KR101571765B1

KR101571765B1 - Novel Pulsatilla saponin D derivatives, preparation and anticancer use therof

Info

Publication number: KR101571765B1
Application number: KR1020130096918A
Authority: KR
Inventors: 정만길; 정원윤; 박광균
Original assignee: 연세대학교 산학협력단
Priority date: 2013-08-14
Filing date: 2013-08-14
Publication date: 2015-11-25
Also published as: KR20150019736A

Abstract

The present invention relates to a novel anticancer agent, such as a polysaccharide derivative, a method for preparing the same, and an intermediate thereof. The present invention can mass produce full-particulate saponin D (PSD) derivatives that can be developed as a global novel cancer-treating agent for lung cancer originating from natural sources through efficient pre-synthesis from inexpensive raw materials, and PSD derivatives are very effective against lung cancer.

Description

Novel pulsatilla saponin D derivatives, preparations and anticancer use therofs,

The present invention relates to a novel anticancer agent, such as a polysaccharide derivative, a method for preparing the same, and an intermediate thereof.

Saponins are glycosides containing triterpenes or steroids and are found in many plants and in certain marine organisms with a variety of biological and pharmaceutical activities. (1 → 4) -α-L-lambda (1 → 2) -α-L-arabinoside}, α-he Serine, δ-hederin, calopanaxsaponin A, calopanax saponin I and sapindoside C show cytotoxicity and hemolytic activity. α-Heterine and δ-Heterine have molluscicidal insecticidal activity and cytotoxic effects, and α-Heterinine exhibits strong hemolytic and cytotoxic effects in various cancer cell lines. Of the heparanin-containing saponins, Hedera Collide A (Fullatilla saponin D: PSD) has strong in vitro anti-cancer activity, as well as strong in vivo antitumor activity than Taxol and oxorubicin in mice suffering from Lewis lung cancer . In addition, the present inventors have reported the full synthesis of full-particulate saponin D (Kim, M .; Lim, E .; Jung, M. Tetrahedron 2013, 69, 5481-5486).

There is a problem that the natural saponin product can be obtained only in a small amount. This problem can be solved by chemical synthesis and can easily provide a suitable compound for structure-activity relationship (SAR) studies or other studies. According to the results of SAR, saponin containing hederagenin having a free carboxy group at the C-28 position has stronger anticancer activity than the sugar or other substituent. The present inventors synthesized saponins having various sugar moieties at the C-3 position of hyderazenin and evaluated their in vitro anti-cancer activity.

It is an object of the present invention to provide novel derivatives of Fusattilis saponin D, a process for producing the same, and a pharmaceutical composition for treating cancer comprising the same.

In one embodiment of the invention, there is provided a compound of formula I:

Formula I

Wherein R ₁ and R ₂ are each independently of the other hydrogen, arabinopyranosyl, rampopyranosyl, glucopyranosyl or mannopyranosyl. In yet another embodiment, R < ₁ > is a compound that is rhamnopyranosyl or mannopyranosyl. In another embodiment, the R < ₂ _> is mannopyranosyl, arabinofuranosyl, or hydrogen. In another embodiment, the R < ₂ > is hydrogen. In another embodiment, the R ₁ is mannopyranosyl and R ₂ is hydrogen. In another embodiment, the arabinopyranosyl is 2,3,4-tri-O-benzyl- alpha -L-arabinopyranosyl and the rampiniranosyl is 2,3,4-tri-O-benzyl -? - L-rhamnopyranosyl, the glucopyranosyl is 2,3,4,5-tetra-O-benzyl-? -D-glucopyranosyl, the mannopyranosyl is 2,3,4,5 -Tetra-O-benzyl- alpha -D-mannopyranosyl.

Also provided in one embodiment of the invention are compounds of formula II:

(II)

In this formula,

R ₁ , R ₂ and R ₃ are each independently of the other hydrogen, arabinopyranosyl, ramanopyranosyl, glucopyranosyl or mannopyranosyl. In another embodiment, the R ₁ is arabinopyranosyl, glucopyranosyl, mannopyranosyl or rampopyranosyl. In another embodiment, the compound is wherein R < ₂ _> is hydrogen or rhamnopyranosyl. In another embodiment, the R < ₃ > is hydrogen. In yet another embodiment, at least one of R < ₂ > and R < ₃ > is hydrogen. In another embodiment, the arabinopyranosyl is? -L-arabinopyranosyl, the ramponopyranosyl is? -L-rhamnopyranosyl, the glucopyranosyl is? -D-glucopyranosyl, Wherein the mannopyranosyl is? -D-mannopyranosyl.

Further, in one embodiment of the present invention, there is provided a pharmaceutical composition for treating cancer comprising the above compound. In another embodiment, the cancer is a lung cancer.

Also, in one embodiment of the present invention, there is provided a process for preparing a compound of formula (I), comprising: (i) introducing a leaving group in the form of a trichloroacetimidate to a compound of formula (ii) reacting an intermediate of formula (IV), formed in step (i), with a compound of formula V: And (iii) deprotecting the compound produced in step (ii) to synthesize the compound of formula (I).

Formula I

(III)

Formula IV

Formula V

Wherein R ₁ and R ₂ are each independently of the other hydrogen, arabinopyranosyl, rampopyranosyl, glucopyranosyl or mannopyranosyl. In yet another embodiment, R < ₁ > is a method wherein R < ₁ _> is rhamnopyranosyl or mannopyranosyl. In another embodiment, R ₂ is mannopyranosyl, arabinopyranosyl, or hydrogen. In another embodiment, there is provided a process wherein said R < ₂ > is hydrogen. In another embodiment, R ₁ is mannopyranosyl and R ₂ is hydrogen. In another embodiment, the arabinopyranosyl is 2,3,4-tri-O-benzyl- alpha -L-arabinopyranosyl and the rampiniranosyl is 2,3,4-tri-O-benzyl -? - L-rhamnopyranosyl, the glucopyranosyl is 2,3,4,5-tetra-O-benzyl-? -D-glucopyranosyl, the mannopyranosyl is 2,3,4,5 -Tetra-O-benzyl- alpha -D-mannopyranosyl.

Also, in one embodiment of the present invention, there is provided a process for preparing a compound of formula (I), comprising: (i) introducing a leaving group in the form of a trichloroacetimidate to a compound of formula (VI) (ii) reacting an intermediate of formula (VII), which is produced in step (i), with a compound of formula (V) And (iii) deprotecting the compound produced in step (ii) to synthesize the compound of formula (II).

(II)

VI

Formula VII

Formula V

Wherein R ₁ , R ₂ and R ₃ are each independently of the other hydrogen, arabinopyranosyl, rampopyranosyl, glucopyranosyl or mannopyranosyl. In another embodiment, the R ₁ is arabinopyranosyl, glucopyranosyl, mannopyranosyl or rampopyranosyl. In yet another embodiment, the R < ₂ _> is hydrogen or ramonopyranosyl. In yet another embodiment, R ₃ is hydrogen. In yet another embodiment, at least one of R < ₂ > and R < ₃ > is hydrogen. In another embodiment, the arabinopyranosyl is? -L-arabinopyranosyl, the ramponopyranosyl is? -L-rhamnopyranosyl, the glucopyranosyl is? -D-glucopyranosyl, Wherein the mannopyranosyl is? -D-mannopyranosyl.

Hereinafter, the entire synthesis process of the full-particulate D saponin derivative will be described.

① Synthesis of compounds 5a to 5i

Arabinose moiety 1, which is a glycosyl acceptor, was stereoselectively and stereoselectively glycosylated with donor and benzoylated trichloroacetimidate a to d to synthesize disaccharides, the following compounds 2a to 2d (Karen, P., Martin, C., Laurence, VN Eur. J. Org. Chem., 2004, 1588-1603; Schmidt, RR, Kinzy, W. Adv. Carbohydr. Chem. Biochem., 1994, 50, 21-125; , Jurisch, C. Tetrahedron: Asymmetry 2000, 11, 3403-3418, and Bernd, B., Richard HF, Folkert R., Oleg AZ Carbohydr. Res. 1999, 315 148-158). Then, the acetyl group was deprotected using acetyl chloride to synthesize the following compounds 3a to 3d (Byramova, NE; Ovchinnikov, MV, Bakinovskii, LV, Kochetkov, NK Carbohydr. Res. The compound a to d were glycosylated at the C-4 free hydroxyl group of the above 3a to 3d under the promoter TMSOTf at -78 ° C to obtain trisaccharides 4a to 4g. In the same manner, the free hydroxy groups of C-3 and C-4 of compound 6 as glycosyl acceptors were stereoselectively glycosylated with the donors b and d (Schmidt, RR, Kinzy, W. Adv. Carbohydr. Chem. Biochem. 1994, 50, 21-125 and Bernd, B., Richard HF, Folkert R., Oleg AZ, Carbohydr. Res., 1999, 315 148-158). The benzyl group at the C-1 position of the compound 2d and 4a to 4h was deprotected selectively using Pd / C catalyst under H ₂ to obtain 5a to 5i.

Ara = ^a 2,3,4- tree -O- benzyl -α-L- arabino-pyrazol nosil, Rha ^b = 2,3,4- tree -O- benzyl -α-L- ramno pyrazol nosil, Glu ^c = 2,3,4,6-tetra-O-benzyl- beta -D-glucopyranosyl, Man ^d = 2,3,4,6-tetra-O- benzyl- 留 -D-mannopyranosyl

(2) Synthesis of compounds 10a to 10i

CCl ₃ CN and DBU were used to treat compounds 5a to 5i to obtain trichloroacetimidate moieties 7a to 7i as glycosyl donors. These compounds were further glycosylated with protected Heterangenine (8) to give fully protected PSD derivatives 9a to 9i. All deprotection of the trisaccharide saponin derivative was carried out in one step (in situ). TBDPS groups were deprotected by TBAF and all benzoyl groups and acetyl groups were deprotected using potassium t-butoxide to give saponin derivatives 10a-10i with arabinose-core.

Ara = ^a 2,3,4- tree -O- benzyl -α-L- arabino-pyrazol nosil, Rha ^b = 2,3,4- tree -O- benzyl -α-L- ramno pyrazol nosil, Glu ^c = 2,3,4,5-tetra -O- benzyl -β-D- glucoside pyrazol nosil, Man ^d = 2, 3,4, 5-tetra -O- benzyl -α-D- manno pyrazol nosil, Arae = α -L-arabinopyranosyl, Rha ^f =? -L-laminopyranosyl, Glu ^g =? -D-glucopyranosyl, Man ^h =? -D-mannopyranosyl

(3) Synthesis of compounds 15a to 15d and compounds 20a to 20c

In order to synthesize saponins having a rhamnose-core, Receptor 11 was glycosylated with donors a to d under standard conditions to give disaccharide moieties 12a to 12d. Hydrolysis of the isopropylidene groups of 12a to 12d yielded diol compounds 13a to 13d in a yield of 84 to 91%. Benzoylation of the diol moieties of compounds 13a-13d followed by selective deprotection of the resulting benzyl group of protected 14a-14d afforded compounds 15a-15d. Compounds 13c and 18 were reacted with triethanolacetate / TsOH followed by deprotection with successive acetic acid to give compounds 16 and 19. Compounds 16 and 19 were synthesized by glycosylation using donors a to c, and compounds 20a to 20c were obtained using hydrogen gas under Pd / C catalyst.

(4) Synthesis of Compound 23a to Compound 23g

To glycosylation, the compound 15a to 15d and 20a to 20c to CCl ₃ with the CN and DBU converted to acetamido imidate of 21a to 21g trichloroethane, and the glycosylation of these compounds into compounds 8 fully-protected 4 22g to 22g of saccharides were obtained. TBDPS and benzoyl groups were then deprotected using TBAF and potassium t-butoxide to give 23a-23g of a saponin derivative having a Raman-core.

Ara = ^a 2,3,4- tree -O- benzyl -α-L- arabino-pyrazol nosil, Rha ^b = 2,3,4- tree -O- benzyl -α-L- ramno pyrazol nosil, Glu ^c = D-glucopyranosyl, Man ^d = 2,3,4,6-tetra-O-benzyl-? -D-mannopyranosyl, Ara ^e = α-L-arabinopyranosyl, Rha ^f = α-L-laminopyranosyl, Glu ^g =? - D-glucopyranosyl, Man ^h =? -D-mannopyranosyl

The pharmaceutical compositions of the present invention may further comprise suitable carriers, excipients and diluents conventionally used in the manufacture of pharmaceutical compositions.

The pharmaceutical composition of the present invention may be formulated in the form of powders, granules, tablets, capsules, suspensions, emulsions, syrups, aerosols and the like, oral preparations, suppositories and sterilized injection solutions according to a conventional method Examples of carriers, excipients and diluents that can be contained in the composition containing the extract include lactose, dextrose, sucrose, sorbitol, mannitol, xylitol, erythritol, maltitol, starch, acacia rubber, alginate, gelatin, calcium phosphate, Calcium silicate, cellulose, methylcellulose, microcrystalline cellulose, polyvinylpyrrolidone, water, methylhydroxybenzoate, propylhydroxybenzoate, talc, magnesium stearate and mineral oil. In the case of formulation, a diluent or excipient such as a filler, an extender, a binder, a wetting agent, a disintegrant, or a surfactant is usually used. Solid formulations for oral administration include tablets, pills, powders, granules, capsules and the like, which may contain at least one excipient such as starch, calcium carbonate, sucrose ), Lactose, gelatin and the like. In addition to simple excipients, lubricants such as magnesium stearate and talc are also used. Examples of the liquid preparation for oral use include suspensions, solutions, emulsions, and syrups. In addition to water liquid paraffin, which is a simple diluent commonly used, various excipients such as wetting agents, sweeteners, fragrances, preservatives and the like may be included. Formulations for parenteral administration include sterilized aqueous solutions, non-aqueous solutions, suspensions, emulsions, freeze-dried preparations, and suppositories. Examples of the suspending agent include propylene glycol, polyethylene glycol, vegetable oil such as olive oil, injectable ester such as ethyl oleate, and the like. Examples of suppository bases include witepsol, macrogol, tween 61, cacao butter, laurin, glycerogelatin, and the like.

The preferred dosage of the pharmaceutical composition of the present invention varies depending on the condition and the weight of the patient, the degree of disease, the drug form, the administration route and the period, but can be appropriately selected by those skilled in the art. However, for the desired effect, the composition of the present invention is preferably administered at 0.2 to 200 mg / kg, preferably 2 to 100 mg / kg, per day. The administration may be carried out once a day or divided into several times. The dose is not intended to limit the scope of the invention in any way.

The pharmaceutical composition of the present invention can be administered to mammals such as rats, mice, livestock, humans, and the like in various routes. All modes of administration may be expected, for example, by oral, rectal or intravenous, intramuscular, subcutaneous, intra-uterine or intracerebroventricular injections.

The present invention can mass-produce novel derivatives of Fusattilis saponin D through efficient pre-synthesis from inexpensive raw materials, which has excellent anti-lung cancer activity.

Hereinafter, the present invention will be described in detail with reference to the following examples. However, the following examples are illustrative of the present invention, and the contents of the present invention are not limited by the following examples.

Example

Example 1. Preparation of compounds 2a to 2d

(1.5 mmol) of the glycosyl acceptor in the presence of TMSOTf (0.3 mmol) in CH ₂ Cl ₂ at -78 < 0 > C was reacted stereoselectively with donor benzoylated trichloroacetimidate a to d Glycosylated to obtain disaccharides 2a to 2d in a yield of 75 to 82%.

