was obtained. For measurements such as elemental analysis, 5ephadexG-10 (water) was used and purified.

400MHz NMR (DzO) 65.226 (d, J 3.6611z, H-
1αβ) 4.940 (d, 2H, J 3.65H
z, H-1b, ll-1d) 4.688 (d,
J 8.24Hz, H-1αβ)4.559 (
d, IH, J 7.9411z, It-I
C) [α) +101.5° (cl, oo, H2
O)R,0,20(4:2:1 butanol-
Ethanol-water) Elemental analysis Calculated value CzzlbsO+q・H2O:C,4
2,31, H, 6,46% Actual value C, 42,42; H, 6,27% Example 17 Compound 20-290, 0.478 mmol) was dissolved in pyridine (5 m) and acetic anhydride ( 1, 1d, 11
After stirring at room temperature for 20 hours, methanol was added to decompose excess acetic anhydride. The solvent was distilled off under reduced pressure, and the residue was dissolved in chloroform, washed with water, 2M hydrochloric acid, water, saturated aqueous sodium bicarbonate solution, and water, and dried over magnesium sulfate. The residue after solvent distillation was purified by flash column chromatography (50 g of silica gel, 1:2 toluene/ethyl acetate) to give 21.463 (87%) α
9 βm1xture R,0,43 (1:2) Lueso Ac0Et) Elemental analysis Calculated value C4J16□0,1:C,49,73;
H, 5,63% Actual value C, 49,72; H, 5,58% Example 18 21 22 Compound 21 (110 ml, 0.09 mol) was dried D
Dissolved in MI'(2-) hydrazine acetic acid (12,0.
14 mmol) was added and heated at 50°C for 1 hour. The residue obtained by evaporating the solvent under reduced pressure was dissolved in chloroform and washed with a saturated aqueous sodium hydrogen carbonate solution and water. It was dried over magnesium sulfate and purified by flash column chromatography (10 g of silica gel, 1:2 toluene-ethyl acetate). 89mg (92%) (a) + 93.1 @(
cl, oOCH (Ji) R, 0,41 (1:2) Lueso Ac0Et) Elemental analysis Calculated value C4JboOs.

・020: C, 4B, 62, H, 5, 75% Actual value C, 4B, 80; H, 5, 56% Example 1
9 Compound 22 (230 μ!, 0.22 wllol) was dissolved in methylene chloride (5d), and trichloroacetonitrile (110 μ!, 1.1 mm) was dissolved in argon atmosphere and water-cooled.
ol) DBU (6, Jul, 0.043+II
mol) was added. After stirring for 1 hour while cooling with water, the solvent was distilled off under reduced pressure, and the residue was purified by flash column chromatography (10 g of silica gel, 1:1) Rueso ethyl acetate). 234■ (89.7%) [α) +95.
9' (cl, 15 CHCj!i) RFo, 41 (
1:1) Lueso Ac0E t) Example 20 Molecular sieves AW-300 with donor 23 (234 mg, 0.193 mmo+) and acceptor 18 (350 μ, 0.380 mmol) dried in advance
and dissolved in dichloromethane (5d). Cool to -20°C and add trifluoroborane.
Etherate (29 μm, 0.23 mmol) was added, and after stirring for 30 minutes, triethylamine was added to neutralize.

After diluting with chloroform and removing insoluble materials by filtration, the mixture was washed with water and dried over magnesium sulfate. Purification by flash column chromatography (60 g of silica gel, 1:1 toluene-ethyl acetate) yielded compound 24210 (53%).

22,5 MHz” CNMR(CDCl3)δ
c 102.5.102.1.100.56.10
0.34.96.9.96.0 [α) + 38.1' (c 1.34 CI
C1z) RFo, 55 (1:1) Lueso Ac0E
t) Elemental analysis Calculated value C3゜581□2041'
C, 61,82; H, 6,03% Actual value C, 61,69; H, 6,21% Example 21 Compound 24 (157 mg, 76.1 mmol) in acetonitrile-water (4:12d) Dissolve and add cerium ammonium nitrate (CAN) (83,5■,
152 μmol) was added and stirred for 2 hours. The residue obtained by evaporating the solvent under reduced pressure was dissolved in chloroform and washed with a saturated aqueous sodium hydrogen carbonate solution and water. Flash column chromatography after drying magnesium sulfate (silica gel 15g
, 1:1 toluene-ethyl acetate) and purified 25 with 83
．． 1 (56%) was obtained.

500MHz' IINMR (CDCl:l)4.
469 (d, III, J 7.26Hz,
fl-1), 4.374 (d, IHl
J 7.9211z, H-1), 2.106 (3H)
, 2.057 (3H) , 2.029 (3H) ,
2.023 (3H), 2.011 (3H), 2.0
07(68), 1.987(68), 1.960(
3tl), 1.924(3H)(α) +36
．． 2° (cl, 00, CHCl :l) R, 0,45
(1: 1 toluene-AcOEt) Elemental analysis Calculated value C911111604°: C, 60, 86; H, 6,
05% Actual value C, 60,87; H, 6,04% Example 22 A: Compound 25 (21.0, 10.7 mmol),
Cupric bromide (7.2 g, 32 Il 1 mol), mercuric bromide (11.6 g, 32 mmol), and tetra-n-butylammonium bromide (1.4 mm, 4.3 mmol) were dried in molecular sieves 4A (300 mmol). 2 with)
0 flask and added nitromethane (lsd).

A nitromethane solution of compound 7 (I
Id) and stirred at room temperature for 2 hours.

The reaction mixture was diluted with chloroform, insoluble matter was filtered off, washed with a saturated aqueous sodium bicarbonate solution and water, and dried over magnesium sulfate. Flash column (6g of silica gel,
10:1 chloroform acetone, 6g silica gel,
20:1 chloroform-acetone) HPTLC (0,
Using 25×20×20.10:1 chloroform-acetone), a mixture of α and β (16.6 μm, 54%) was obtained. 5 pieces) IPTLc (0.5mmX 20
CIIX 20cI11, chloroformacetone 10:
1.3 expansions) to separate α and β, and the α body (26a)
8.0■ and β-isomer (26b) 6.0■ were obtained.

26a Rr O,36 (10:1 chloroform-
acetone) 26b RF O, 33 (10: 1 chloroform-acetone) elemental analysis Calculated value C1□48
14□044=C, 63,74ill, 6.13% Actual value C, 63,74ill, 6.13%Example 23 Put into a container containing ①) and add dichloromethane (1.0d).
It was dissolved in Cool to -20''C under argon atmosphere, trifluoroborane ethyl ether <3.1 ul, 0.
030 mmol) was added and stirred. Triethylamine was added to neutralize the mixture, and the molecular sieves were filtered off, diluted with chloroform, and washed with saturated deuterated water and water. Dry with magnesium sulfate and concentrate under reduced pressure. The residue is subjected to preparative TLC (1
: 1) Purified with ethyl acetate) to obtain compound 2
6a (1.0■, 4%) was obtained.

Example 24 Compound 23 (24,3■, 0.020 mmol), Compound 28a (12,9111 g, 0.010+mol)
l) Molecular sieves AW pre-dried
300 (100 Compound 26a (8,0■, 3.4
μmol) was dissolved in 0.1M sodium methoxide ld and stirred for 20 hours. After neutralizing with Amberlyst 15 and removing Amberlyst by filtration, 10 μm of palladium on carbon was added, and the mixture was stirred for 24 hours under a hydrogen atmosphere. After filtering off the catalyst,
Column chromatography (Sephadex G-
25.5 g, water) to obtain 2.3 ■ of compound 27a.

500MHz 'HNMR (DzO, 60℃) 65.2
Example 25, J=3.96, J=3.30.

, JP3.62 1, J=7.92, Jyo7.59, J=7.59, Jyo7.92 2:1, II~1aα) H-1 (e or f or g)) H- 1(e or f or g)), H-1aβ), H-1(b or C or d)), H-1(b!l is C or d)), H-1(b or C or d) )) 3.5 µm of n-butanol-ether compound 26b was deprotected in the same manner as for deprotecting 26a to obtain 1.5 µm of 27b.

500M1lz'H-NMR (DzO, 60°C) 65
．． 199 (, J=4.03, H-1aα).

4.923 (Ill, J・3.66
, H-1(f or g)).

4.911 (IH, J・4.03, H-1
(fmadahag)).

4.631 (, J=8.06, old 1aβ).

4.567 (ill, J=8.06,
H-1(b or +Jhlid)).

4.520 (IH, J, 8.06, 1(-1
(b or C or ud)).

4.512 (ill, J=7.70,
H-1 (btLl!c or d)).

4.441 (IH, J=7.69, H-1e)R
,0,27 (4:2:1 butanol-ethanol-water) Example 26 2→30 Promide 2 (22.7g, 66.9 mmof)
was dissolved in methylene chloride (110 m), allyl alcohol (46 tdl, 670 sa+of), tetra-n-butylammonium bromide (65 g+20
0mmof) triethylamine (111I11.80
mmoffi) was added thereto, and the mixture was stirred under reflux for 1 hour. It was diluted with chloroform and washed with water. After drying with magnesium sulfate, the orthoester 30 (20,
1 g, 94.8%).

A small amount of oil was taken, recrystallized from ethyl acetate-hexane, and subjected to elemental analysis.

500) IZ'HNMR (CDI3) δ5.887
(m, A11yl), 5.571 (d, J 4.
39) fz, H-1) 5.155 (dq, J 1
．． 47 and 10.25 Hz), 4.207
(m.

), 4.039 (dt, J 1.29 and 5
．． 50 Hz), 3.918 (dd, J 5.13
and 12.46)fz)l-5), 3.67
7 (dd.

J 6.96. 12.07 HzH-5')RF
O,56(Toluene-AcOEt1:
1) mp, 44-46 °C Elemental analysis, calculated value C+ 4HtoOs: C, 53,
16, H, 6,37% Actual value: C, 52,80, H, 6,37% Example 27 30 → 31 Compound 30 (19,1 g + 60.4 mmoj2
) was dissolved in 0.01M sodium methoxide 55II11 and stirred at room temperature for 2 hours. The solvent was then distilled off under reduced pressure, and the residue was dissolved in 400ml of anhydrous DMF. Sodium hydride (50% oil base, 8.7 g, 180
ma+o1) followed by benzyl bromide (22IItl
) was added dropwise.

After returning to room temperature and stirring for 1 hour, methanol was added to decompose excess benzyl bromide. The solvent was distilled off under reduced pressure, and the residue was dissolved in ethyl acetate and washed with water. After drying over magnesium sulfate, the residue was concentrated under reduced pressure and purified by flash silica gel column chromatography (900 g of silica gel, toluene-ethyl acetate 15:1 triethylamine 1%) to obtain Compound 31 (24.8 g, 99.6%).

RF O, 46 (Toluene-8cOEtlO:
1) Elemental analysis, calculated values C,,I! . 0°: C, 69,89; H, 6,84% Actual value: C,
69,98; H, 6,78% Example 28 31→32 Orthoester 31 30.3g (73,5g+eo
f) was dissolved in dichloroethane (600m) and placed in a container containing 60g of Molecular Sieves 4A.

Cool to 20°C and add trimethylsilyl triflate (
1,3d, 7.3mmoj2) was added. After 30 minutes, triethylamine was added to neutralize the mixture, and the molecular sieves were filtered off, diluted with chloroform, and washed with water. After drying with magnesium sulfate, it was purified by flash silica gel column chromatography (SiOz 850 g toluene-hexane-ethyl acetate 10:10:1) and 32 (25,9
g, 85%) was obtained.