2,3,4-O- Tribenzoyl -α-L-O- Arabinopyranosyl - (1) -4-O-acetyl-2-O- Benzoyl -1-O-benzyl-a-L- Arabinophilanoside (2a)

White _{solid, R f = 0.31 (n-} Hexane / EtOAc, 4: 1, v / v) [α] D + 165 ° (c 0.1, CHCl 3) 1 H NMR (250 MHz, CDCl 3) 7.04 - 8.08 ( m, 25 H) 5.65 (dd , J = 8.13, 5.61 Hz, 2 H) 5.47 - 5.56 (m, 2 H) 5.28 - 5.35 (m, 1 H) 4.97 (d, J = 5.53 Hz, 1 H) 4.71 (d, J = 12.79 Hz, 1 H) 4.48 - 4.58 (m, 2 H) 4.26 (dd, J = 12.56, 4.66 Hz, 1 H) 4.10 - 4.22 (m, 2 H) 3.85 (dd, J = 12.48 , 2.21 Hz, 1 H) 3.55-3.64 (m, 1H) 1.28 (s, 3 H) ¹³ C NMR (63 MHz, CDCl ₃ )? 170.56 165.67 165.51 164.88 164.81 136.77 133.46 133.37 133.16 133.08 129.91 129.85 129.74 129.68 129.42 129.33 129.06 129.01 128.53 128.39 128.36 128.25 127.99 127.79 127.68 100.68 98.62 75.48 70.80 70.16 69.79 69.59 69.32 67.91 61.99 21.07 IR v max cm -1 (KBr) 2866.75 1732.20 1455.43 1380.39 1300.49 1242.33 1122.47 1063.88 1032.16 MALDI-TOF-MS m / z 853.4013 [M + Na] ⁺ ( ^Calcd for C ₄₇ H ₄₂ O ₁₄ Na _, found: 853.2472)

2,3,4-O-benzoyl- alpha -L-O-rhamnopyranosyl- (1) -4-O- Acetyl -2-O-benzoyl-1-O-benzyl-a-L- Arabinophilanoside (2b)

White _{solid, R f = 0.32 (n-} Hexane / EtOAc, 4: 1, v / v) [α] D + 59 ° (c 0.1, CHCl 3) 1 H NMR (250 MHz, CDCl 3) 7.17 - 8.11 ( (m, 2H), 5.77-5.85 (m, 1H) 5.58-5.69 (m, 2H) 5.51 (dd, J = 3.08, 1.66 Hz, 1H) , J = 1.26 Hz, 1 H ) 4.94 (d, J = 12.48 Hz, 1 H) 4.63 - 4.73 (m, 2 H) 4.19 - 4.38 (m, 3 H) 3.72 (dd, J = 12.48, 2.05 Hz, ¹³ H NMR (63 MHz, CDCl ₃ ) 隆 170.63 165.80 165.18 165.12 165.00 136.93 133.38 133.22 133.04 129.99 129.82 129.77 129.65 129.47 129.23 128.48 (d, J = 6.16 Hz, 128.41 128.34 128.25 127.82 98.78 97.86 74.31 71.68 70.76 70.69 70.05 69.24 68.77 67.49 61.95 21.16 17.66 IR v _max cm ^-1 (KBr) 2864.87 1730.13 1452.43 1384.31 1307.43 1246.33 1123.45 1061.75 1031.12; MALDI-TOF-MS m / z 867.4801 [M + Na] ⁺ (Calcd for C ₄₈ H ₄₄ O ₁₄ Na _, found: 867.2629)

O-benzoyl-beta-D-O-glucopyranosyl- (1) -4-O-acetyl- Arabinophilanoside (2c)

White _{solid, R f = 0.33 (n-} Hexane / EtOAc, 4: 1, v / v) [α] D + 34 ° (c 0.1, CHCl 3) 1 H NMR (250 MHz, CDCl 3) δ 6.95 - 8.11 (m, 30 H) 5.82 ( t, J = 9.56 Hz, 1 H) 5.67 (t, J = 9.64 Hz, 1 H) 5.56 (dd, J = 9.56, 7.82 Hz, 1 H) 5.42 (dd, J = 7.90, 6.00 Hz, 1H) 5.28 (br.s, 1H) 5.02 (d, J = 7.90 Hz, 1H) 4.62 (d, J = 2.69 Hz, 1H) 4.58 H) 4.37 - 4.55 (m, 3 H) 4.02 - 4.18 (m, 3 H) 3.44 (dd, J = 12.48, 1.90 Hz, 1 H) 2.09 (s, 3 H) 13 C NMR (63 MHz, CDCl 3 )? 170.48 166.03 165.72 165.11 164.76 164.70 136.66 133.46 133.23 133.10 132.83 129.80 129.75 129.69 129.58 129.26 128.94 128.66 128.42 128.31 128.26 128.20 128.15 127.84 127.64 101.46 98.31 72.85 72.11 71.60 70.70 69.44 69.31 68. 62.80 61.87 21.03 IR v _max cm ^-1 (KBr) 2865.85 1732.13 1454.41 1381.35 1301.01 1242.35 1122.44 1063.81 1032.12; MALDI-TOF-MS m / z 987.5419 [M + Na] ⁺ (Calcd for C ₅₅ H ₄₈ O ₁₆ Na _, found: 987.2840)

Mannopyranosyl- (1) -4-O-acetyl-2-O-benzoyl-1-O- benzyl- alpha -L-arabinopyrano The seed (2d)

White _{solid, R f = 0.30 (n-} Hexane / EtOAc, 4: 1, v / v) [α] D + 24 ° (c 0.1, CHCl 3) 1 H NMR (250 MHz, CDCl 3) δ δ 7.17 - 8.20 (m, 30 H) 6.03 (t, J = 10.19 Hz, 1 H) 5.62 - 5.73 (m, 3 H) 5.43 (br.s., 1 H) 5.27 (s, 1 H) 4.95 (d, J = 12.48 Hz, 1 H) 4.60 - 4.76 (m, 2 H) 4.50 (dd, J = 12.24, 1.97 Hz, 1 H) 4.15 - 4.37 (m, 3 H) 3.99 (dd, J = 12.32, 3.63 Hz, 1 H) 3.64 (d, J = 12.64 Hz, 1H) 2.33 (s, 3 H) ¹³ C NMR (63 MHz, CDCl ₃ ) δ 170.86 166.00 164.97 164.84 136.88 133.57 133.37 133.14 133.08 129.88 129.85 129.72 128.57 128.51 128.47 128.33 128.26 127.93 127.83 99.09 96.01 74.27 70.58 70.07 69.90 69.85 69.18 66.12 66.03 62.82 62.07 21.02 IR v _max cm ^-1 (KBr) 2865.82 1732.17 1455.44 1380.32 1300.45 1242.36 1122.41 1063.87 1032.13; MALDI-TOF-MS m / z 987.5505 [M + Na] ⁺ (Calcd for C ₅₅ H ₄₈ O ₁₆ Na _, found: 987.2840)

Example 2. Preparation of compounds 3a-3d

Thereafter, a solution of 2a-d (0.72 mol) dissolved in methylene chloride-methanol (20 mL) using acetyl chloride (800 μL) was stirred at room temperature for 12 hours to concentrate and separate the acetyl group into the following compounds 3a to 3d Were synthesized.

2,3,4-O- Benzoyl -α-L-O- Arabinopyranosyl - (1) -2-O- Benzoyl -1-O-benzyl-a-L- Arabinophilanoside (3a)

White _{solid, R f = 0.21 (n-} Hexane / EtOAc, 2: 1, v / v) [α] D + 219 ° (c 0.1, CHCl 3) 1 H NMR (250 MHz, CDCl 3) δ 6.94 - 8.17 (m, 20 H) 5.84 ( dd, J = 9.40, 7.03 Hz, 1 H) 5.70 (br s, 1 H.) 5.51 - 5.62 (m, 1 H) 5.40 (d, J = 4.42 Hz, 1 H) 4.99 (d, J = 7.11 Hz, 1H) 4.41-4.62 (m, 3H) 4.29-4.40 (m, 1H) 3.87-4.22 s, 1 H) ¹³ C NMR (63 MHz, CDCl ₃ )? 165.76 165.56 165.03 164.97 136.88 133.56 133.39 133.17 133.03 129.94 129.75 129.69 129.34 129.27 128.61 128.39 128.32 128.19 127.84 127.54 101.54 97.18 78.46 71.03 70.65 69.50 68.68 68.62 66.11 63.94 62.47 IR v _max ^{cm -1 (KBr) 3461.52 3112.97 3032.07} 2986.34 2934.95 1728.52 1601.66 1497.44 1454.94 1380.81 1245.62 1213.19 1123.04 1078.52 1044.62 MALDI-TOF-MS m / z 811.4034 [m + Na] + (Calcd for C 45 H 40 O 13 Na, found: 811.2367 )

2,3,4-O- Benzoyl -α-L-O- Laminopyranosyl - (1) -2-O- Benzoyl -1-O-benzyl-a-L- Arabia Notoranoside (3b)

White solid, R _f = 0.23 (n-Hexane / EtOAc, 2: 1, v / v) [?] _D + 137 ° ( c _{^{0.1, CHCl 3) 1 H NMR}} (250 MHz, CDCl 3) δ 7.15 - 8.20 (m, 25 H) 5.83 - 5.98 (m, 1 H) 5.60 - 5.78 (m, 3 H) 5.31 - 5.44 (m, 1 H) 4.92 (d, J = 12.32 Hz, 1 H) 4.62 - 4.78 (m, 2 H) 4.33 - 4.51 (m, 1 H) 4.13 - 4.29 (m, 3 H) 3.71 (d, J = 9.64 Hz, 1 H) 3.00 (br.s, 1 H) 1.38 (d, J = 6.16 Hz, 3 H) ¹³ C NMR (63 MHz, CDCl ₃ )? 165.84 165.43 165.24.11 137.13 133.44 133.25 133.11 129.95 129.87 129.80 129.70 129.52 129.30 129.14 129.12 128.54 128.46 128.39 128.27 127.77 127.69 98.21 97.85 76.73 71.66 70.72 70.23 69.81 69.53 67.71 66.93 63.18 17.72 IR v _max cm ^-1 (KBr) 3460.53 3113.91 3031.99 2985.31 2934.93 1728.54 1601.69 1497.45 1454.93 1380.82 1245.62 1219.19 1120.09 1078.57 1044.63; MALDI-TOF-MS m / z 825.0341 [M + Na] ⁺ (Calcd for C ₄₆ H ₄₂ O ₁₃ Na _, found: 825.2523)

2,3,4,6-O- Benzoyl -β-D-O- Glucopyranosyl - (1) -2-O- Benzoyl -1-O-benzyl-a-L- Arabinophilanoside (3c)

White _{solid, R f = 0.28 (n-} Hexane / EtOAc, 2: 1, v / v) [α] D + 29 ° (c 0.1, CHCl 3) 1 H NMR (250 MHz, CDCl 3) δ 6.96 - 8.15 (m, 30 H) 5.86 - 5.98 (m, 1 H) 5.54 - 5.74 (m, 2 H) 5.40 (t, J = 6.24 Hz, 1 H) 5.09 (d, J = 7.74 Hz, 1 H) 4.68 - 4.82 (m, 1H), 3.45 (d, J = 12.00 Hz, 1H) 2.96-3.13 (m, 1H) ^{m, 1 H) 13 C NMR} (63 MHz, CDCl 3) δ 166.07 165.70 165.20 164.87 164.74 136.94 133.61 133.35 133.31 133.08 133.01 132.93 129.86 129.80 129.70 129.64 129.40 129.31 128.48 128.31 128.24 128.18 127.79 127.52 101.42 97.69 79.67 72.64 72.54 71.49 70.47 69.52 68.79 66.55 63.12 62.71 IR v _max cm ^-1 (KBr) 3460.51 3113.97 3032.01 2986.32 2934.92 1728.53 1601.61 1495.43 1451.93 1381.85 1248.63 1214.13 1121.18 1074.34 1044.18; MALDI-TOF-MS m / z 945.0593 [M + Na] ⁺ (Calcd for C ₅₃ H ₄₆ O ₁₅ Na _, found: 945.2734)

2,3,4,6-O- Benzoyl -α-D-O-mannopyranosyl- (1) -2-O- Benzoyl -1-O-benzyl-a-L- Arabinophilanoside (3d)

White solid, Rf = 0.25 (n-Hexane / EtOAc, 2: 1, v / v) [?] _D + 8 ° ( c 0.1, CHCl ₃ ) ¹ H NMR (250 MHz, CDCl ₃ )? 7.13 - 8.22 ) 6.09 (t, J = 10.03 Hz, 1 H) 5.91 (br.s., 1 H) 5.74 - 5.86 (m, 2 H) 5.44 (s, 1 H) 4.96 (d, J = 12.48 Hz, 1 H ) 4.66 - 4.79 (m, 2 H) 4.59 (d, J = 10.90 Hz, 2 H) 4.21 - 4.38 (m, 3 H) 4.10 - 4.21 (m, 1 H) 3.68 (d, J = 9.32 Hz, 1 ^{H) 13 C NMR (63 MHz} , CDCl 3) δ 165.76 165.56 165.03 164.97 136.88 133.56 133.39 133.17 133.03 129.94 129.75 129.69 129.34 129.27 128.61 128.39 128.32 128.19 127.84 127.54 101.54 97.18 78.46 71.03 70.65 69.50 68.68 68.62 66.11 63.94 62.47 IR v max cm ^-1 (KBr) 3462.31 3115.81 3034.11 2987.35 2934.93 1728.55 1601.63 1497.46 1454.91 1380.83 1245.64 1219.15 1120.01 1078.53 1044.65; MALDI-TOF-MS m / z 945.0593 [M + Na] ⁺ (Calcd for C ₅₃ H ₄₆ O ₁₅ Na _, found: 945.2734)

Example 3. Preparation of compounds 4a to 4h

The above compounds a to d were glycosylated at the C-4 free hydroxyl group of 3a to 3d under the promoter TMSOTf at -78 ° C to obtain trisaccharides 4a to 4h. The free hydroxy groups of C-3 and C-4 of compound 6 as the glycosyl acceptor were stereoselectively glycosylated in the same manner in the yields of 72 to 87% with the donors b and d.