400MH, NMR (cocL) 65.831 (m, IH, Al1yl),
5.248 (m, LH, A11yl) 5.16
3 (m, IH, A11yl), 4.943
(dd, IH, J=7.32°8.8511Z
H-2), 4.826 (d, IH,, r=
11.60. σ+CHt).

4.703 (d, IH, J=7.63. @-c
t+z), 4.681 (d, IH.

J 11.6011z, @-CHz), 4.3
80 (d, III, J 7.328zH-1
), 4.268. 4.037 (g+, 2H
, A11yl), 3.976 (dd.

18, J 4.89 and 11.60Hz l
l-5), 3.674 (ddd, IH.

J 4.88, 8.55 and 9.46Hz,
H-4), 3.582 (q, IH.

J 8.55Hz, H-3), 3.248
(dd, ill, J 9.46 andll,
59Hz) [α)a” +89.3° (c=1.58 CHC
j! 3) Rf O, 33 (Toluene-AcOE
t10: 1) Elemental analysis, calculated value CzJz
e06 C, 69,89, H, 6,84%.

Actual value: C, 69, 63, 11, 6, 81%.

Example 29 32→33 Compound 32 (24.9g, 60.3 mo+o
f) was dissolved in 0.02M sodium methoxide (120d) and stirred at room temperature for 3 hours. Neutralized with Amberlyst 15. After the resin was filtered off, the residue was concentrated under reduced pressure and recrystallized from ethyl acetate-hexane to obtain 33 (19.6 g).

88%) 400 M II NMR (cDcf:+) δ5.92
7 (dddd, lit, J=5.50 6.41
16.79Hz.

Al1y+) , 5.311 (ddd, IH, J=
1.32 3.05°17.0911z, A11yl
), 5.206 (ddd, ill, J 1.22
゜3.05 and 10.37Hz, A11yl
), 4.836 (s, 2H.

■-CH,), 4.693.4.623 (2d, 2
H, J 11.60tlz.

■-coz), 4.373 (ill, H-1),
4.317 (ddt, IHJ 1.53.5
．． 19 and 12.82Hz, 81yl
), 4.095 (ddt, IH, J 1.38.6
．． 10 and 12.51Hz.

Al1yl), 3.988 (dd, ltl, J
4.25 and 11.7511z.

H-5), 3.302 (dd, IH, J 8.39
．． 11.75) 1z, H-5) α) n” 36
．． 8' (c 1.00 CHCl, +)RF O
,33 (Toluene-AcOEt5: 1) Elemental analysis, calculated value CZZ++□60°: C,71,3
3, H, 7,07% Actual value: C, 71,12; H,
7,13% Example 30 34→35 Promide 34 (61gt o, 15d) was mixed with dichloroethane (500d) and methanol (30m, 1.5m
of) and added tetra-n-butylammonium bromide (14 g + 44 mmol) at 60°C.
After stirring for 1.5 hours, the solvent was distilled off under reduced pressure. It was dissolved in chloroform, washed with water, and dried over magnesium sulfate. The solvent was distilled off under reduced pressure and the resulting oil was purified by flash silica gel column chromatography (1 kg of silica gel, 4:1 ethyl acetate, 1% triethylamine) to obtain orthoester 35 (53.7 g,
96%).

RF O,41,0,47(Toluene-^cO
Etl: 1) (17) DI7.4 (c 1
．． 62 CHCl1) Elemental analysis, calculated value c+sTo
□010: C, 49,72, H, 6,12%; Actual value: C, 49,79, H, 6,10%; Example 31 35→37 Compound 35 (52 g, 0.14 mol to 0.01 M
Dissolved in sodium methoxide (200d) at room temperature
Stir for hours. The reaction solvent was then distilled off under reduced pressure, and the residue was dissolved in anhydrous DMF (500d). While cooling with water, sodium hydride (33 g, oily 50%, 0.69 moj) was added, and then benzyl bromide (22d) was added dropwise.

After returning to room temperature and stirring for 1 hour, methanol was added to decompose excess benzyl bromide. The solvent was distilled off under reduced pressure, and the residue was dissolved in ethyl acetate and washed with water. After drying with magnesium sulfate, concentrate the residue under reduced pressure and flash the residue with silica gel column chromatography (1 kg of silica gel, l-ethylhexane-ethyl acetate lO:5:l) and 1% ethylamine.
) to obtain oily compound 37 (71.2 g, 9
8%).

Ry O, 35 (Toluene-AcOtitl O
: 1) Elemental analysis, calculated value C3゜113s 071
/411□0: C, 70,50; 11 6.80% Actual value: C, 70,55, 11,6,69% Example 3
2 37→38 Orthoester 37 (46.5g, 91.8 +
u+offi) was dissolved in acetic acid-water (9:l 500Id) and stirred under heating at 90°C for 5 hours. After the solvent was distilled off under reduced pressure, toluene was added and distilled off under reduced pressure. This operation was repeated three times to remove water. The residue was dissolved in pyridine (300d), acetic anhydride (50#+1) was added, and the mixture was stirred overnight. The solvent was concentrated under reduced pressure, and the residue was dissolved in chloroform, washed with 2M hydrochloric acid saturated deuterium chloride water and water, and dried over magnesium sulfate. The residue was purified by flash silica gel column chromatography (1 kg of silica gel, 15:1 ethyl acetate) to obtain Compound 38 (36.3 g, 74%) as an oil.