Compound 6,

2,3,4-O- Benzoyl -α-L-O- Arabinopyranosyl - (1) - [2,3,4-O- Benzoyl -α-L-O- Laminopyranosyl - (1)] - 2-O- Benzoyl -1-O-benzyl-a-L- Arabinophilanoside (4a)

White _{solid, R f = 0.35 (n-} Hexane / EtOAc, 4: 1, v / v) [α] D + 106 ° (c 0.1, CHCl 3) 1 H NMR (250 MHz, CDCl 3) δ 7.09 - 8.13 (m, 40 H) 5.87 - 5.96 (m, 1 H) 5.84 (d, J = 1.11 Hz, 1 H) 5.64 - 5.81 (m, 4 H) 5.33 - 5.46 (m, 2 H) 5.21 (d, J = 4.26 Hz, 1 H) 4.70 (d, J = 2.37 Hz, 1 H) 4.54 - 4.68 (m, 2 H) 4.49 (s, 1 H) 4.32 - 4.47 (m, 2 H) 4.26 (d, J = 3.00 Hz, 2 H) 3.97 - 4.11 (m, 1 H) 3.67 (d, J = 6.48 Hz, 1 H) 13 C NMR (63 MHz, CDCl 3) δ165.83 165.79 165.46 165.16 164.97 164.90 136.90 133.35 133.20 133.15 132.87 130.03 129.90 129.81 129.75 129.65 129.44 129.31 129.23 129.18 128.51 128.46 128.41 128.31 128.25 128.20 128.09 127.84 127.59 99.31 97.34 96.85 71.82 70.71 70.27 69.87 69.06 67.40 67.27 60.84 IR v _max cm ^-1 (KBr) 2932.24 1733.66 1602.54 1451.15 1381.63 1266.15 1095.14 MALDI-TOF-MS m / z 1269.5721 [M + Na] ⁺ (Calcd for C ₇₂ H ₆₂ O ₂₀ Na _, found: 1269.3732)

2,3,4-O- Benzoyl -α-L-O- Arabinopyranosyl - (1) - [2,3,4,6-O- Benzoyl -β-D-O- Glucopyranosyl - (1)] - 2-O- Benzoyl -1-O-benzyl-a-L- Arabinophilanoside (4b)

White solid, Rf = 0.35 (n-Hexane / EtOAc, 4: 1, v / v) [?] _D + 65 ° ( c 0.1, CHCl ₃ ) ¹ H NMR (250 MHz, CDCl ₃ )? 7.03-8.11 5.52 (m, 1H), 5.32 (t, J = 9.72 Hz, 1H) 4.99 (br, s, 1H) 4.58-4.72 (m, 2 H) 4.43-4.54 (m, 3 H) 4.35-4.43 (m, J = 11.74, 6.24 Hz, 1 H) 3.74 (d, J = 10.64 Hz, 1 H) 3.56 (br. s., 1 H) 13 C NMR (63 MHz, CDCl 3) δ 165.96 165.91 165.71 165.52 165.44 165.05 164.96 164.78 137.01 133.51 133.47 133.42 133.34 133.14 133.00 132.95 130.14 129.98 129.86 129.82 129.74 129.45 129.36 129.20 128.64 128.50 128.45 128.41 128.33 128.26 128.18 127.87 127.67.14 97.61 96.67 71.95 71.07 70.80 70.32 69.96 69.57 69.31 67.77 66.67 66.44 62.51 62.30 IR v _max cm ^-1 (KBr ) 2936.14 1736.81 1603.47 1452.11 1380.31 1263.71 1092.12; MALDI-TOF-MS m / z 1389.5853 [M + Na] ⁺ (Calcd for C ₇₉ H ₆₆ O ₂₂ Na _, found: 1389.3943)

2,3,4-O-benzoyl-a-L-O- Arabinopyranosyl - (1) - [2,3,4,6-O-benzoyl- alpha -D-O-mannopyranosyl- (1)] - 2-O- Benzoyl -1-O-benzyl-a-L- Arabinophilanoside (4c)

White _{solid, R f = 0.37 (n-} Hexane / EtOAc, 4: 1, v / v) [α] D + 15 ° (c 0.1, CHCl 3) 1 H NMR (250 MHz, CDCl 3) δ 7.15 - 8.21 (m, 1H), 5.67 (m, 2H), 6.26 (t, J = 9.90 Hz, 1H) 6.10-6.17 (m, 1H) 5.88 (br.s. s., 1 H) 5.48 (br.s., 1 H) 5.39 (br.s., 1 H) 5.19 (br.s., 1 H) 4.91 (br.s., 1 H) 4.73 - 4.81 m, 2 H) 4.64 - 4.73 (m, 2 H) 4.52 (t, J = 13.57 Hz, 2 H) 4.39 (br.s., 2 H) 4.06 - 4.19 (m, 2 H) 3.56 (d, J ^{= 11.37 Hz, 1 H) 13} C NMR (63 MHz, CDCl 3) δ165.96 165.91 165.71 165.52 165.44 165.05 164.96 164.78 137.01 133.51 133.47 133.42 133.34 133.14 133.00 132.95 130.14 129.98 129.86 129.82 129.74 129.45 129.36 129.20 128.64 128.50 128.45 128.41 128.33 128.26 128.18 127.87 127.67.14 97.61 96.67 71.95 71.07 70.80 70.32 69.96 69.57 69.31 67.77 66.67 66.44 62.51 62.30 IR v _max ^{cm -1 (KBr) 2936.61 1735.41 1602.31} 1455.68 1383.73 1263.48 1091.74 MALDI-TOF-MS m / z 1389.5853 [M + Na] + (Calcd for C 79 H 66 O 22 Na, found: 1389.3943)

2,3,4-O- Benzoyl -a-L-O- Laminopyranosyl - (1) - [2,3,4,6-O- Benzoyl -a-D-O- Manno pyra Nosyl- (1)] - 2-O- Benzoyl -1-O-benzyl-a-L- Arabinophilanoside (4d)

White _{solid, R f = 0.34 (n-} Hexane / EtOAc, 4: 1, v / v) [α] D + 57 ° (c 0.1, CHCl 3) 1 H NMR (250 MHz, CDCl 3) δ 7.10 - 8.24 (m, 45 H) 6.32 ( t, J = 10.09 Hz, 1 H) 5.87 - 6.08 (m, 3 H) 5.75 - 5.86 (m, 2 H) 5.59 (d, J = 11.74 Hz, 1 H) 5.43 - 5.55 (m, 2 H) 5.00 (d, J = 12.47 Hz, 1 H) 4.88 - 4.97 (m, 1 H) 4.61 - 4.83 (m, 4 H) 4.44 - 4.61 (m, 4 H) 3.84 (d, J = 6.24 Hz, 1 H) 1.54 (d, J = 5.87 Hz, 3 H) ¹³ C NMR (63 MHz, CDCl ₃ )? 166.20 166.02 165.78 165.33 165.26 165.16 164.80 163.72 137.12 133.95 133.57 133.50 133.40 133.30 133.22 133.16 133.05 130.18 130.08 129.91 129.86 129.79 129.73 129.64 129.55 129.40 129.32 129.13 128.90 128.84 128.79 128.60 128.52 128.44 128.37 128.31 128.25 127.92 127.79 127.61 101.57 92.31 90.45 74.01 73.18 72.42 72.58 70.32 69.76 69.40 68.52 67.73 63.07 62.63 17.83 IR v _max cm ^-1 (KBr) 2934.47 1734.18 1603.61 1454.77 1383.99 1263.37 1091.58; MALDI-TOF-MS m / z 1403.9052 [M + Na] ⁺ (Calcd for C ₈₇ H ₇₂ O ₂₄ Na _, found: 1403.4100)

2,3,4,6-O- Benzoyl -β-D-O- Glucopyranosyl - (1) - [2,3,4-O- Benzoyl -α-L-O- rha &Lt; RTI ID = 0.0 > laminopyranosyl- (1)] - 2-O- Benzoyl -1-O-benzyl-a-L- Arabinophilanoside (4e)

White _{solid, R f = 0.39 (n-} Hexane / EtOAc, 4: 1, v / v) [α] D + 60 ° (c 0.1, CHCl 3) 1 H NMR (250 MHz, CDCl 3) δ 7.01 - 8.28 (m, 45 H) 6.04 ( dd, J = 10.03, 3.24 Hz, 1 H) 5.93 (d, J = 7.58 Hz, 2 H) 5.81 - 5.90 (m, 2 H) 5.72 (t, J = 9.95 Hz, (M, 1H), 5.59 (br.s, 1H), 5.39-5.51 (m, 1H) 5.20 (d, J = 3.63 Hz, 1H) 4.59-4.76 H) 4.03 - 4.34 (m, 4 H) 3.50 (d, J = 12.16 Hz, 1 H) 1.27 - 1.45 (m, 3 H) 1.32 (d, J = 6.16 Hz, 3 H) 13 C NMR (63 MHz , CDCl ₃ )? 166.09 165.78 165.41 165.10 165.06 164.65 164.56 136.94 133.30 133.03 132.82 129.42 128.93 128.49 128.36 128.17 127.99 101.59 98.10 95.08 73.02 72.36 72.21 71.98 71.57 71.48 70.80 70.74 69.74 69.63 69.30 68.61 67.08 62.91 17.69 IR v _max ^{cm -1 (KBr) 2934.32 1735.78 1603.71} 1454.22 1387.39 1265.13 1094.83 MALDI-TOF-MS m / z 1403.4297 [M + Na] + (Calcd for C 80 H 68 O 22 Na, found: 1403.4100)

2,3,4,6-O- Benzoyl -α-D-O- Mannpyranosil - (1) - [2,3,4-O- Benzoyl -α-L-O- Arabia Nopyranosyl- (1)] - 2-O- Benzoyl -1-O-benzyl-a-L- Arabinophilanoside (4f)

White _{solid, R f = 0.36 (n-} Hexane / EtOAc, 4: 1, v / v) [α] D + 74 ° (c 0.1, CHCl 3) 1 H NMR (250 MHz, CDCl 3) δ 7.12 - 8.20 (m, 1H) 6.04 (t, J = 9.95 Hz, 1H) 5.70-5.95 (m, 5H) 5.58-5.70 (m, 1H) J = 12.32 Hz, 1 H) 4.62 - 4.78 (m, 2 H) 4.31 - 4.59 (m, 5 H) 4.04 - 4.29 (m, 3 H) 3.69 (d, J = 10.27 Hz, 1 H) 13 C NMR (63 MHz, CDCl ₃ )? 165.95 165.80 165.63 165.43 165.38 165.24 165.04 164.64 137.16 133.32 132.98 130.02 129.96 129.88 129.75 129.66 129.61 129.44 129.31 129.20 128.83 128.49 128.41 128.33 128.25 128.20 127.79 100.66 99.01 97.08 72.04 70.92 70.85 70.24 69.78 69.72 69.66 69.60 69.33 68.08 66.43 62.30 IR v _max cm ^-1 (KBr) 2932.87 1734.36 1602.74 1452.80 1383.65 1262.13 1092.57; MALDI-TOF-MS m / z 1389.2213 [M + Na] ⁺ (Calcd for C ₇₉ H ₆₆ O ₂₂ Na _, found: 1389.3943)

(1 → 3) - [2,3,4-O-benzoyl- 留 -L0-rhamnopyranosyl- (1 → 4)] - 2-O- Benzoyl -1-O-benzyl-a-L- Arabinophilanoside (4g)

White solid, R _f = 0.37 (n-Hexane / EtOAc ,, 4: 1, v / v) [α] D + 131 ° (c 0.1, CHCl 3) 1 H NMR (250 MHz, CDCl 3) δ 6.72 - 8.28 (m, 40 H) 6.20 (dd, J = 10.27,3.30 Hz, 1H) 5.85-5.98 (m, 5H) 5.62 (br.s, 2 H) 5.43 (s, 1H) 4.96-5.08 J = 6.4 Hz, 3 H) 1.56 (m, 1 H), 4.72-4.84 (m, 2 H) 4.52-4.64 (d, J = 6.24 Hz, 3 H) 13 C NMR (63 MHz, CDCl 3) δ166.21 165.96 165.59 165.42 165.33 165.12 164.87 137.42 133.58.42 133.33 133.05 132.83 132.56 130.01 129.94 129.89 129.79 129.71 129.57 129.31 129.28 129.20 129.09 128.62 128.55 128.40.34 128.06 127.92 127.89 127.73 98.50 96.86 95.69 73.72 71.92 71.36 71.17 70.82.45 70.03 69.99 68.69 68.12 67.62 18.07 17.75 IR v _max cm ^-1 (KBr) 2935.86 1735.15 1602.61 1453.13 1386.44 1263.23 1092.41; MALDI-TOF-MS m / z 1283.1238 [M + Na] ⁺ (Calcd for C ₇₃ H ₆₄ O ₂₀ Na _, found: 1283.3889)

2,3,4,6-O- Benzoyl -α-D-O- Mannpyranosil - (1- > 3) - [2,3,4,6-O- Benzoyl -α-D-O- Mannpyranosil - (1- > 4)] - 2-O- Benzoyl -1-O-benzyl-a-L- Arabinophilanoside (4h)

White _{solid, R f = 0.31 (n-} Hexane / EtOAc, 4: 1, v / v) [α] D + 8 ° (c 0.1, CHCl 3) 1 H NMR (250 MHz, CDCl 3) δ 6.82 - 8.18 (m, 50 H) 6.28 - 6.39 (m, 1 H) 6.16 - 6.28 (m, 2 H) 6.02 (d, J = 2.53 Hz, 2 H) 5.90 - 6.00 (m, 1 H) 5.76 (t, J = 4.58 Hz, 1 H) 5.55 (d, J = 15.95 Hz, 2 H) 5.00 (d, J = 12.00 Hz, 1H) 4.78-4.91 (m, - 4.59 (m, 4 H) 4.17 (dd, J = 12.40, 3.24 Hz, 1 H) 3.76 (d, J = 10.74 Hz, 1 H) 13 C NMR (63 MHz, CDCl 3) δ166.18 166.11 165.74 165.49 165.47 165.44 165.19 165.11 164.95.0 133.44 133.35 133.28 132.95 132.87 129.98 129.90 129.80 129.75 129.67 129.42. 36 129.19 129.15 128.96 128.92 128.56 128.41 128.33 128.20 128.12 128.01 127.97 98.20 98.10 96.63 77.03 71.08 70.94 70.09 69.58 66.37 66.18 62.82 62.47; IR v _max cm ^-1 (KBr) 2931.12 1734.52 1602.11 1453.47 1383.81 1263.97 1093.56; MALDI-TOF-MS m / z 1523.3742 [M + Na] ⁺ (Calcd for C ₈₇ H ₇₂ O ₂₄ Na _, found: 1523.4311)

Example 4. Preparation of compounds 5a to 5i

The benzyl group at C-1 position of the compound 2d and 4a to 4h was selectively deprotected using a Pd / C catalyst under a H2 / THF / methanol (1: 1) solution to obtain 5a to 5i in 80 to 93% Respectively.

2,3,4-O- Benzoyl -α-L-O- Arabinopyranosyl - (1- > 3) - [2,3,4-O- Benzoyl -α-L-O- Ram Nopyranosyl- (1 → 4)] - 2-O- Benzoyl -α-L- Arabinophilanoside (5a)

¹ H NMR (250 MHz, CDCl ₃ )? 8.02 - 8.11 (m, 6 H) 7.96 - 8.02 (m, 3 H) 5.82 - 5.90 (m, 5.73 - 5.81 (m, 3 H ) 5.65 (dd, J = 8.07, 3.30 Hz, 1 H) 5.57 (br s, 1 H..) 5.41 - 5.48 (m, 1 H) 5.36 (dd, J = 8.44, (M, 1H), 4.16-4.38 (m, 1H), 4.16-4.38 (m, 1H), 5.19 (d, J = 5.50 Hz, 1H) J = 5.14 Hz, 1H), 1.39 (d, J = 6.24 Hz, 3H), 3.97 (dd, J = 12.47, 4.40 Hz, 1H) ^{13 C NMR (63 MHz, CDCl} 3) δ 165.98 165.85 165.61 165.53 165.15 165.04 133.38 133.33 133.22 133.17 133.09 133.01 132.89 129.97 129.92 129.84 129.73 129.53 129.40 129.32 129.22 129.12 128.44 128.37 128.31 128.16 101.23 98.69 91.15 74.49 72.03 70.97 70.85 70.26 70.08 69.94 69.90 67.91 67.25 62.21 62.01

2,3,4-O- Benzoyl -α-L-O- Arabinopyranosyl - (1- > 3) - [2,3,4,6-O- Benzoyl -β-D-O-glucopyranosyl- (1 → 4)] - 2-O- Benzoyl -α-L- Arabinophilanoside (5b)

White solid, (α: β = 7: 1) ¹ H NMR (250 MHz, CDCl ₃ ) δ 76.89-8.08 (m, 40 H) 6.15 (t, J = 9.56 Hz, 1H) 5.87 (br s. (M, 2H), 5.68 (t, J = 9.56 Hz, 3H) 5.48-5.63 (m, 1H) 5.33 (br s, 1H) 5.00-5.16 (m, 2H) 4.58 , 2 H) 4.41 (d, J = 5.53 Hz, 2 H) 4.17 -.. 4.33 (m, 2 H) 4.11 (d, J = 12.32 Hz, 1 H) 3.92 (br s, 1 H) 3.76 (d , J = 12.00 Hz, 1 H ) 3.03 (d, J = 3.16 Hz, 1 H) 13 C NMR (63 MHz, CDCl 3) δ166.05 165.77 165.67 165.54 165.50 165.45 165.14 164.70 133.44 133.27 130.00 129.85 129.71 129.60 129.40 129.24 129.17 129.06 128.93 128.74 128.6 128.47 128.41 128.38 128.33 128.28 128.14 101.93 99.56 90.98 74.34 73.43 73.18 72.29 72.23 70.99 70.74 70.19 69.82 68.92 63.17 62.71

2,3,4-O- Benzoyl -α-L-O- Arabinopyranosyl - (1- > 3) - [2,3,4,6-O- Benzoyl -α-D-O-mannopyranosyl- (1 → 4)] - 2-O- Benzoyl -α-L- Arabinophilanoside (5c)

White solid, (α: β = 5: 1) 1 H NMR (250 MHz, CDCl 3) δ 7.01 - 8.33 (m, 40 H) 6.25 - 6.32 (m, 1 H) 6.06 (dd, J = 10.27, 3.30 Hz, 1 H) 5.89 (br.s. , 1 H) 5.78 - 5.87 (m, 1 H) 5.69 (br s, 2 H) 5.56 -.. 5.67 (m, 1 H) 5.35 (dd, J = 10.09 , 3.12 Hz, 1H) 5.26 (s, 1H) 5.16 (d, J = 7.34 Hz, 1H) 5.11 (d, J = 7.34 Hz, 1H) 4.82-4.89 (m, 2 H) 4.41 - 4.48 (m, 2 H) 3.99 - 4.10 (m, 2 H) 3.81 - 3.89 (m, 1 H) 3.43 (br.s., 1 H) 13 C NMR (63 MHz, CDCl ₃ ) δ 165.96 165.83 165.72 165.59 165.35 165.25 165.22 165.05 133.43 133.36 133.27 133.22 133.07 132.89 132.72 130.28 130.17 130.13 129.82 129.75 129.58 129.52 129.49 129.44 129.22 129.07 128.93 128.48 128.41 128.33 128.13 102.88 95.06 90.91 73.57 73.42 71.60 70.98 70.71 70.63 69.69 69.62 69.13 66.26 64.17 62.26 58.74

2,3,4-O- Benzoyl -α-L-O- Laminopyranosyl - (1- > 3) - [2,3,4,6-O- Benzoyl -α-D-O- Manno Pyranosyl- (1 → 4)] - 2-O- Benzoyl -α-L- Arabinophilanoside (5d)

White solid, (α: β = 5: 1) 1 H NMR (250 MHz, CDCl 3) δ 7.10 - 8.24 (m, 40 H) 6.40 (t, J = 10.09 Hz, 1 H) 6.12 (dd, J = (M, 2H), 5.10 (d, J = 11.74 Hz, 1H) 4.95 (m, 4H) , J = 9.54 Hz, 1 H ) 4.67 - 4.76 (m, 2 H) 4.38 - 4.50 (m, 2 H) 4.09 (br.s., 1 H) 3.49 (d, J = 3.67 Hz, 1 H) 1.46 (d, J = 6.24 Hz, 3 H); ¹³ C NMR (63 MHz, CDCl ₃ )? 166.22 165.90 165.85 165.67 165.55 165.45 165.24 133.68 133.43 133.38133.27 133.23 133.17 133.14 132.99 130.07 130.01 129.96 129.90 129.75 129.59 129.51 129.43 129.22 129.11 128.88 128.69 128.54 128.47 128.43 128.36 128.30 101.06.54 91.08 72.85 72.63 71.09 70.53 70.44 69.67 69.51 69.47 69.18 68.59 66.59 62.68 62.50 60.49 17.17

2,3,4,6-O- Benzoyl -α-L-O- Glucopyranosyl - (1- > 3) - [2,3,4-O- Benzoyl -α-L-O- Laminopyranosyl - (1- > 4)] - 2-O- Benzoyl -α-L- Arabinophilanoside (5e)

White solid, (α: β = 7: 1) 1 H NMR (250 MHz, CDCl 3) δ 7.00 - 8.19 (m, 40 H) 6.04 (dd, J = 10.03, 3.24 Hz, 1 H) 5.79 - 6.00 ( m, 1H) 5.72 (t, J = 9.95 Hz, 1H) 5.55 (br.s., 1H) 5.39-5.52 (m, 1H) 5.14-5.28 (m, 1H) 4.59-4.75 J = 6.16 Hz, 3 H). ¹³ C NMR (DMSO-d6, J = 8.3 Hz, 1H) 63 MHz, CDCl ₃ )? 166.09 165.78 165.41 165.10 165.06 164.65 164.56 136.94 133.30 133.03 132.82 130.09 129.93 129.64 (129.62 129.42 128.93 128.49 128.36 128.17 127.99 101.59 98.10 95.08 73.02 72.36 72.21 71.98 71.57 71.48 70.80 70.74 69.74 69.63 69.30 68.61 67.08 62.91 17.69

2,3,4,6-O- Benzoyl -α-D-O- Mannpyranosil - (1- > 3) - [2,3,4-O- Benzoyl -α-L-O- Ara Binopyranosyl- (1 → 4)] - 2-O- Benzoyl -α-L- Arabinophilanoside (5f)

White solid, (α: β = 5: 1) 1 H NMR (250 MHz, CDCl 3) δ 7.19 - 8.17 (m, 40 H) 6.08 (d, J = 10.27 Hz, 1 H) 5.87 - 5.94 (m, H) 5.84 (d, J = 5.87 Hz, 2 H) 5.74 - 5.80 (m, 1H) 5.72 (br.s, 1H) 5.67 (br.s. , 1 H) 5.36 - 5.44 ( m, 2 H) 4.65 (d, J = 9.54 Hz, 1 H) 4.33 - 4.52 (m, 4 H) 4.17 - 4.29 (m, 3 H) 4.02 (d, J = 12.10 Hz, 1 H) ¹³ C NMR (63 MHz, CDCl ₃ ) δ 166.24 166.00 165.61 165.52 165.32 165.30 165.27 165.00 133.58.42 133.24 133.19 133.12 133.06 130.05 129.93 129.88 129.79 129.75 129.68 129.24.67 128.61 128.53 128.49 128.43 128.31 101.31 98.27 90.92 74.86 73.24 72.48 72.39 70.86 70.07 69.08 68.62 68.29 63.06 62.77 60.51

2,3,4-O- Benzoyl -α-L-O- Laminopyranosyl - (1- > 3) - [2,3,4-O- Benzoyl -α-L-O- Rhamnopi Lanosyl- (1 → 4)] - 2-O- Benzoyl -α-L- Arabinophilanoside (5g)

White solid, (α: β = 5: 1) 1 H NMR (250 MHz, CDCl 3) δ 6.82 - 8.21 (m, 35 H) 5.94 - 6.04 (m, 2 H) 5.86 (br.s., 2 H ) 5.72-5.82 (m, 3 H) 5.46-5.44 (m, 2 H) 5.37-5.45 (m, 1H) 4.58 (t, J = 8.62 Hz, 4.24 - 4.34 (m, 2 H ) 4.10 (d, J = 9.90 Hz, 1 H) 3.60 (br s, 1 H..) 1.45 - 1.52 (m, 3 H) 1.36 - 1.45 (m, 3 H) 13 _{C NMR (63 MHz, CDCl 3} ) δ166.14 166.06 165.42 165.10 165.02 133.58 133.44 133.35 133.29 132.99 132.84 132.80 130.11 129.95 129.88.75 129.69 129.52 129.49 129.39 129.33 129.24 129.11 128.58 128.50 128.44 128.22 .15 128.11 128.05 98.81 98.70 91.17 71.77 71.60 71.24 71.09 71.00 70.13 69.94.82 67.94 67.70 67.61 61.55 60.47 17.97 17.66

2,3,4,6-O- Benzoyl -α-D-O- Mannpyranosil - (1- > 3) - [2,3,4,6-O- Benzoyl -α-D-O- Mannpyranosil - (1- > 4)] - 2-O- Benzoyl -α-L- Arabinophilanoside (5h)

White solid, (α: β = 5: 1) 1 H NMR (250 MHz, CDCl 3) δ 6.82 - 8.16 (m, 45 H) 6.30 (t, J = 9.35 Hz, 1 H) 6.15 - 6.22 (m, J = 8.99 Hz, 1H) 6.02 (br.s, 1H) 5.88 (br.s, 2H) 5.78-5.86 (m, 3 H) 5.51 (d, J = 13.57 Hz, 3 H) 4.81-4.96 (m, 3 H) 4.78 (d, J = 9.17 Hz, 1H) 4.59-4.71 (m, m, 2 H) ¹³ C NMR (63 MHz, CDCl ₃ ) δ 166.27 166.20 165.79 165.75 165.37 165.35 165.24 165.11 133.35 133.20 133.08 132.81 130.16 129.85 129.73 129.62 129.38 129.05 129.00 128.69 128.49 128.41 128.32 128.22 128.13 128.06 128.01 95.53 94.68 91.38 71.72 70.96 70.85 70.69 70.36 70.05 68.97 66.41 65.91 65.83 62.74 62.53 57.36

2,3,4,6-O- Benzoyl -α-D-O- Mannpyranosil - (1? 3) -4-O-acetyl-2-O- Benzoyl -α-L-arabinopyranoside (5i)

White solid, (α: β = 5: 1) 1 H NMR (250 MHz, CDCl 3) δ 87.16 - 8.22 (m, 25 H) 5.99 - 6.09 (m, 1 H) 5.71 (d, J = 3.32 Hz, 1 H) 5.56 - 5.68 (m , 3 H) 5.52 (d, J = 2.69 Hz, 1 H) 5.28 - 5.37 (m, 1 H) 4.67 - 4.78 (m, 1 H) 4.64 (d, J = 1.90 Hz , 1 H) 4.54 (br s , 1 H) 4.16 -.. 4.37 (m, 2 H) 3.74 - 3.87 (m, 1 H) 2.30 (s, 3 H) 13 C NMR (63 MHz, CDCl 3) δ 166.08 165.52 165.30 165.06 137.27 133.46 133.38 133.20 133.10 129.93 129.74 129.55 128.98 128.77 128.55 128.47 128.37 128.31 127.85 98.61 96.99 77.15 70.66 70.33 70.19 69.79 69.22 66.23 64.78 63.52 62.44

Example 5. Preparation of compounds 7a to 7i

Compounds 5a to 5i were dissolved in methylene chloride using CCl3CN and DBU and treated at 0 < 0 > C to obtain trichloroacetimidate moieties 7a to 7i as glycosyl donors in 78-85% yield. These promoters were used in the synthesis of 9a to 9i without separation immediately upon production.

Example 6. Preparation of compounds 9a to 9i

The compound 7a to 7d (0.24 mmol) and the protected hederagenin 8 (0.24 mmol) were dissolved in methylene chloride, and TMSOTf (0.04 mmol) was added to the solution. The solution was stirred at -78 < 0 > C for 1 hour and then neutralized with triethylamine. Concentration and separation yielded 9-9 i of PSD derivatives fully protected by glycosylation in 49-75% yield. All deprotection of the trisaccharide saponin derivative was carried out in one step (in situ).

28-O-t- Butyl diphenylsilyl -23-O- Benzoyl - Hederagenin -3-O-2,3,4-O- Benzoyl -α-L-O-arabinopyranosyl- (1 → 3) - [2,3,4-O- Benzoyl -α-L-O- Laminopyranosyl - (1- > 4)] - 2-O- Benzo Yl-alpha-L- Arabinophilanoside (9a)

White _{solid, R f = 0.50 (n-} Hexane / EtOAc, 2: 1, v / v) [α] D + 106 ° (c 0.05, CHCl 3) 1 H NMR (400 MHz, CDCl 3) δ 7.07 - 8.17 (m, 1 H) 5.59-5.93 (m, 7 H) 5.35-5.45 (m, 2 H) 5.25 (br s, 1 H) (M, 1H), 4.96-4.44 (m, 1H) 4.24-4.32 (m, 2H) 4.17-4.24 J = 8.44 Hz, 1H) 3.42-3.50 (m, 1H) 2.78-2.94 (m, 1H) 1.39 (d, J = 6.24 Hz, s, 9 H) 0.97 (s , 3 H) 0.93 (s, 3 H) 0.89 (s, 3 H) 0.84 (s, 3 H) 0.74 (s, 3 H) 0.35 (s, 3 H) 13 C NMR (100 MHz, CDCl ₃ ) δ 166.05 165.77 165.67 165.54 165.50 165.45 165.14 164.70 133.44 133.27 130.00 129.85 129.71 129.60 129.40 129.24 129.17 129.06 128.93 128.74 128.6 128.47 128.41 128.38 128.33 128.28 128.14 101.93 99.56 90.98 74.34 73.43 73.18 72.29 72.23 70.99 70.74 70.19 69.82 68.92 63.17 62.71 48.54 47.56 47.18 43.76 42.61 42.48 40.16 38.95 37.31 34.92 33.25 31.44 30.44 28.80 26.59 25.92 24.50 24.29 24.17 20.46 19.12 18.6 3 17.97 16.46 14.18 14.04 IR v _max cm ^-1 (KBr) 2933.51 2864.11 1728.71 1604.57 1453.54 1384.32 1265.76 1092.14 MALDI-TOF-MS m / z 1975.7391 [M + Na] ⁺ (Calcd for C ₁₁₈ H ₁₂₄ O ₂₄ SiNa _, found: 1975.8150)

28-O-t- Butyl diphenylsilyl -23-O- Benzoyl - Hederagenin -3-O-2,3,4-O- Benzoyl -α-L-O-arabinopyranosyl- (1 → 3) - [2,3,4,6-O- Benzoyl -β-D-O- Glucopyranosyl - (1 → 4)] - 2-O-benzoyl-α-L- Arabinophilanoside (9b)

White _{solid, R f = 0.53 (n-} Hexane / EtOAc, 2: 1, v / v) [α] D + 66 ° (c 0.1, CHCl 3) 1 H NMR (400 MHz, CDCl 3) δ δ 7.12 - 8.08 (m, 55H) 6.04-6.18 (m, 1H) 5.68-5.79 (m, 2H) 5.55-5.67 (m, 3H) 5.43-5.55 (m, 1H) 5.26 J = 7.42, 2.53 Hz, 2H), 4.95 (br.s, 1H) 4.52-4.70 (m, 2H) 4.40-4.52 (m, 1H) 4.23-4.40 (M, 1H), 2.88 (dd, J = 13.27, 3.16 Hz, 1H), 1.28 (s, 3H), 3.78-3.10 3 H) 0.91 (s, 3 H) 0.78 (s, 3 H) 0.33 (s, 3 H) (s, 3 H) ¹³ C NMR (100 MHz, CDCl ₃ ) δ 166.27 166.20 165.79 165.75 165.37 165.35 165.24 165.11 133.35 133.20 133.08 132.81 130.16 129.85 129.73 129.62 129.38 129.05 129.00 128.69 128.49 128.41 128.32 128.13 128.06 128.01 95.53 94.68 91.38 71.72 70.96 70.85 70.69 70.36 70.05 68.97 66.41 65.91 65.83 62.74 62.53 57.36 48.54 47.56 47.18 43.76 42.61 42.48 40.16 38.95 37.31 34.92 33.25 31.44 30.44 28.80 26.59 25.92 24.50 24.29 24.17 20.46 19.12 18.63 17.97 16.46 14.18 14.04 IR v _max cm ^-1 (KBr) 2936.23 2859.88 1723.51 1602.51 1456.18 1381.56 1262.22 1097.72 MALDI-TOF-MS m / z 2096.1011 [M + Na] ⁺ (Calcd for C ₁₂₅ H ₁₂₈ O ₂₆ SiNa _, found: 2095.8361)

28-O-t- Butyl diphenylsilyl -23-O- Benzoyl - Hederagenin -3-O-2,3,4-O- Benzoyl -α-L-O-arabinopyranosyl- (1 → 3) - [2,3,4,6-O- Benzoyl -α-D-O- Mannpyranosil - (1 → 4)] - 2-O-benzoyl- alpha -L-arabinopyranoside (9c)