38 is a known compound Example 33 38→40 Compound 38 (10 g, 18.7 mmol) was DM
Dissolved in F (100d), hydrazine acetic acid (2,2
4 g, 24.3 mmof) was added. After stirring at 50°C for 2 hours, DMF was distilled off under reduced pressure, and the residue was dissolved in chloroform, washed with water, and dried over magnesium sulfate. Franche column chromatography (silica gel 850g
) to obtain 8.1 g (88%) of hemiacetal (40). (
α:βζ2:1) 500Mllz N M R α δ5.440 (t, J 3.24Hz, H-
1) RF O, 09 (Toluene-AcOEt
10: 1) Elemental analysis, calculated value CtqHst07
: C, 70,71; H, 6,55% Actual value: C, 70,47; , 1d) and diluted with trichloroacetonitrile 2.2rd (22 mmol) DBIJ (
130 μff1O, 9 mmol was added. After stirring at room temperature for 2 hours, the solvent was distilled off under reduced pressure. The residue was purified by Furanoshu silica gel column chromatography (90 g, toluene-ethyl acetate 1 ol) to obtain compound 41 (2
, 5g, 90%) was obtained.

500MH2NMR (CDCl2.) 66.529 (d, IH, J 3.56Hz
If-1), 5.507 (ad.

IL J 3.56 and 10.36Hz, H-
2) 4,962°J 6.14. 7.12Hz
H-5) 4.10 (m.

4.035 (dd, H-1, J 2.59 a
ndfl-3) 3.659 (dd, IH,
J 7.93 and H-6) 3.577 (d
d, LH, J 5.50 and H-6”) (Toluene-AcOEt 5:1) (
dd, IFI.

IH, H-4) 10.36) 1z.

9.2311z.

9.06Hz.

RF O,53 Example 35 Compound 41 (160 0.25 mmof) and Compound 33 (62 mg 0.17 mmof) were mixed with pre-dried molecular sieves AW-300 (
Carbon tetrachloride (di-component) was added and dissolved in a container containing 500 mg). While cooling to -20°C and stirring, 37 μl of trifluoroboron ethyl ether was added.

After 10 minutes, triethylamine was added to neutralize the mixture, and insoluble matter was filtered off. The reaction solution was diluted with chloroform, washed with water, and then dried over magnesium sulfate. Compound 42 (103%, 73%) purified by flash silica gel column chromatography and recovered acceptor (23%) were concentrated under reduced pressure.
■ 14%).

Compound 42 400MHz NMR (CDCl3) 65.820
(m, IH, A11yl)8.240 and
10.07Hz, H2S, 390 (dd, 1
8. J26), 5.237, 5.069 (2m, 2H, A11yl), 4.949 (d
, Ill, J 11.9011z.

■-GHz) 4.778 (d, IH, J 8.24
Hz, H-1b), 3.954 (d, IH,
J 2.75Hz, tl-4b), 1.772(s
+38+Ac) Rv O,44(Toluene-AcOt!t5
: 1) Elemental analysis Calculated value: C5Js+0+
I-HzO: C, 70,98; H+ 6.77%
Actual value: C, 71,20; H+ 6.60% Another synthesis example 3 of 42 38→39→42 Compound 38 (6.9 g, 13 mmoj2) was dissolved in methylene chloride (140 d), and the odor was reduced to 30% under water cooling. Hydrogen-acetic acid was added dropwise. After 4 hours, the reaction solution was poured into saturated deuterated water containing ice and stirred vigorously.

The organic layer was diluted with chloroform, washed with saturated deuterated water and water, and dried over magnesium sulfate. The solvent was distilled off to obtain Procyto 39. This was used in the next reaction without purification.

RF O, 64 (Toluene-AcOEt 2
: 1) Compound 33 (3.2g, 8.6+u+
oj2) and silver triflate (3.7g, 1
4.4+u+oj2) was placed in a container containing pre-dried Molecular Sheeps 4A (5 g), and the dichloroethane solution (3011 dl) of bromide (39) prepared above was added under an argon atmosphere while cooling with water.

After stirring for 3.5 hours, molecular sieves neutralized with triethylamine were filtered. It was diluted with chloroform, washed with water, and dried over magnesium sulfate. The residue was concentrated under reduced pressure and subjected to flash silica gel column chromatography (
Silica gel 400g toluene-ethyl acetate 15:1)
Compound 42 (3.8 g, 52%) was obtained.

Example 36 42→43 Compound 42 (432■, 0.511 n+moffi
) was dissolved in 0.05M sodium methoxide (4m) and stirred at 60°C for 2 hours. After returning to room temperature, Ambe
Neutralized with rlyst15. After removing the resin by filtration, the residue was concentrated under reduced pressure and recrystallized from methanol to obtain compound 43 (385g
94%).

400MHz NMR (CDCl3) δ5.848
(m, 1■, Al1yl), 5.226 (+++
, IH.

A11y Ri, 5.057 (Tsu, III, A11y
l), 4.885 (d, lit, J 11.29
Hz, ■-GHz), 4.9023 (d, 18. J
8.3B, +l-1b), 4.860 (d, 1
8゜J 11.29Hz, (ToCHri, 4.727
(d,ill.

J 12.20Hz, ■-GHz), 4.648 (d
, L.H.

J 11.90Hz, ■-CH,), 4.251 (d
dt, 18°J 1.53. 5.50 and 1
3.13Hz, A11yl), 4.058(d
dt, Ill, J 1.53. 5.80a
nd 12.82Hz, A11yl) RF O, 39
(Toluene-AcOEt5: 1) Elemental analysis, calculation (+! C49H5401°: C,7
3,30, H, 6,78% Actual value: C, 73,13,
H, 6,79% Example 37 Compound 44 (1,51 g, 3.24 mmol)
and compound 43 (1.30 g, 1.62 m+wo
Roughly dried molecular sieves 4A (
4g) and dissolved in anhydrous ether (10m).

Methyl triflate (44oμf, 3.89m) was cooled with water.
mol) was added. After returning to room temperature and stirring for 2 hours, the mixture was neutralized with triethylamine. After filtering through molecular sieves, it was diluted with ethyl acetate and washed with saturated deuterated water and saturated brine. After drying over magnesium sulfate, the residue was purified by flash silica gel column chromatography (400 g of silica gel, ethyl acetate 10:1) to obtain a mixture of compounds 45a and 45b (1,732 g, 87
．． 8%). This mixture was recrystallized from ethyl acetate-hexane to obtain Compound 45a (0,862 g). Flash silica gel column chromatography (
Compound 45a (0,280 g) was obtained by purification with 1 kg of silica gel (hexane-ethyl acetate 5:1) and recrystallization from ethyl acetate-hexane.

Compound 45a 400MHz NMR 65,853 (m, IH, A11y, 5.760
(d, IH, J 3.6611z, H-1c), 5
．． 326 (dq, IH, J 1.83 and17
．． 09Hz, A11yυ, 5.055 (dq, I
H, J 1.83 andlo, 68Hz, AI summer yl), 4.954 (d, IH, J 11
,60Hz.

[α) o” 51.0 (c 1.00. CF
ICj! 5) RF O,63(Toluene-Ac
OEt 5: 1) mp, 107.5 ~
108.5 °C elemental analysis, calculated value CyJszO+
4: C, 74,85; H, 6,79% Actual value:
C, 74,52: H, 6,71% Example 38 Allyl glycoside 45a (2,05g + 1.68
mn+of) to ethanol-benzene-water (7:3:1
,60r! rhodium tristriphenylphosphine chloride (160 mg, 0.17 mm
of) DABCO (381tg O, 34mmol
2) was added, and the mixture was stirred at 50°C for 12 hours under reflux for 3 hours. The solvent was distilled off under reduced pressure and the residue was diluted with acetone-water (9:l 5
HgC1z (1.6g 5.9
mmol2) HgO (36 mg.

0.17 vavaol) was added thereto, and the mixture was stirred at room temperature for 30 minutes.

The solvent was distilled off under reduced pressure, and the residue was dissolved in chloroform and washed with 10% potassium iodide solution. After drying with magnesium sulfate, flash silica gel column chromatography (silica gel, 200 g, toluene-ethyl acetate 6
:1) and purified with hemiacetal 46 (1.95g,
98%).

Example 39 46→49 Compound 46 (120■, 0.102 m5o l) was added to T
Dissolved in HF methanol (1:1.2d) and added 10% palladium-carbon 30w11. Stirred under hydrogen atmosphere overnight. The catalyst was filtered through Celite and mixed with methanol-water (1
: I washed it with 1). LH-20 (5g, MeOH
-Hzo 1:2) and purified with compound 49 (4
4.8ffig, 96%) was obtained.

500 MHz NMR (Dzo, 60°C) δ5.
376 (d, 0.71+, J=3.63Hz,
1-1aα)+5.297 (d, 0.7H, J
=3.96Hz, fl-1c), 5.274(
d, 0.3H, J=3.9611z, H-1c
), 4.875 (d.

0.311. J=7.92Hz, H-1a
β), 4.665 (d.

0.7t1. J=7.59Hz, If-1b)
, 4.628 (d, 0.3H.

J=7.5911z, lt-1b) (RT)65.
396 (d, 0.7H, J=3.63Hz,
H-1aα).

5.293 (d, 0.7H, J=3.9611
z, H-1c).

5.262 (d, 0.311. J=3.95
Hz, H-1c).

4.881 (d, 0.3H, J=7.5911
z, ll-1a β).

4.652 (d, 0.7H, J=7.5911
z, H-1b).

4.619 (d, 0.3H, J=7.59Hz,
H-1b).

4.520 (q, 0.711. J=7.2
6Hz, H-5).

4.463 (q, 0.3H, J, = 1.26H
z, H-5).

1.23 (d, 0.3H, J=6.59)1z
, lt-6c).

1.224 (d, 0.7H, J=6.6011
z, H-6c)Ccx]2S-68,4° (c
1.0011zO)RF O,31(n-BuOHEt
OHtlzo 2:1:1) Elemental analysis, calculated value CI? H3゜0,4・y2++20
:C, 43, 68; 11. 6.68% actual value: (
:, 43.71; 11.6.55% Example 40 0b Compound 49 (25.8■, 56.3μmol) was dissolved in pyridine (ld), and acetic anhydride 85μm900μ
mof) was added and stirred at room temperature overnight. The solvent was evaporated under reduced pressure, and the residue was dissolved in chloroform and washed successively with 2N hydrochloric acid saturated deuterated water and water. After drying with magnesium sulfate, the residue was subjected to flash silica gel column chromatography to obtain 3 g of silica gel and toluene (38 ml, 81%).

500 MHz NMR 50a: 66.186 (d, Ill,
J=3.9611z, tl-1a).

4.558 (d, IH, J=7.58Hz,
ll-1b), 4.337(q, LH, J=
6.6011z, H-5c), 1.9-2.3
(27H, 9Ac), 1.198 (d,
3H, J=6.59Hz, H-6c) 50b:
δ 5.689 (d, Ill, J=6.
93Hz, lt-1a).

4.554 (d, 18. J=7.59Hz
, H-1b), 4.394(q, Ill,
J=6.69Hz, H-5c), 1.9~2.3
(2711, 98c), 1.181 (d,
311. J=6.60Hz, H-6c) RF
O,36()Lueso Ac0Et 1:1) Example 41 50a,b →51 Compound 50a,b (300■, 0.359+nmo
1) was dissolved in anhydrous DMF, and then water-cooled and stirred dorazine-acetic acid (50 μm, 0.54 mmol) was added. After stirring at 50°C for 1 hour, the solvent was distilled off under reduced pressure, and the residue was dissolved in chloroform and washed with saturated deuterated water and water.

After drying magnesium sulfate, the compound 51 (217 g,
76%).