White _{solid, R f = 0.55 (n-} Hexane / EtOAc, 2: 1, v / v) [α] D + 48 ° (c 0.05, CHCl 3) 1 H NMR (400 MHz, CDCl 3) δ 7.02 - 8.13 (m, 1H) 6.20-6.31 (m, 1H) 6.06-6.15 (m, 1H) 5.89 (br s, 1H) 5.67-5.77 H) 5.39 - 5.51 (m, 1H) 5.23-5.33 (m, 2H) 5.04-5.19 (m, 1H) 4.82-4.97 (m, 1H), 2.89 (dd, J = 13.27, 3.16 Hz, 1H) 1.27 (m, 2H), 3.92-4.20 (S, 3 H) 0.91 (s, 3 H) 0.90 (s, 3 H) 0.35 (s, 3 H) s, 3 H) ¹³ C NMR (100 MHz, CDCl ₃ ) 166.14 166.06 165.42 165.10 165.02 133.58 133.44 133.35 133.29 132.99 132.84 132.80 130.11 129.95 129.88.75 129.69 129.52 129.49 129.39 129.33 129.24 129.11 128.58 128.50 128.44 128.22 .15 128.11 128.05 98.81 98.70 91.17 71.77 71.60 71.24 71.09 71.00 70.13 69.94.82 67.94 67.70 67.61 61.55 60.47 48.54 47.56 47.18 43.76 42.61 42.48 40.16 38.95 37.31 34.92 33.25 31.44 30.44 28.80 26.59 25.92 24.50 24.29 24.17 20.46 19.12 18.63 17.97 17.66 16.46 14.18 14.04 IR v max (KBr) cm -1 2931.54 2862.43 1722.36 1602.11 1455.16 1382.56 1261.63 1094.69 MALDI-TOF-MS m / z 2095.8275 [M + Na] + (Calcd for C 125 H 128 O ₂₆ SiNa _, found: 2095.8361)

2-O-benzoyl-hederagenin-3-O-2,3,4-O-benzoyl- alpha -L0-rhamnopyranosyl- (1 → 3) - [2, (1? 4)] - 2-O-benzoyl-? -L-arabinopyranoside (9d)

White _{solid, R f = 0.55 (n-} Hexane / EtOAc, 2: 1, v / v) [α] D + 28 ° (c 0.05, CHCl 3) 1 H NMR (400 MHz, CDCl 3) δ 7.14 - 8.15 (m, 3 H) 5.46 (br s, 1 H) 5.39 (s, 1 H) 5.74 - 4.30 (br.s., 1H) 4.59-4.83 (m, 3 H) 4.48-4.59 (m, 2 H) 4.38-4.48 (m, 2 H) 4.11-4.24 (m, 2 H) 3.61-3.79 (m, 2 H) 2.90 (dd, J = 13.02, 2.75 Hz, 1 H) 1.29 H) 1.00-1.04 (m, 3 H) 0.97 (s, 3 H) 0.93 (s, 3 H) 0.91 (s, 3 H) 0.37 (s, 3 H) ¹³ C NMR (100 MHz, CDCl ₃ ) .22 165.90 165.85 165.67 165.55 165.45 165.24 133.68 133.43 133.37 133.14 132.99 130.07 130.01 129.96 129.90 129.75 129.59 129.51 129.43 129.22 129.11 128.88 128.69 128.54 128.47 128.43 128.36 128.30 101.06.54 91.08 72.85 72.63 71.09 70.53 70.44 69.67 69.51 69.47 69.18 68.59 66.59 62.68 62.50 60.49 48.54 47.56 47.18 43.76 42.61 42.48 40.16 38.95 37.31 34.92 33.25 31.44 30.44 28.80 26.59 25.92 24.50 24.29 24.17 20.46 19.12 18.63 17.97 16.46 14.18 14.04 IR v max cm -1 (KBr) 2939.42 2861.69 1724.54 1602.75 1452.71 1382.38 1262.11 1094.76 MALDI-TOF-MS m / z 2110.4089 [M + Na] + (Calcd for C 126 H 130 O 26 SiNa, found: 2109.8517)

3-O-2,3,4,6-O- benzoyl- beta -Do- glucopyranosyl- (1? 3) -? - benzodiazyl- 2-O-benzoyl-a-L-arabinopyranoside (9e)

White _{solid, R f = 0.55 (n-} Hexane / EtOAc, 2: 1, v / v) [α] D + 74 ° (c 0.05, CHCl 3) 1 H NMR (400 MHz, CDCl 3) δ 7.02 - 8.32 (m, 1H) 6.09 (d, J = 9.90 Hz, 1H) 5.95-6.03 (m, 1H) 5.88 (br.s, 3H) 5.69-5.78 (m, 1H) 5.57 . s, 1 H) 5.42 - 5.52 (m, 1 H) 5.27 (br.s., 1 H) 5.16 (d, J = 6.97 Hz, 1 H) 4.69 (d, J = 11.74 Hz, 1 H) 4.38 J = 9.17 Hz, 1H), 4.01 (d, J = 13.20 Hz, 1 H), 4.56 (br s, H) 3.94 (d, J = 11.37 Hz, 1 H) 3.74 (d, J = 11.37 Hz, 1 H) 3.46 - 3.54 (m, 1 H) 3.41 (d, J = 12.84 Hz, 1 H) 2.84 - 2.94 (m, 1 H) 1.31 (d, J = 6.24 Hz, 3 H) 1.18 - 2.00 (m, 22 H) 1.13 (br s, ) 0.92 (s, 3 H) 0.86 (s, 3 H) 0.57 (s, 3 H) 0.34 (s, 3 H) 13 C NMR (100 MHz, CDCl 3) δ166.09 165.78 165.41 165.10 165.06 164.65 164.56 136.94 133.30 133.03 132.82 130.09 129.93 129.64 (129.62 129.42 128.93 128.49 128.36 128.17 127.99 101.59 98.10 95.08 73.02 72.36 72.21 71.98 71.57 71.48 70.80 70.74 69.74 69.63 69.30 68.61 67.08 62.91 48.54 47.56 47.18 43.76 42.61 42.48 40.16 38.95 37.31 34.92 33.25 31.44 30.44 28.80 26.59 25.92 24.50 24.29 24.17 20.46 19.12 18.63 17.97 16.46 14.18 14.04 IR v _max cm ^-1 (KBr) 2936.33 2861.89 1723.55 1602.67 1451.54 1381.54 1262.18 1093.33; MALDI-TOF-MS m / z 2109.5001 [M + Na] ⁺ (Calcd for C ₁₂₆ H ₁₃₀ O ₂₆ SiNa _, found: 2109.8517)

2-O-benzoyl-hederagenin-3-O-2,3,4,6-O- benzoyl- alpha -D-mannopyranosyl- (1 → 3) - [ 2-O-benzoyl-a-L-arabinopyranoside (9f)

White _{solid, R f = 0.50 (n-} Hexane / EtOAc, 2: 1, v / v) [α] D + 215 ° (c 0.05, CHCl 3) 1 H NMR (400 MHz, CDCl 3) δ 7.20 - 8.13 (m, 1 H) 6.07 (s, 1 H) 5.81 (d, J = 2.20 Hz, 3 H) 5.74 - 5.79 H) 5.33 (s, 1H) 5.28 (br.s, 2H) 4.64-4.70 (m, 1H) 4.41-4.46 (m, 4 H) 3.56 - 3.69 (m, 2 H) 2.84 - 2.94 (m, 1 H) 1.28 (s, 3 H) 1.16 - 1.96 , 3 H) 1.00 (s, 3 H) 0.89 (s, 3 H) 0.87 (s, 3 H) 0.38 (s, 3 H) 13 C NMR (100 MHz, CDCl 3) δ165.96 165.83 165.72 165.59 165.35 165.25 165.22 165.05 133.43 133.36 133.27 133.22 133.07 132.89 132.72 130.28 130.17 130.13 129.82 129.44 129.52 129.52 129.49 129.44 129.22 129.07 128.93 128.48 128.41 128.33 128.22 128.13 102.88 95.06 90.91 73.57 73.42 71.60 70.98 70.71 69.13 66.26 64.17 62.26 58.74 48.54 47.56 47.18 43.76 42.61 42.48 40.16 38.95 37.31 34.92 33.25 31.44 30.44 28.80 26.59 25.92 24.50 24.29 24.17 20.46 19.12 18.63 1 7.97 16.46 14.18 14.04 IR v _max cm ^-1 (KBr) 2932.53 2861.53 1722.56 1603.27 1453.26 1381.64 1262.71 1094.78; MALDI-TOF-MS m / z 2095.3085 [M + Na] + (Calcd for C 125 H 128 O 26 SiNa, found: 2095.8361)

2-O-benzoyl-hederagenin-3-O-2,3,4-O-benzoyl- alpha -L0-rhamnopyranosyl- (1 → 3) - [2, 4-O-benzoyl-a-L-arabinopyranoside (9 g)

White _{solid, R f = 0.55 (n-} Hexane / EtOAc, 2: 1, v / v) [α] D + 28 ° (c 0.05, CHCl 3) 1 H NMR (400 MHz, CDCl 3) δ 6.86 - 8.14 (m, 5H), 5.31 (s, 1H), 5.29 (br, s, 1H) ) 4.90 (s, 1H) 4.62-4.71 (m, 1H) 4.51-4.60 (m, 1H) 4.39-4.50 (m, 2H) 4.22-4.30 ) 3.77 - 3.86 (m, 1 H) 3.66 (dd, J = 11.55, 4.22 Hz, 1 H) 2.89 (dd, J = 13.02, 3.48 Hz, 1 H) 1.52 (d, J = 6.24 Hz, 3 H) 1.47 (s, 3H), 1.47 (d, J = 6.24 Hz, 3H) 1.17-2.03 H) 0.37 (s, 3 H ) 13 C NMR (100 MHz, CDCl 3) δ166.14 166.06 165.42 165.10 165.02 133.58 133.44 133.35 133.29 132.99 132.84 132.80 130.11 129.95 129.88.75 129.69 129.52 129.49 129.39 129.33 129.24 129.11 128.58 128.50 128.44 128.22. 15 128.11 128.05 98.81 98.70 91.17 71.77 71.60 71.24 71.09 71.00 70.13 69.94.82 67.94 67.70 67.61 61.55 60.47 17.97 17.66 48.54 47.56 47.18 43.76 42.61 42.48 40.16 38.95 37.31 34.92 33.25 31.44 30.44 28 .80 26.59 25.92 24.50 24.29 24.17 20.46 19.12 18.63 17.97 16.46 14.18 14.04 IR v _max ^{cm -1 (KBr) 2936.13 2863.42 1722.76} 1602.28 1451.34 1381.61 1263.93 1096.58 MALDI-TOF-MS m / z 1990.1177 [M + Na] + (Calcd for C 119 H 126 O 24 SiNa, found: 1989.8306)

28-O-t- Butyl diphenylsilyl -23-O- Benzoyl - Hederagenin -3-O-2,3,4,6-O- Benzoyl -α-L-O- only Nofilano (1? 3) - [2,3,4,6-O- Benzoyl -α-D-O- Mannpyranosil - (1- > 4)] - 2-O- Benzo 1-alpha-L-arabinopyranoside (9h)

White _{solid, R f = 0.52 (n-} Hexane / EtOAc, 2: 1, v / v) [α] D + 38 ° (c 0.05, CHCl 3) 1 H NMR (400 MHz, CDCl 3) δ 6.75 - 8.20 (m, 1H) 6.27 (m, 1H) 6.22 (d, J = 10.27 Hz, 1H) 6.14-6.20 (m, 1H) 5.94-6.02 (M, 1H), 4.74 (s, 1H), 5.73 (br.s, 1H) 4.81 (m, 1H), 4.81 (m, 1H), 4.62-4.72 (m, (M, 2 H) 2.93 (dd, J = 13.20, 2.93 Hz, 1 H) 1.23-2.11 3H) 0.41 (s, 3 H) ¹³ C NMR (100 MHz, CDCl ₃ )? 165.98 165.85 165.61 165.53 165.15 165.04 133.38 133.33 (s, 3H) 133.22 133.17 133.09 133.01 132.89 129.97 129.92 129.84 129.73 129.53 129.40 129.32 129.22 129.12 128.44 128.37 128.16 101.23 98.69 91.15 74.49 72.03 70.97 70.85 70.26 70.08 69.94 69.90 67.91 67.25 62.21 62.01 48.54 47.56 47.18 43.76 42.61 42.48 40.16 38.95 37.31 34.92 33.25 31.44 30.44 28.80 26.59 25.92 24.50 24.29 24.17 20.46 19.12 18.63 16.46 14.18 14.04 IR v _max ^{cm -1 (KBr) 2932.23 2862.48 1726.94} 1601.59 1451.17 1383.68 1264.11 1094.41 MALDI-TOF-MS m / z 2229.7166 [M + Na] + (Calcd for C 133 H 134 O 28 SiNa, found: 2229.8729)

28-O-t-butyl Diphenylsilyl -23-O-benzoyl-hederagenin-3-O- alpha -D-O-mannopyranosyl- (1 → 3) -4-0- Benzoyl -α-L- Arabinophilanoside (9i)

White _{solid, R f = 0.54 (n-} Hexane / EtOAc, 2: 1, v / v) [α] D + 46 ° (c 0.05, CHCl 3) 1 H NMR (400 MHz, CDCl 3) 7.23 - 8.22 ( m, 1 H) 6.01-6.10 (m, 1H) 5.53-5.69 (m, 3 H) 5.38-5.43 (M, 1 H) 4.51-4.57 (m, 1H) 4.26 (br.s, 2 H) 4.09-4.16 H) 2.89 (dd, J = 13.75, 3.48 Hz, 1 H) 1.28 (s, 3 H) 1.21 - 1.99 (m, 22 H) 1.13 (s, 9 H) 1.01 (s, 3 H) 0.96 (s, 3 H) 0.93 (s, 3 H) 0.92 (s, 3 H) 0.74 (s, 3 H) 0.37 (s, 3 H) ¹³ C NMR (100 MHz, CDCl ₃ )? 166.08 165.52 165.30 165.06 137.27 133.46 133.38 133.20 133.10 129.93 129.74 129.55 128.98 128.77 128.55 128.47 128.37 128.31 127.85 98.61 96.99 77.15 70.66 70.33 70.19 69.79 69.22 66.23 64.78 63.52 62.44 48.54 47.56 47.18 43.76 42.61 42.48 40.16 38.9537.31 34.92 33.25 31.44 30.44 28.80 26.59 25.92 24.50 24.29 24.17 20.46 19.12 18.63 17.97 16.46 14.18 14.04 IR v _max ^{cm -1 (KBr) 2935.22 2865.38 1724.14} 1602.34 1452.15 1381.45 1266.61 1092.84 MALDI-TOF-MS m / z 1694.0912 [M + Na] + (Calcd for C 101 H 110 O 20 SiNa, found: 1693.7257)

Example 7. Preparation of compounds 10a to 10i

TBDPS groups were deprotected by TBAF and all benzoyl groups and acetyl groups were deprotected using potassium t-butoxide to give saponin derivatives 10a-10i with arabinose-core. All protected compounds 9a to 9i (0.027 mmol) were dissolved in THF (3 mL), TBAF (0.054 mmol) was added, and the mixture was stirred at room temperature until the reaction was completed. Potassium t-butoxide (0.4 mmol) was added thereto and stirred for 24 hours. Amberlite acid resin was added to adjust the pH to 7, followed by concentration and separation to obtain saponin derivatives 10a to 10i in 65-84% yield.