500 Mllz NMR (CDCf3) 1.95~
2.25 (24H, 8c), 1.1B9. 1
．． 176 (2d, 3H, J=6.47Hz,
ll-6c) R,0,41()ruhen-8cOEt
1: 1) Elemental analysis, calculated value C3:1l14
1,0□2:C,49,88; If, 5.8
3% actual value: C, 49,76; H, 5, 86% Example 42 51→52 Compound 51 (300 mg, 0.40 mn+of) was dissolved in methylene chloride (2d), and trichloroacetonitrile (207 μf, 2 .0 mmol), D B
U (12 μf, 0.08 mmol) was added. After stirring at room temperature for 2 hours, the reaction solution was concentrated under reduced pressure. The residue was immediately subjected to flash silica gel column chromatography (15 g of silica gel, toluene-ethyl acetate 1:1).
) and containing a small amount of starting material 51, compound 52 (3
10■, 82%).

RF O,60(CI(C/!,1-Acetone
5: l) Example 43 Compound 52 (310 mg, 0.334 mmof) was pre-dried on Molecular Sieves AW-300 (4
00■) and dichloroethane (dissolved in 4 ml). Next, tributyltin methyl sulfide (566+ng, 1°67I) was added with stirring.
IIInol), trifluoroboron diethyl ether (49 μf, 0.40 mmof) was added. After 30 minutes, the mixture was neutralized with triethylamine, the molecular sieves were filtered off, diluted with chloroform, and washed with water.

After drying with magnesium sulfate, the residue was purified by repeating flash silica gel column chromatography (20 g of silica gel, toluene-ethyl acetate-2:l) twice to obtain compound 53 (177μ, 64%).
I got it.

500 MHz NMR (CDC1*) 65.332
(d, IH, J=4.27Hz, H-1c) 5
．． 257 (d, IH, J=5.49Hz, H-1a
), 4.558 (d, LH, J=7.63Hz,
ll-1b), 4.329 (q, 18. J=
6.40. H-5c).

4.060 (dd, ill, J=5.49 and 1
0.07ttz, tl-2a).

3.951 (dd, Ill, J=7.63 and 1
0.07Hz, H-2b).

2.216.2.150.2.144.2.083.2
．． 065.2.029°1.972. 1.96B,
1.965 (9S, 27H, 8Ac and SMe)
.

1.245 (d, IH, J=6.7111z, H
-6c) Cff” -79,3° (c 1.00
CICIt 3) R,0,50(1-Lueso Ac0Et 1 : 1
) Elemental analysis, calculated value C5allaeO□, s-'/
2u, o: C, 48, 98, 11, 15, 80; s
+ 3.85% actual value: C, 48,78; H, 5,
79; S, 3.56% Example 44 54→55 Compound 54 (500, 0.79 mmoj2) was dissolved in dichloromethane (10), and trichloroacetonitrile (400, czf, 3.9 mmoj2) was added.

DBU (23d, 0.16 mmoj2) was added under water cooling and stirred for 1 hour. The solvent was distilled off under reduced pressure, and flash silica gel column chromatography (silica gel 50g
, t-ethyl acetate 1:1) to give compound 5.
5 (410μ, 70%) was obtained.

400M)lz')INMR δ8.656 (S, Ill, NH), 6.490
<a, IH, lt-1a), 4.547 (d,
Ill, )I-1b), 2.120.2.097.2
．． 045°2.033.2.016.2.010.1.
989 (7S, 21H, Ac) RF O, 3B (
CHCj! :1-Acetone 10:1)
Example 45 55+18→56 Compound 55 (31■, 42 μl 1101), Compound 18
(50 μmol, 49 μmol) was placed in a container containing pre-dried molecular sieves AW-300 (400 μmol), and then 1,2-dichloroethane (2d) was added and dissolved. Cool to -20°C under an argon atmosphere and add trifluoroboron ethyl ether (6 μl, 49 μl).
mof) was added. After stirring for 30 minutes, triethylamine was added to neutralize. It was diluted with chloroform, filtered through molecular sieves, and washed with water. Dry with magnesium sulfate and concentrate under reduced pressure.The residue is subjected to flash silica gel column chromatography (13 g of silica gel) with ethyl acetate.
:1) to obtain compound 56 (49.9 mm, 80%).

400 MIIz' HNMR (CDCl 3) 63.
779 (S, 38.+0CHa), 2.060
(311).

1.991 (38), 1.974 (311),
1.965 (6H), 1.945 (3H), 1.
847 (3t(), (6S, 2111. Ac)
R,0,58 (Toluene-AOEt2:1) Example 46 56→57 Compound 56 (470■, 0.294 mmof) was dissolved in acetonitrile-water (4:1.10d) and cerium ammonium nitrate (CAN) was added under water cooling. (320■, 0
．． 59n+moI! , ) was added. After 10 minutes, the mixture was diluted with ethyl acetate and washed with saturated sodium chloride water and saturated brine. After drying with magnesium sulfate, the residue was concentrated under reduced pressure and subjected to flash silica gel column chromatography (50 g of silica gel,
) and purified with ethyl acetate (2:1) to give compound 57 (
290+ng, 66%).

400Mtlz'tlNMR(CDCl3)δ2
．． 072.2.001.1.995.1.989.1.
970.1.943 (6S, 21+1.8C) [α] 24-12.2° (c 1.00 ClIC
l:l)R,0,64()cOEt 1
: 1) Elemental analysis, calculated value C8゜11920□
1l=C, 63,99; I+, 6.18% actual value:
C, 63,63; H, 6, 21% Example 47 53 +57→58a (72■, 48 μmol), cupric bromide (24■, 10
8μmoj2), tetra n-butylammonium bromide (4,7■, 14μmof), mercuric bromide (39μmof),
, 108 μmol was placed in a container containing pre-dried molecular sieves 4A, ether was added under an argon atmosphere, and the mixture was stirred for 5 hours. Chloroform and saturated aqueous solution were added, and after stirring for 5 minutes, insoluble matter was removed by filtration through Celite, and the mixture was dried over magnesium sulfate. The residue was concentrated under reduced pressure and subjected to flash silica gel column chromatography (30 g of silica gel, toluene-ethyl acetate) and then Bio
-Purified with Beads 5X-3 column (5g, toluene) and purified with a mixture of 58a and 58b (7:1.23■, 2
1%). The mixture was subjected to preparative TLC (developed twice with 1-luesoethyl acetate 3:2 and twice with 1:1).