Hederagenin -3-O- [alpha] -L- Arabinopyranosyl - (1 → 3) - [α-L- Laminopyranosyl - (1 → 4)] - α-L- Arabinophilanoside (10a)

White _{solid, R f = 0.25 (CHCl 3} / MeOH / H 2 O, 40: 10: 1, v / v / v) [α] D + 12 ° (c 0.05, MeOH) 1 H NMR (400 MHz, Pyr J = 6.97 Hz, 2H), 4.97 (d, J = 7.34 Hz, 2H), 4.66 (d, J = 1.83 Hz, 1H) 4.50-4.56 (m, 1H) 4.42-4.50 (m, 1H) 4.25-4.36 (m, 4H) 4.17-4.22 (m, 1H) 4.03-4.12 3.72 (br.s, 2 H) 3.42-3.51 (m, 2 H) 3.24-3.37 (m, 1H) 1.62 (d, J = 6.24 Hz, (s, 3 H) 0.94 ( s, 3 H) 0.93 (s, 3 H) 0.92 (s, 3 H) 0.91 (s, 3 H) 0.90 (s, 3 H) 13 C NMR (100 MHz, Pyr)隆 180.32 144.63 106.17 105.17 105.05 81.62 80.71 78.15 77.99 76.60 75.40 73.79 72.52 71.87 71.24 68.48 65.94 65.85 63.93 62.39 47.92 47.28 46.43 43.25 41.91 41.74 39.52 38.51 36.68 33.98 33.01 32.63 30.71 28.10 25.89 23.62 23.54 23.44 17.88 17.24 15.86 13.3 IR v _max cm ^-1 KBr) 3435.61 2933.11 1702.54 1632.56 1455.68 1387.31 1266.32 1071.24; MALDI-TOF-MS m / z 905.5343 [M + Na] ⁺ (Calcd for C ₄₆ H ₇₄ O ₁₆ Na _, found: 905.4875)

Hederagenin -3-O- [alpha] -L- Arabinopyranosyl - (1 → 3) - [β-D- Glucopyranosyl - (1 → 4)] - α-L- Arabinophilanoside (10b)

_{white solid, R f = 0.30 (} CHCl 3 / MeOH / H 2 O, 40: 10: 1, v / v / v) [α] D + 104 ° (c 0.05, MeOH) 1 H NMR (400 MHz, Pyr ) δ 5.45 (br.s., 1 H ) 5.36 (d, J = 6.97 Hz, 2 H) 4.91 (d, J = 6.97Hz, 1 H) 4.50 - 4.60 (m, 3 H) 4.40 - 4.49 (m J = 8.25 Hz, 1H), 3.89 (br.s, 1H), 3.82 (d, J = 11.00 Hz, 1 H) 3.67 ( d, J = 10.64 Hz, 1 H) 3.62 (d, J = 12.10 Hz, 1 H) 3.22 - 3.31 (m, 1 H) 1.23 - 2.18 (m, 22 H) 1.21 ( s, 3 H) 0.99 (s, 3 H) 0.98 (s, 3 H) 0.91 (s, 6 H) 0.86 (s, 3 H) ¹³ C NMR (100 MHz, Pyr)? 180.75 144.63 105.05 81.62 80.71 78.15 77.99 76.60 75.40 73.79 72.52 71.87 71.24 68.48. 96 65.85 63.93 63.18 62.39 47.92 47.28 46.43 43.25 41.91 41.74 39.52 .51 36.68 33.98 33.01 32.63 30.71 28.10 25.89 23.62 23.54 23.44 17.88 17.24 15.86 13.37 IR v _max cm ^-1 (KBr) 3433.21 2935.32 1705.72 1631.66 1451.21 1383.15 1262.73 1072.63; MALDI-TOF-MS m / z 921.4430 [M + Na] ⁺ (Calcd for C ₄₆ H ₇₄ O ₁₇ Na _, found: 921.4824)

Hederagenin -3-O- [alpha] -L- Arabinopyranosyl - (1 → 3) - [α-D- Mannpyranosil - (1 → 4)] - α-L- Arabinophilanoside (10c)

White _{solid, R f = 0.25 (CHCl 3} / MeOH / H 2 O, 40: 10: 1, v / v / v) [α] D + 38 ° (c 0.05, MeOH) 1 H NMR (400 MHz, Pyr ): 5.57 (s, 1H) 5.45 (br.s, 1H) 5.04 (d, J = 6.60 Hz, 2H) 4.89-4.96 J = 8.62, 2.75 Hz, 1H) 4.02 (dd, J = 9.54,2.93 Hz, 1H), 4.54 (m, 3H), 4.35-4.43 , 1 H) 3.75 (d, J = 11.37 Hz, 1 H) 3.68 (d, J = 10.64 Hz, 1 H) 3.47 (d, J = 12.84 Hz, 1 H) 3.23 - 3.31 (m, 1 H) 1.26 - 2.19 (m, 22 H) 1.22 (s, 3 H) 0.98 (.. br s, 6 H) 0.91 (s, 3 H) 0.88 (s, 3 H) 0.86 (s, 3 H) 13 C NMR ( 100 MHz, Pyr)? 180.75 144.61 122.29 106.96 106.42 98.10 81.87 74.09 73.55 72.62 72.43 72.27 71.77 71.60 70.36 69.04 66.52 63.86 .35 47.90 47.26 46.43 46.20 43.26 41.91 41.7439.52 38.49 36.66 33.97 33.02 32.64 30.71 28.10 25.91 23.61 23.54 23.43 .89 17.23 15.81 14.32 13.35 IR v _max cm ^-1 3434.23 2932.67 1702.71 1634.65 1453.55 1382.51 1264.36 1073.41 MALDI-TOF-MS m / z 921.4034 [M + Na] ⁺ (Calcd for C ₄₆ H ₇₄ O ₁₇ Na _, found: 921.4824)

Hederagenin -3-O- [alpha] -L- Laminopyranosyl - (1 → 3) - [α-D- Mannpyranosil - (1 - > 4)] - [alpha] -L- Rabino Piranhosi (10d)

White _{solid, R f = 0.63 (CHCl 3} / MeOH / H 2 O, 40: 10: 1, v / v / v) [α] D + 44 ° (c 0.05, MeOH) 1 H NMR (400 MHz, Pyr ), 4.38 (d, J = 8.4 Hz, 1H), 5.78 (s, 1H) (D, J = 10.64 Hz, 1H), 3.40 (d, J = 12.84 Hz, 1H) 3.26-3.34 (m, 1H) (D, J = 6.24 Hz, 3 H) 1.27-2.21 (m, 22 H) 1.25 (s, 3 H) 1.02 H) 0.91 (s, 3 H ) 0.86 (s, 3 H) 13 C NMR (100 MHz, Pyr) δ 180.75 145.31 135.46 130.78 128.81 124.46 123.43 117.10 107.45 103.48 98.11 82.51 77.01 75.34 75.24 73.14 72.99 72.88 72.63 72.56 72.43 70.82 69.91 64.5862 .51 48.60 47.94 47.11 46.89 43.92 42.62 42.44 40.22 40.16 39.21 37.36 34.67 33.71 33.35 31.41 30.44 28.80 26.60 24.32 24.24 24.15 19.18 18.57 17.93 16.52 14.04 IR v _max cm ^-1 (KBr) 3431.23 2932.62 1702.411633.41 1453.76 1384.13 1263.78 1073.28; MALDI-TOF-MS m / z 935.5480 [M + Na] ⁺ (Calcd for C ₄₇ H ₇₆ O ₁₇ Na _, found: 935.4980)

(1 → 3) - [α-L-rhamnopyranosyl- (1 → 4)] - α-L-aryla-3-O-β-D-glucopyranosyl Rabino Piranhosi (10e)

White _{solid, R f = 0.33 (CHCl 3} / MeOH / H 2 O, 40: 10: 1, v / v / v) [α] D + 26 ° (c 0.05, MeOH) 1 H NMR (400 MHz, Pyr ) 5.97 (s, 1H) 5.48 (br.s., 1H) 5.15 (d, J = 7.70 Hz, 1H) 4.98 ) 4.38 - 4.57 (m, 4 H) 4.20 - 4.34 (m, 4 H) 4.05 - 4.14 (m, 1 H) 3.92 - 4.01 (m, 1 H) 3.73 (d, J = 10.64 Hz, 1 H) 3.66 (d, J = 11.74 Hz, 1 H) 3.30 (dd, J = 13.39, 3.48 Hz, 1 H) 1.62 (d, J = 5.87 Hz, 3 H) 1.27 - 2.22 (m, 22 H) 1.25 (s, ¹³ H NMR (100 MHz, Pyr)? 181.30 145.28 (s, 3 H) 0.91 (s, 123.02 106.91 106.89 103.28 83.99 82.48 79.09 78.60 76.16 75.36 72.92 72.51 72.24 71.94 70.76 66.34 64.62 63.27 48.61 47.99 47.11 43.99 42.61 42.43 40.22 39.24 37.38 35.59 34.66 33.75 33.35 31.41 28.81 26.60 24.30 24.22 24.14 19.02 18.59 17.93 16.52 14.1 IR v _max cm ^-1 (KBr ) 3433.76 2935.271704.22 1632.12 1452.61 1382.35 1264.72 1074.54; MALDI-TOF-MS m / z 935.7244 [M + Na] ⁺ (Calcd for C ₄₇ H ₇₆ O ₁₇ Na _, found: 935.4980)

Hederagenin -3-O- [alpha] -D- Mannpyranosil - (1 → 3) - [α-L- Arabinopyranosyl - (1 → 4)] - α-L- Arabinophilanoside (10f)

White _{solid, R f = 0.27 (CHCl 3} / MeOH / H 2 O, 40: 10: 1, v / v / v) [α] D + 50 ° (c 0.05, MeOH) 1 H NMR (400 MHz, Pyr ) 5.88 (br.s., 1 H) 5.48 (br.s., 1 H) 4.92 (d, J = 5.87 Hz, 2 H) 4.88 (br.s., 1 H) 4.75 - 4.82 J = 6.60 Hz, 2H), 4.32-4.37 (m, 2H), 4.66 (d, J = (m, 2 H) 4.26 ( d, J = 11.74 Hz, 1 H) 4.20 (br.s., 3 H) 4.00 (d, J = 6.97 Hz, 1 H) 3.64 (dd, J = 15.77, 12.10 Hz , 2 H) 3.55 (d, J = 12.10 Hz, 1 H) 3.30 (d, J = 11.74 Hz, 1 H) 1.29 - 2.23 (m, 22 H) 1.25 (br.s., 3 H) 1.02 (s , 3 H) 1.01 (s, 3 H) 0.94 (br s, 9 H) ¹³ C NMR (100 MHz, Pyr)? 180.71 145.29 123.02 107.44 106.96 99.30 82.55 77.72 75.26 74.81 73.29 72.85 72.53 71.59 69.99 69.63 67.56 66.37 64.87 .54 48.60 48.03 47.11 46.87 43.89 42.62 42.43 40.22 39.16 37.38 34.66 33.71 33.35 31.40 30.44 28.79 26.61 26.55 24.32 24.24 24.14 18.60 17.94 16.54 14.17 IR v _max cm ^-1 (KBr) 3434.82 2932.64 1703.671635.87 1455.68 1385.81 1263.33 1072.31; MALDI-TOF-MS m / z 921.5866 [M + Na] ⁺ (Calcd for C ₄₆ H ₇₄ O ₁₇ Na _, found: 921.4824)

(1 → 3) - [α-L-Raminopyranosyl- (1 → 4)] - α-L-arabinopyranoside (10 g)

White _{solid, R f = 0.28 (CHCl 3} / MeOH / H 2 O, 40: 10: 1, v / v / v) [α] D + 16 ° (c 0.05, MeOH) 1 H NMR (400 MHz, Pyr ) δ 5.94 (br.s., 1 H ) 5.80 (br.s., 1 H) 5.44 (br.s., 1 H) 4.92 (d, J = 6.24 Hz, 1 H) 4.68 (d, J = 12.84 Hz, 2 H) 4.58 ( d, J = 7.34 Hz, 1 H) 4.10 - 4.52 (m, 9 H) 3.60 - 3.71 (m, 2 H) 3.41 - 3.52 (m, 2 H) 3.26 (d, J = 11.74 Hz, 1H) 1.64 (d, J = 5.87 Hz, 3 H) 1.58 (d, J = 5.87 Hz, 3 H) 1.25-2.21 , 3 H) 0.91 (s, 3 H) 0.90 (s, 3 H) 0.87 (br.s., 6 H) 13 C NMR (100 MHz, Pyr) δ180.75 144.64 122.27 106.48 103.19 103.09 81.87 78.94 75.56 73.87 73.79 72.48 72.35 71.96 70.19 69.97 63.90 58.61 47.90 47.23 46.43 46.23 43.25 41.91 41.75 39.52 38.49 36.66 34.00 33.03 32.96 32.64 30.71 28.10 25.91 23.88 23.62 23.56 23.46 19.78 18.49 18.30 17.89 17.25 15.82 13.54 13.42 IR v _max cm ^-1 (KBr) 3436.83 2934.34 1703.211633.56 1453.61 1383.98 1264.77 1074.51; MALDI-TOF-MS m / z 919.6133 [M + Na] ⁺ (Calcd for C ₄₇ H ₇₆ O ₁₆ Na _, found: 919.5031)

(1 → 3) - [α-L-mannopyranosyl- (1 → 4)] - α-L-arabinopyranoside (10h)

White _{solid, R f = 0.30 (CHCl 3} / MeOH / H 2 O, 40: 10: 1, v / v / v) [α] D + 140 ° (c 0.05, MeOH) 1 H NMR (400 MHz, Pyr ) δ 5.98 (br.s., 1H) 5.57 (br.s., 1H) 4.34 - 4.43 (m, 3 H) 4.17 - 4.27 (m, 2 H) 4.14 (m, 1 H) 3.62 (d, J (Br.s., 3 H) 0.98 (br.s, 6 H) 0.91 (s, 2 H) 1.26-2.18 3 H) 0.88 (br.s, 6 H) ¹³ C NMR (100 MHz, Pyr)? 180.75 144.61 122.29 106.44 98.57 97.34 82.24 75.43 .10 74.54 72.50 72.18 71.97 70.59 69.08 68.78 68.59 64.33 63.40 62.83 62.04 47.89 47.41 46.41 46.19 43.13 41.91 41.73 39.51 38.45 36.68 33.96 33.02 32.96 32.67 30.70 28.09 25.90 25.71 23.62 23.54 23.43 17.91 17.22 15.81 13.39 IR v _max cm ^-1 (KBr) 3433.56 2937.16 1703.631634.71 1454.89 1385.78 1266.21 1072.46; MALDI-TOF-MS m / z 951.7219 [M + Na] ⁺ (Calcd for C ₄₇ H ₇₆ O ₁₈ Na _, found: 951.4929.5031)

Hederagenin 3-O- [alpha] -D- Mannpyranosil - (1 → 3) -α-L- Arabinophilanoside (10i)

White solid, R _f = 0.28 (CHCl ₃ / MeOH / H ₂ O, 40: 10: 1, v / v / v) [?] _D + 146 ° ( c 0.05, MeOH) ¹ H NMR ): 5.83 (s, 1H) 5.45 (br.s., 1H) 4.91 4.95 (m, H) 4.45 s, 2 H) 4.25 - 4.37 (m, 3 H) 4.21 (d, J = 12.47 Hz, 2 H) 0.99 (s, 3 H) 0.98 (s, 3 H) 0.93 (s, 3 H) ^{0.91 (s, 6 H) 13} C NMR (100 MHz, Pyr) δ 180.75 144.67 106.44 98.09 81.79 77.65 74.64 72.71 72.09 70.73 68.97 66.64 65.22 64.20 62.93 47.90 47.33 46.42 43.22 41.91 41.73 41.39 39.51 38.48 36.68 34.00 33.64 32.65 30.69 28.13 25.88 23.54 23.43 17.91 17.24 15.82 13.47 IR v _max cm ^-1 (KBr) 3432.36 2934.32 1702.781636.31 1453.66 1382.54 1263.79 1073.45; MALDI-TOF-MS m / z 789.4209 [M + Na] ⁺ (Calcd for C ₄₁ H ₆₆ O ₁₃ Na _, found: 789.4401)

Example 8. Preparation of compounds 12a to 12d

To synthesize saponins having a lambda-core, Receptor 11 was glycosylated with donors a to d under standard conditions to give disaccharide moieties 12a to 12d. TMSOTf (0.32 mmol) was added to a solution of isopropylidene (11) (1.6 mmol) and trichloroacetimidate ad (2.4 mmol) in methylene chloride (20 mL) After the reaction, it was neutralized with triethylamine. Concentration and isolation afforded protected 12a-12d in 81-87% yield.