Compound 58a 500 MHz NMR (CDCjl! 3) δ 2.
201. 2.110. 2.096°2.015.
2.003. 1.993°1.953. 1.940
．． 1.936°2.068. 2.045°1.96B, 1.964, 1.955°1.862
(15S, 458. Ac).

1.187 (d, 31L J=6.47Hz
, ll-6j)(α)”-11,5”
(C1,00CHCffi3)R,0,40()Ruesor^cOEt 1 : 1) Elemental analysis, calculated value C11311136049・^cOEt: C,59,
39; 6.13% Actual value: C, 59,09; H, 5
, 99% Example 48 8a Deprotection of Compound 58a Compound 58a (4.5 mg, 0.2 μmol) was dissolved in 0.05 M sodium methoxide methano-J solution (1
ml)? The mixture was stirred at room temperature for 4 hours. Neutralize with Amberlyst 15, remove the resin by filtration, and remove the solvent with methanol.
Water (changed to 1:1.1 m). 10% palladium on carbon (
4) was added, and the mixture was stirred overnight under a hydrogen atmosphere. After filtration through Celite, the product was purified using a 5 ephadex G25 column (5 g, water) to obtain Compound 59a (2.1 mg, 92%). 500MIIz NMR (DJ, 60°C)6
5.274 (d, IH, J=3.6711z, I
f-Iα), 5.220 (d, , J=3.66
Hz, tl-1a cx), 5.118 (d,
IH, J=3.6611z, H-1e), 4.65
8 (d, , J=7.94Hz, ll-1aβ
) + 4.618 (d, III, J=7.631
1z, ll-1h), 4.528(d, 18.
J=7.93Hz, H4b, c or dL 4.5
08(d, 211. J=7.6311z, H-1
b, c or d), 1.255(d, 3tl,
J=6.7111z, H-6j)RrO,15(n
-BuOHEtOIl)Izo2:1:
1) Example 49 52 + 57 → 58b Compound 57 (51■, 30μm) was placed in a container containing pre-dried molecular sieves AW-300, and compound 52 (32μ, 34μm) was placed in a container containing pre-dried molecular sieves AW-300.
A solution of n+ol in 1,2-dicoo ethane (ld) was added. Cool to -23°C and 10μ of trifluoroboron diethyl ether! was added, stirred for 15 minutes, and then neutralized with triethylamine.

After diluting with chloroform and removing the molecular sieves by filtration, the mixture was washed with water, saturated deuterated water, and water, and dried over magnesium sulfate. A mixture (20 ml) of the concentrated residue under reduced pressure was obtained by flash silica gel column chromatography (12 g of silica gel) with ethyl acetate (3:2). The mixture was purified using old 0-Beads S-X3 column chromatography (SX-315g, toluene) to obtain compound 58.
b(4,9■) was obtained. (Total yield 11.2■, 14%
) Example 50 58b→59b Compound 58b (601 ng, 2.6 μmol) was added to 0.0
2 M sodium methoxide-methanol solution (0,5
ml1) and stirred for 2 hours. Amberlys
After neutralization at t 1s and filtering off the resin, the solvent was distilled off under reduced pressure.

Dissolve the residue in methanol-water (2:1.1-) and dilute for 10
% palladium on carbon (1 .mu.) was added and stirred overnight.

After filtering the catalyst through Celite, the afi residue was filtered under reduced pressure.
Compound 59b was purified with adexc-25 (5g water)
(2,3111 g, 79%) was obtained.

R,0,12 (butanol-ethanol-water 2:1:
1) Example 51 53+25=60a (77■, 0.039nw+oIl), 2nd bromide
Copper (13.5 mg, 0.060 mmoj2), tetra-n-butylammonium (2■, 0.006 mm
of), mercuric bromide (22■, 0.06 mmof)
Molecular sieves 4 pre-dried
The mixture was placed in a flask containing A (200 ml), and diethyl ether (2 relative) was added under an argon atmosphere. After stirring at room temperature for 16 hours, the mixture was diluted with chloroform, saturated sodium chloride water was added, and the mixture was stirred for about 5 minutes. The organic layer was filtered through Celite, washed with water, and dried over magnesium sulfate. Flash silica gel column chromatography (silica gel 15g,)
ethyl acetate 1:1), gel permeation (
Biobeads 5X-220g, toluene) and mixture 60a and 60b (21ffig, 26% α:
β#3: 1) was obtained. This mixture was analyzed by preparative TLC (
It was purified by developing with carbon tetrachloride-acetone 5:2.3 times and further purified again (with chloroform-acetone 7:I, developing twice) to obtain 8.7 mg of Compound 60a.

60a: 500MIIz NMR (CDCl2)
δ 2.214.2.125.2.115.2.064
．． 2.053°2.04B, 2.014.2.010
．． 2.008X2.2.003゜1.997.1.98
L 1.976, 1.963.1.956°1.954
．． 1.928.1.921 (], 9S, 57H, 1
9Ac) 1.203 (d, 3H, J=6.6011
z, H-6j) [α) n +18.3' (C
O,87CHCj23)R,0,17()Rueso Ac
0Et 1 : 1) Elemental analysis of mixture of 60a and 60b, calculated value CI: IIH1□. 0&I:C,5
7,83,)1. 6.30% Actual value: C, 57,43; H, 5,93% Example 52 60a → 61a Deprotection of compound 60a Compound 60a (8.7 mg, 3.2 μmof) was added to 0.05 M sodium methoxide methanol. The solution was stirred at room temperature for 5 hours. After neutralizing with Amberlyst 15 and filtering it off, it was dissolved in methanol-water (2:1, lxi), 10% palladium-carbon (5 mg) was added, and the mixture was stirred overnight under a hydrogen atmosphere.The catalyst was filtered through Celite. The residue was removed and purified using an Ephadex G-25 column (5 g, water) to obtain Compound 61a (2.6 mm, 54%).

500MHz NMR (DzO, 60°C) 65.27
5 (d, LH, J=3.66Hz, H-1j),
5.220(d, J=3.67Hz, It
-1aα)+5.118 (d, LH, J=3.9
6Hz, H-1e), 4.940.4.929 (d
, 211. J=3.97Hz.

H-1f and g), 4.658 (d, J=7
．． 94Hz, Lla β).

4.621 (d, 1B, J=7.13Hz, H
-1b, c or d).

4.535 (d, 28. J=8.24Hz, H
-1b, c or d).

1.257 (d, 3H, J=6.71Hz,
H-6j)RrO,17(n-BuOHEtOHH
zo 2 : 1 : 1) Example 53 b a 0.066 mmof), tetra-n-butylammonium proscito (31 g, 0.01 mmol, mercuric bromide (24 μ, 0.066 m+++ol) were dried in advance. Sif, - Molecular Thieves 4A (150
①-), and diethyl ether-dichloroethane (4:1.1.5 d) was added thereto and dissolved. Stirred overnight at room temperature. After adding saturated aqueous solution and stirring for about 5 minutes, the mixture was filtered through Celite, and the organic layer was washed with aqueous solution and water.

After drying magnesium sulfate, the residue was concentrated under reduced pressure and subjected to flash silica gel column chromatography (20 g of silica gel).
,) ethyl acetate 4:1) followed by preparative TLC
Compound 62a (20 μ, 38%), Compound 62b (4
■), unreacted compound 17 (32■, 55%) was obtained.

Compound 62a 500 MHz NMR (CDCjl! 3) 64.5
92 (d, III, J=7.3311z, H-
1h), 4.481(d, IH, J=8.06Hz
, H-1a or b), 4.474 (dIII,
J=7.69Hz, H-1a or bL 4.22
0 (q, III, J=6.60flz, H-
5j), 2.200.2.129.2.046.2.
0201.9B0.1.970.1.963.1.84
7 (8S, 24H, 8Ac) 1.232 (d,
3H, J=6.22Hz, H-6j) (α) D −
6,9° (c 1.06.CIICj23)Rr O
,3B (CIIcjl! 3-^cetone 2
0: 1) Elemental analysis, calculated value CIl? H.I. 20
．． 3□: C, 62,96; H, 6,19 Actual value: C, 62,95, H, 6, 24 Example 54 62a → 63a Compound 62a (10,6■) in IM sodium methoxide l relative The mixture was dissolved and stirred for 4 hours. ^mberlyst1
After neutralization with 5, the solvent was methanol-water (2:1.1In1
), 10% palladium-carbon (2) was added, and the mixture was stirred overnight under a hydrogen atmosphere. After celite filtration, 5eph
Purification with adex G25 column gave compound 63a. (Quantitative) 500M1lz NMR (DzO, RT) 65.280
(d, J 4.03Hz), 5.268 (d,
J 4.03Hz).

5.216(d, J 3.6611z), 5.11
1 (d, J 3.66Hz) Example 55 7 + 17 ba (176 mg, 0.20 mmof), cupric bromide (
44■, 0.20 a+moi! , ) , tetra-n-
Butylammonium bromide (6,4■, 0.02 m
Place the sample into a container containing pre-dried molecular sieves 4A (150 μg), and add diethyl ether-dichloroethane (4:1.2 relative) under an argon atmosphere.
was added and dissolved. The mixture was immediately cooled on ice, allowed to warm to room temperature for 30 minutes, and stirred overnight. Chloroform and saturated deuterated water were added, and the mixture was stirred for 5 minutes and then filtered through Celite.

The organic layer was washed with saturated deuterated water and water, and dried over magnesium sulfate. The residue was concentrated under reduced pressure and subjected to flash silica gel column chromatography (20 g of silica gel, toluene-
Purification with ethyl acetate 10:1) gave compound 28a (51■,
40%), mixture 73■, unreacted compound 17 (94■
, 53%). The mixture was further purified by preparative TLC (toluene-ethyl acetate 6:1) to yield compound 28a.
(16■, 12%) and compound 28b (27■, 21%)
I got it. A portion of Compound 28a was recrystallized from ether-hexane and used as a sample for analysis.

500 MHz NMR (CDCl3) 64.52
1 (d, IH, J=3.66Hz.

(d, IH, J=8.06Hz, H-1a).

9.16Hz, H-4a), 3.638 (t.

3.396 (dd, IH, J=3.67HzR
,0,53()Luesor AcOEt m, p, 109-111°C Elemental analysis, calculated value Cl1IH11401511-1e
), 4.500 3.696 (t, 18., y=It(, J
=8.98Hz, ll-4b).

and 9.1611z, L2e) 4: l) C, 74,75; H, 6,59% Actual value: C, 74,65; II, 6.58% Example 56 28a→29a Deprotected compound of compound 28a 28a (7.8 mg, 6.1 μmol
Dissolved in THF-methanol (1:1, Id) to 10%
Palladium-carbon (3) was added and stirred overnight. The reaction solution was filtered through Celite and washed with methanol-water (1:1). Purification on a Sephadex G-25 column (5 g, water) gave compound 29a (2.3 mg, 89%).

500 Mllz NMR (DzO, 50°C) 65.
219 (d, 0.2H, J=3.66Hz, H-
1a a).

4.931 (d, 0.8H, J=3.671 (z,
H-1e), 4.916 (d.

Claims (4)

[Claims] (1) Zyloglucan oligosaccharide represented by the formula below ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) Zyloglucan oligosaccharide Xy represented by the following formula
lα1→6Glcβ1→4Glc (3) Zyloglucan oligosaccharide represented by the formula below ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (4) Zyloglucan oligosaccharide Fu represented by the following formula
cα1→2Galβ1→2Xylα1→6Glcβ1→
4Glc