,

2,3,4-O- Benzoyl -α-L- Arabinopyranosyl - (1- > 4) -2,3- Isopropylidene -1-O-benzyl-a-L- Rhamnopyranoside (12a)

White _{solid, R f = 0.48 (n-} Hexane / EtOAc, 2: 1, v / v) [α] D + 115.3 ° (c 0.1, CHCl 3) 1 H NMR (250 MHz, CDCl 3) δ 8.03 - 8.11 (m, 4 H) 7.87 - 7.93 (m, 2 H) 7.23 - 7.64 (m, 14 H) 5.66 - 5.77 (m, 2 H) 5.54 - 5.62 (m, 1 H) 5.23 (d, J = 6.95 Hz , 1 H) 5.02 (s, 1 H) 4.65 (d, J = 11.50 Hz, 1 H) 4.46 (d, J = 11.75 Hz, 1 H) 4.32 (dd, J = 13.03, 3.08 Hz, 1 H) 4.03 - 4.07 (m, 2 H) 3.88 (dd, J = 13.03, 1.34Hz, 1 H) 3.56 - 3.77 (m, 2 H) 1.56 (s, 3 H) 1.35 (d, J = 5.84 Hz, 3 H) ^{1.30 (s, 3 H) 13} C NMR (63 MHz, CDCl 3) δ 165.89 165.76 165.52 136.98 133.50 133.40 133.32 130.03 129.92 129.67 129.61 129.15 128.61 128.44 128.42 128.38 128.09 109.38 100.52 96.12 80.37 78.25 76.14 71.35 70.23 69.20 68.95 64.21 63.56 28.03 26.32 IR v _max cm ^-1 (KBr) 2932.25 1731.83 1602.61 1453.34 1382.41 1313.41 1263.91 1116.21 MALDI-TOF-MS m / z 761.0698 [M + Na] ⁺ (Calcd for C ₄₂ H ₄₂ O ₁₂ Na _, found: 761.2574)

2,3,4-O- Benzoyl -α-L- Laminopyranosyl - (1- > 4) -2,3- Isopropylidene -1-O-benzyl-a-L-lamb Nopirano city (12b)

White _{solid, R f = 0.59 (n-} Hexane / EtOAc, 2: 1, v / v) [α] D + 81.3 ° (c 0.1, CHCl 3) 1 H NMR (250 MHz, CDCl 3) δ8.08 - 8.15 (m, 2H) 7.93-7.99 (m, 2H) 7.77-7.84 (m, 2H) 7.32-7.65 H) 5.68 (t, J = 9.64 Hz, 1 H) 5.60 (d, J = 1.42 Hz, 1 H) 5.10 (s, 1H) 4.76 (d, J = 11.75 Hz, 1 H) 4.56 (d, J = 11.75 Hz, 1 H) 4.34 ( dd, J = 7.11, 5.69 Hz, 1 H) 4.16 - 4.25 (m, 2 H) 3.91 (dd, J = 9.95, 6.16 Hz, 1 H) 3.65 (dd, J = 9.79 , 7.27 Hz, 1 H) 1.55 (s, 3 H) 1.43 (d, J = 6.16 Hz, 3 H) 1.38 (d, J = 6.32 Hz, 3 H) 1.33 (s, 3 H) 13 C NMR (63 MHz, CDCl ₃ )? 165.86 165.67 165.50 137.10 133.51 133.44 133.20 130.08 129.83 129.78 129.58 129.35 129.27 128.68 128.65 128.54 128.37 128.13 109.71 96.28 96.16 78.20 77.79 76.28 71.83 70.84 70.07 69.37 67.38 64.15 28.04 26.46 18.31 17.83 IR v _max cm ^-1 (KBr) MALDI-TOF-MS m / z 775.1827 [M + Na] ⁺ (Calcd for C ₄₃ H ₄₄ O ₁₂ Na _, found: 775.2730)

2,3,4,6-O- Benzoyl -D-D- Glucopyranosyl - (1- > 4) -2,3- Isopropylidene -1-O-benzyl-a-L- Rhamnopyranoside (12c)

White _{solid, R f = 0.48 (n-} Hexane / EtOAc, 2: 1, v / v) [α] D + 6.3 ° (c 0.1, CHCl 3) 1 H NMR (250 MHz, CDCl 3) δ 8.01 (dd , J = 7.03, 1.34Hz, 4 H) 7.89 - 7.94 (m, 2 H) 7.80 - 7.86 (m, 2 H) 7.23 - 7.58 (m, 17 H) 5.93 (t, J = 9.56 Hz, 1 H) 5.66 (t, J = 9.71 Hz , 1 H) 5.50 (dd, J = 9.48, 8.06 Hz, 1 H) 5.35 (d, J = 8.06 Hz, 1 H) 4.99 (s, 1 H) 4.58 - 4.71 (m (M, 2H), 3.48 (d, J = 9.79, 5.37 Hz, 2H), 1.48 (s, 3H) H) 1.29 (d, J = 5.69 Hz, 3 H) 1.25 (s, 3 H) ¹³ C NMR (63 MHz, CDCl ₃ ) 隆 166.23 165.95 165.41 165.39 136.91 133.58 133.34 133.28 130.04 129.93 129.85 129.79 129.60 129.50 128.93 128.84 128.59 128.51 128.40 128.36 128.08 109.34 100.47 96.00 80.80 78.06 76.08 73.16 72.32 72.13 70.03 69.16 28.04 26.27 17.58 IR v _max cm ^-1 (KBr) 2935.33 1734.49 1601.49 1452.84 1381.33 1312.46 1262.78 1114.69; MALDI-TOF-MS m / z 895.5116 [M + Na] ⁺ (Calcd for C ₅₀ H ₄₈ O ₁₄ Na _, found: 895.2942)

2,3,4,6-O- Benzoyl -α-D- Mannpyranosil - (1- > 4) -2,3- Isopropylidene -1-O-benzyl-a-L- Rhamnopyranoside (12d)

White _{solid, R f = 0.67 (n-} Hexane / EtOAc, 2: 1, v / v) [α] D -21.3 ° (c 0.1, CHCl 3) 1 H NMR (250 MHz, CDCl 3) δ8.12 - 8.18 (m, 2 H) 8.05 - 8.11 (m, 2 H) 7.94 - 8.00 (m, 2 H) 7.84 - 7.90 (m, 2 H) 7.21 - 7.64 (m, 17 H) 6.32 (t, J = 10.27 Hz, 1 H) 5.82 - 6.03 (m, 2 H) 5.68 (dd, J = 3.16, 1.74 Hz, 1 H) 5.26 (d, J = 1.42 Hz, 1 H) 5.10 (s, 1 H) 4.69 - 4.81 (m, 3 H) 4.44 - 4.60 (m, 2 H) 4.33 (dd, J = 7.19, 5.61 Hz, 1 H) 4.20 - 4.25 (m, 1 H) 3.91 (dd, J = 10.11, 6.32 Hz, 1 H) 3.55 (dd, J = 10.11, 7.42 Hz, 1 H) 1.61 (s, 3 H) 1.33 - 1.41 (m, 6 H) 13 C NMR (63 MHz, CHCl 3) δ166.36 165.75 165.61 165.56 137.07 134.00 133.85 133.60 133.48 133.35 133.08 130.14 130.05 129.92 129.88 129.85 129.18 129.13 128.84 128.76 128.68 128.53 128.44 128.41 128.15 109.59 98.32 96.11 81.77 76.91 76.30 70.66 70.18 69.42 69.00 66.50 65.06 62.30 28.34 26.58 17.45 IR v _max cm ^-1 (KBr) 2932.73 1732.81 1602.64 1453.12 1382.49 1313.72 1264.36 1112.39 MALDI-TOF-MS m / z 895.3927 [M + Na] ⁺ (Calcd for C ₅₀ H ₄₈ O ₁₄ Na _, found: 895.2942)

Example 9. Preparation of compounds 13a to 13d

Hydrolysis of the isopropylidene groups of the above-mentioned 12a to 12d to obtain diol compounds 13a to 13d in a yield of 84 to 91%. P-TsOH (1.12 mmol) was added to a solution of 12a to 12d (1.4 mmol) in methylene chloride-methanol (1: 2, 30 mL) and the mixture was stirred at room temperature. After completion of the reaction, the reaction mixture was completely dissolved with triethylamine, and then concentrated and separated to obtain 13a to 13d.

2,3,4-O- Benzoyl -α-L- Arabinopyranosyl - (1 → 4) -1-O-benzyl-α-L- Rhamnopyranoside (13a)

White _{solid, R f = 0.15 (n-} Hexane / EtOAc, 1: 1, v / v) [α] D + 97.4 ° (c 0.1, CHCl 3) 1 H NMR (250 MHz, CDCl 3) δ 7.98 - 8.11 (m, 4 H) 7.85 - 7.95 (m, 2 H) 7.20 - 7.63 (m, 14 H) 5.66 - 5.79 (m, 2 H) 5.56 - 5.63 (m, 1 H) 5.19 (d, J = 6.48 Hz , 1 H) 4.82 (s, 1 H) 4.66 (d, J = 11.85 Hz, 1 H) 4.44 (d, J = 11.85 Hz, 1 H) 4.30 (dd, J = 12.87, 3.7 1Hz, 1 H) 3.62 (D, J = 6.00 Hz, 3 H) ¹³ C NMR (63 MHz, CDCl ₃ )? 165.79 165.65 165.57 137.17 133.58133.51 133.42 129.96 129.86 129.83 129.49 129.19 129.07 128.65 128.60 128.54 128.43 128.06 127.98 101.16 98.56 81.04 71.51 71.29 70.97 70.59 69.19 68.60 66.62 62.95 17.92 IR v _max cm ^-1 (KBr) 3453.45 2925.25 1726.86 1602.31 1451.45, 1383.73 1315.25 1264.44 1176.21 1093.15 MALDI-TOF-MS m / z 721.1608 [M + Na] ⁺ (Calcd for C ₃₉ H ₃₈ O ₁₂ Na _, found: 721.2261)

(L > 4) -1-O-benzyl- alpha -L-rhamopyranoside (13b)

White _{solid, R f = 0.33 (n-} Hexane / EtOAc, 1: 1, v / v) [α] D + 68.7 ° (c 0.1, CHCl 3) 1 H NMR (250 MHz, CDCl 3) δ8.01 - 8.07 (m, 2H) 7.94-8.00 (m, 2H) 7.78-7.84 (m, 2H) 7.19-7.60 H) 5.48 (d, J = 1.42 Hz, 1 H) 4.89 (d, J = 1.26 Hz, 1 H) 4.74 (d, J = 12.00 Hz, 1 H) 4.52 (d, J = 11.85 Hz, 1 H) 4.29 (dd, J = 9.40, 6.24 Hz, 1 H) 4.06 - 4.18 (m, 1 H) 4.00 (td, J = 3.48, 1.58 Hz, 1 H) 3.88 (dd, J = 9.40, 6.08 Hz, 1 H ) 3.68 (t, J = 9.24 Hz, 1 H) 3.49 (d, J = 6.79 Hz, 1 H) 3.09 (d, J = 3.00 Hz, 1 H) 1.41 (d, J = 6.16 Hz, 3 H) 1.36 (d, J = 6.16 Hz, 3 H) ¹³ C NMR (63 MHz, CDCl ₃ )? 166.02 165.99 165.87 137.37 133.60 133.45 133.30 130.05 129.82 128.36 129.16 128.64 128.60 128.54 128.40 128.06 127.97 99.18 98.76 81.52 71.84 71.73 71.67 71.22 70.28 69.30 67.58 66.67 18.21 17.68 IR v _max cm ^-1 (KBr) 3453.31 2926.67 1722.56 1603.15 1454.67, 1382.98 1313.65 1262.38 1171.78 1093.89; MALDI-TOF-MS m / z 735.1319 [M + Na] + (Calcd for C 40 H 40 O 12 Na, found: 735.2417)

1-O-benzyl-α-L-rhamopyranoside (13c) was obtained in the same manner as in Example 1,

White _{solid, R f = 0.19 (n-} Hexane / EtOAc, 1: 1, v / v) [α] D -28 ° (c 0.1, CHCl 3) 1 H NMR (250 MHz, CDCl 3) δ8.01 - 8.06 (m, 2 H) 7.94 - 8.00 (m, 2 H) 7.88 - 7.93 (m, 2 H) 7.78 - 7.85 (m, 2 H) 7.22 - 7.58 (m, 17 H) 5.92 (t, J = 9.64 Hz, 1 H) 5.67 (t , J = 9.71 Hz, 1 H) 5.53 (dd, J = 9.79, 8.06 Hz, 1 H) 5.24 (d, J = 7.90 Hz, 1 H) 4.79 (s, 1 H) 4.58 - 4.72 (m, 2 H ) 4.37 - 4.51 (m, 2 H) 4.09 - 4.21 (m, 1 H) 3.58 - 3.85 (m, 4 H) 2.62 (d, J = 4.74 Hz, 1 H) 2.50 ( 1 H) 1.28 (d, J = 6.00 Hz, 3 H) ¹³ C NMR (63 MHz, CDCl ₃ ) δ 166.22165.88 165.34 165.29 137.11 133.60 133.56 133.37 133.32 129.93 129.84 129.55 129.10 128.82 128.78 128.65 128.56 128.54 IR v _max cm ^-1 (KBr) 3455.34 2923.65 1724.68 1605.16 1453.45, 1383.96 1315.18 1265.64 1172.31 1095.89; MALDI-TOF-MS m / z 855.2320 [M + Na] ⁺ (Calcd for C ₄₇ H ₄₄ O ₁₄ Na _, found: 855.2629)

2,3,4,6-O- Benzoyl -α-D- Mannpyranosil - (1 → 4) -1-O-benzyl-α-L- Rhamnopyranoside (13d)

_{C 47 H 44 O 14, white} solid, R f = 0.33 (n-Hexane / EtOAc, 1: 1, v / v) [α] D -76.7 ° (c 0.1, CHCl 3) 1 H NMR (250 MHz, _{CDCl 3) δ 8.11 (d,} J = 7.74 Hz, 2 H) 7.99 (d, J = 7.58 Hz, 4 H) 7.86 (d, J = 7.58 Hz, 2 H) 7.20 - 7.60 (m, 17 H) 6.17 (t, J = 10.19 Hz, 1 H) 5.92 (dd, J = 10.19, 1.97 Hz, 1 H) 5.70 (br.s., 1 H) 5.23 (s, 1 H) 4.81 - 4.94 (m, 3 H ) 4.69 (d, J = 12.00 Hz, 1 H) 4.36 - 4.48 (m, 2 H) 3.85 - 4.09 (m, 3 H) 3.73 (d, J = 6.79 Hz, 1 H) 3.66 (t, J = 9.16 Hz, 1 H) 3.25 (d , J = 2.53 Hz, 1 H) 1.43 (d, J = 6.00 Hz, 3 H) 13 C NMR (63 MHz, CDCl 3) δ 166.50 165.64 165.55 165.44 137.26 133.55 133.34 133.24 129.90 129.84 129.78 129.70 129.16 129.01 128.94 128.61 128.54 128.40 128.02 127.95 99.20 98.82 84.41 71.34 70.61 70.21 69.91 69.69 69.36 66.84 66.63 66.62 17.85 IR v _max cm ^-1 (KBr) 3453.43 2924.67 1726.86 1602.34 1452.64, 1382.48 1316.71 1263.38 1173.46 1095.92; MALDI-TOF-MS m / z 855.2320 [M + Na] ⁺ (Calcd for C ₄₇ H ₄₄ O ₁₄ Na _, found: 855.2629)

Example 10. Preparation of compounds 14a to 14d

The diol moieties of the compounds 13a to 13d were benzoylated to give protected compounds 14a to 14d. 13a to 13d (0.9 mmol) in pyridine (10 ml) was added benzyl chloride (3.6 mmol) at 0 ° C and the temperature was raised to room temperature. After completion of the reaction with water for 24 hours, pyridine was removed with 10% hydrochloric acid, followed by extraction with methylene chloride, followed by concentration and separation to obtain 96 to 99% of compounds 14a to 14d.

(1? 4) -2,3-O-benzoyl-1-O-benzyl-? L-rhamnopyranoside (14a)

White _{solid, R f = 0.39 (n-} Hexane / EtOAc, 2: 1, v / v) [α] D + 138.3 ° (c 0.1, CHCl 3) 1 H NMR (250 MHz, CDCl 3) δ7.94 - 8.08 (m, 4 H) 7.76 - 7.86 (m, 4 H) 7.11 - 7.63 (m, 22 H) 5.56-5.70 (m, 4 H) 5.39 (dd, J = 9.00, 3.48 Hz, d, J = 6.48 Hz, 1 H) 4.95 (d, J = 1.42 Hz, 1 H) 4.76 (d, J = 12.00 Hz, 1 H) 4.59 (d, J = 12.25 Hz, 1 H) 4.34 (dd, J = 12.87, 3.71 Hz, 1 H) 4.00 - 4.15 (m, 2 H) 3.91 (dd, J = 12.72, 1.50 Hz, 1 H) 1.51 (d, J = 5.53 Hz, 3 H) 13 C NMR (63 _{MHz, CDCl 3) δ165.80 165.60 165.41} 165.19 164.96 136.78 133.75 133.55 133.47 133.42 133.29 133.11 130.26 129.96 129.93 129.82 129.66 129.59 129.49 128.98 128.92 128.64 128.61 128.57 128.53 128.41 128.26 128.19 128.08 101.15 96.63 76.74 72.91 70.86 70.69 69.98 69.43 68.48 67.38 63.02 18.32 IR v _max cm < ^-1 > (KBr) 2935.36 1732.36 1602.66 1453.61 1381.35 1268.51 1092.61; MALDI-TOF-MS m / z 929.3611 [M + Na] ⁺ (Calcd for C ₅₃ H ₄₆ O ₁₄ Na _, found: 929.2785)

(1 → 4) -2,3-O-benzoyl-1-O-benzyl-α-L-rhamnopyranoside (14b )

White _{solid, R f = 0.63 (n-} Hexane / EtOAc, 2: 1, v / v) [α] D + 147.8 ° (c 0.1, CHCl 3) 1 H NMR (250 MHz, CDCl 3) δ 7.98 - 8.04 (m, 2 H) 7.92 - 7.97 (m, 2 H) 7.85 (d, J = 7.11 Hz, 2 H) 7.73 - 7.78 , 20 H) 5.85 (dd, J = 9.24, 3.40 Hz, 1 H) 5.78 (dd, J = 10.11, 3.32 Hz, 1 H) 5.72 (dd, J = 3.32, 1.74 Hz, 1 H) 5.59 (t, J = 9.87 Hz, 1 H) 5.48 (dd, J = 3.16, 1.58 Hz, 1 H) 5.37 (s, 1 H) 5.04 (d, J = 1.58 Hz, 1 H) 4.84 (d, J = 12.00 Hz, 1 H) 4.66 (d, J = 12.00 Hz, 1 H) 4.25 - 4.40 (m, 1 H) 4.09 - 4.22 (m, 2 H) 1.54 (d, J = 5.25 Hz, 3 H) 1.38 (d, J ^{= 6.16 Hz, 3 H) 13} C NMR (63 MHz, CDCl 3) δ165.79 165.45 165.24 165.19 164.47 136.79 133.65 133.46 133.32 133.07 132.90 130.20 129.86 129.80 129.70 129.61 129.48 129.37 129.16 129.09 128.65 128.58 128.50 128.35 128.21 128.15 128.11 99.46 96.75 78.71 72.69 71.64 70.92 70.63 69.77 69.40 67.97 66.96 18.46 17.61 IR v _max cm ^-1 (KBr) 2935.32 1731.74 1602.31 1454.12 1383.39 1262.90 1092.18; MALDI-TOF-MS m / z 943.1461 [M + Na] ⁺ (Calcd for C ₅₄ H ₄₈ O ₁₄ Na _, found: 943.2942)

Benzoyl- beta -D-glucopyranosyl- (1 → 4) -2,3-O-benzoyl-1-O- benzyl- alpha -L-rhamphyranoside (14c )

White _{solid, R f = 0.33 (n-} Hexane / EtOAc, 2: 1, v / v) [α] D + 12 ° (c 0.1, CHCl 3) 1 H NMR (250 MHz, CDCl 3) δ 8.02 - 8.09 (m, 2 H) 7.85 - 7.94 (m, 4 H) 7.67 - 7.77 (m, 4 H) 7.17 - 7.61 (m, 23 H) 7.07 (t, J = 7.74 Hz, 2 H) 5.62 - 5.79 (m (M, 2H) 5.08 (d, J = 7.90 Hz, 1H) 4.91 (d, J = 1.42 Hz, 1H) 4.70-4.82 m, 2 H) 4.56 (d , J = 10.00 Hz, 1 H) 4.46 (dd, J = 12.00, 5.21 Hz, 1 H) 4.16 - 4.26 (m, 1 H) 4.03 (d, J = 7.42 Hz, 2 H) 1.44 (d, J = 4.74 Hz, 3 H) ¹³ C NMR (100 MHz, CDCl ₃ )? 165.26 165.80 165.35 165.32 165.26 164.88 136.76 133.62 133.36 132.97 129.94 129.83 129.79 129.73 129.62 129.43 128.81 128.74 128.62 128.56 128.37 128.23 128.09 101.45 96.53 77.65 72.94 72.48 72.04 71.87 70.66 69.84 69.39 67.33 63.08 18.17 IR v max cm -1 (KBr) 2937.32 1736.24 1602.70 1453.54 1382.89 1264.15 1092.36; MALDI-TOF-MS m / z 1063.5254 [M + Na] ⁺ (Calcd for C ₆₁ H ₅₂ O ₁₆ Na _, found: 1063.3153)

(1 → 4) -2,3-O-benzoyl-1-O-benzyl-α-L-rhamnopyranoside (14d )

White _{solid, R f = 0.39 (n-} Hexane / EtOAc, 2: 1, v / v) [α] D + 52 ° (c 0.1, CHCl 3) 1 H NMR (250 MHz, CDCl 3) δ 7.74 - 8.10 (m, 12 H) 7.18 - 7.65 (m, 23 H) 6.14 (t, J = 10.19 Hz, 1 H) 5.91 (dd, J = 9.32, 3.48 Hz, 1 H) 5.77 (dd, J = 10.27, 3.16 J = 1.26 Hz, 1H) 5.03 (d, J = 1.42 Hz, 1H) 4.85 (d, J = 12.00 Hz, 1H) 4.66 (d, J = 12.00 Hz , 1 H) 4.18 - 4.28 (m, 2 H) 4.15 (d, J = 9.32 Hz, 1 H) 4.07 (dd, J = 12.32, 2.69 Hz, 1 H) 3.69 (dd , J = 12.72, 1.66 Hz, 1 H) 1.60 (d, J = 6.00Hz, 3 H) 13 C NMR (63 MHz, CDCl 3) δ 165.91 165.72 165.70 165.65 165.58 165.22 136.73 133.68 133.64 133.54 133.48 133.38 132.98 129.94 129.86 129.74 129.67 129.60 129.47 129.23 129.09 128.97 128.73 128.62 12846 128.43 128.31 128.24 98.95 96.70 80.29 71.04 70.83 69.91 69.78 69.36 67.89 65.90 61.80 18.35 IR v _max cm ^-1 (KBr) 2937.54 1734.15 1602.76 1454.89 1383.56 1263.93 1095.42; MALDI-TOF-MS m / z 1063.2619 [M + Na] ⁺ (Calcd for C ₆₁ H ₅₂ O ₁₆ Na _, found: 1063.3153)

Example 11. Structure of compounds 15a to 15d and compounds 20a to 20c

The benzyl groups of the compounds 14a to 14d (0.33 mmol) were selectively deprotected using 10% Pd / C (80 mg) to obtain compound disaccharides 15a to 15d in 96-99% yield. In addition, compounds 13c and 18 (1.05 mmol) were treated with triethylorthoacetate (4.20 mmol) and p-TsOH (0.53 mmol) and then cleaved in aqueous AcOH to yield C-2 monoacetylated glycosyl donor, C Compounds 16 and 19 having a free hydroxyl group at the -3 position were obtained in 72-87% yield. Receptors 16 and 19 (0.34 mmol) with donor a to c (0.53 mmol) were glycosylated at -78 <0> C using TMSOTf (0.07 mmol) to give trisaccharide moieties 17a-c, 78-87% , After which the benzyl group was selectively deprotected with Pd / C in THF-methanol solution under a hydrogen atmosphere to give 20a-20c in 82-87% yield.

(1? 4) -2,3-O-benzoyl-? -L-rhamopyranoside (15a)

White solid, (α: β = 5: 1) 1 H NMR (400 MHz, CDCl 3) δ 7.14 - 8.07 (m, 25 H) 5.57 - 5.68 (m, 4 H) 5.39 (dd, J = 9.17, 3.30 Hz, 1 H) 5.30 (d , J = 3.67 Hz, 1 H) 5.05 (d, J = 5.87 Hz, 1 H) 4.34 (dd, J = 12.84, 3.30 Hz, 1 H) 4.23 - 4.29 (m, 1 H) 4.11 (t, J = 9.17 Hz, 1 H) 3.92 (d, J = 12.47 Hz, 1 H) 3.51 (d, J = 3.67 Hz, 1H) 1.50 (d, J = 6.60 Hz, 3 H) 13 _{C NMR (100 MHz, CDCl 3} ) δ165.85 165.64 165.56 165.27 165.04 133.67 133.55 133.47 133.43 133.32 133.20 133.13 130.07 129.96 129.94 129.82 129.67 129.61 129.57 129.50 129.35 129.24 128.99 128.93 128.85 128.65 128.58 128.53 128.43 128.28 101.11 92.30 76.71 72.55 71.12 70.86 70.07 68.53 67.21 63.09 18.37

(L > 4) -2,3-O-benzoyl- alpha -L-rhamopyranoside (15b)

White solid, (α: β = 5: 1) 1 H NMR (250 MHz, CDCl 3) d ppm 7.05 - 8.06 (m, 25 H) 5.88 (dd, J = 9.71, 3.40 Hz, 1 H) 5.75 - 5.83 (m, 1H) 5.70 (dd, J = 3.32, 1.74 Hz, 1H) 5.59 (t, J = 9.95 Hz, 1H) 5.50 (dd, J = 3.40, 1.82 Hz, 1H) J = 1.58 Hz, 2 H) 4.27 - 4.46 (m, 2 H) 4.15 (t, J = 9.56 Hz, 1 H) 3.85 - 3.94 (m, 1 H) 1.55 (d, J = 6.16 Hz, 3 H) 1.38 (d, J = 6.32 Hz, 3 H) ¹³ C NMR (63 MHz, CDCl ₃ ) d ppm 165.88 165.64 165.33 164.57 133.49 133.36 133.11 132.96 130.05 129.91 129.84 129.75 129.67 129.53 129.39 129.18 129.12 128.61 128.53 128.39 128.24 128.21 99.43 92.19 78.76 72.38 71.70 71.43 70.70 69.50 67.98 66.76 18.59 17.62

(L > 4) -2,3-O-benzoyl- alpha -L-rhamopyranoside (15c)

white solid, (α: β = 5: 1) 1 H NMR (400 MHz, CDCl 3) δ8.05 (d, J = 7.34 Hz, 2 H) 7.93 (d, J = 7.34 Hz, 2 H) 7.88 ( d, J = 7.34 Hz, 2 H) 7.69 - 7.77 (m, 4 H) 7.05 - 7.60 (m, 20 H) 5.72 - 5.78 (m, 1 H) 5.64 (t, J = 9.90 Hz, 1 H) 5.54 - 5.59 (m, 2 H) 5.47 - 5.53 (m, 1 H) 5.27 (d, J = 2.93 Hz, 1 H) 5.10 (d, J = 8.07 Hz, 1 H) 4.77 (d, J = 8.80 Hz, 1 H) 4.48 (dd, J = 11.74, 5.14 Hz, 1 H) 4.22 (d, J = 9.54 Hz, 2 H) 4.04 (t, J = 9.54 Hz, 1 H) 3.52 (d, J = 3.67 Hz, 1 H) 1.43 (d, J = 5.87 Hz, 3 H) ¹³ C NMR (100 MHz, CDCl ₃ )? 165.99 165.82 165.48 165.32 164.94 133.57 133.49 133.37 133.33 133.07 132.98 129.98 129.82 129.77 129.71 129.68 129.62 129.43 129.33 129.07 128.81 128.74 128.72 128.57 128.56 128.51 128.35 128.22 101.37 92.23 77.69 72.93 72.13 72.04 71.95 71.05 69.87 67.07 63.08 18.23

Mannopyranosyl- (1? 4) -2,3-O-benzoyl-? -L-rhamphyranoside (15d)

White solid, (α: β = 5: 1) 1 H NMR (400 MHz, CDCl 3) δ 7.18 - 8.13 (m, 30 H) 6.14 (t, J = 9.90 Hz, 1 H) 5.95 (d, J = (Br.s., 1 H) 5.39 (br.s, 1 H) 5.79 (d, J = 10.27 Hz, 4.07 (m, 2 H) 3.73 (d, J = 12.47 Hz, 1 H) 3.48 (br.s., 1 H) 4.26 (d, J = 10.27 Hz, 1.60 (d, J = 5.87 Hz , 3 H) 13 C NMR (100 MHz, CDCl 3) δ165.99 165.76 165.70 165.29 133.93 133.69 133.63 133.54 133.48 133.37 132.99 130.28 130.11 129.97 129.88 129.76 129.70 129.65 129.54 129.28 129.12 129.01 128.85 128.77 128.72 128.62 128.46 98.92 92.27 80.31 71.44 70.82 70.48 69.98 69.42 67.74 65.99 61.89 18.49

2,3,4-O-benzoyl-? -L-arabinopyranosyl- (1? 3) - [2,3,4,6-O-benzoyl-? -D-glucopyranosyl- )] - 2-O-acetyl-α-L-rhamphyranoside (20a)

White solid, (α: β = 5: 1) 1 H NMR (400 MHz, CDCl 3) δ 7.23 - 8.33 (m, 35 H) 5.59 - 5.70 (m, 2 H) 5.43 - 5.51 (m, 2 H) 5.38 (dd, J = 10.27, 3.67 Hz, 1 H) 5.30 (br.s., 1 H) 5.27 (br.s., 1 H) 5.06 (br.s., 1 H) 4.64 (d, J = 8.07 Hz, 1 H) 4.47 ( d, J = 7.34 Hz, 1 H) 4.42 (dd, J = 12.10, 3.30 Hz, 1 H) 4.19 (br.s., 2 H) 3.92 (dd, J = 9.54, 5.87 Hz, 1H) 3.84 (d, J = 11.74 Hz, 1H) 3.60 (t, J = 9.54 Hz, 1H) 3.31 (d, J = 3.67 Hz, 1H) 2.51-2.58 ) 2.39 (d, J = 13.20 Hz, 1 H) 2.22 (s, 3 H) 1.22 (d, J = 6.60 Hz, 3 H) 13 C NMR (100MHz, CDCl 3) δ 170.25 165.99 165.92 165.75165.23 165.06 164.87 134.20 134.10 133.64 133.48 133.43 133.40 133.28 130.35 130.24 130.22 130.04 129.88 129.82 129.78 129.72 129.62 129.58 129.47 129.39 129.06 128.83. 128.62 128.57 128.52 128.48 128.47 100.66 100.30 92.36 77.44 73.68 72.87 72.57 71.18 71.08 70.42 69.36 68.49 66.76 63.82 62.34 21.09 17.86

(1 → 3) - [2,3,4-O-benzoyl- alpha -L-rhamnopyranosyl- (1 → 4)] - 2-O-acetyl-a-L- Rhamnopyranoside (20b)

¹ H NMR (400 MHz, CDCl ₃ )? 7.08 - 8.02 (m, 30 H) 6.04 (br s, 1 H) 5.94 - 6.02 (m, 2 H ) 5.88 (br.s., 1H) 5.79 (t, J = 9.90 Hz, 1H) 5.65 (t, J = 9.90 Hz, 1H) (br.s., 1H) 5.27 (br.s., 1H) 4.34-4.45 (m, 2H) 4.10-4.23 (m, 2H) 3.94 (t, J = 9.54 Hz, (d, J = 3.67 Hz, 1 H) 2.26 (s, 3 H) 1.49 (d, J = 5.87 Hz, 3 H) 1.41 (d, J = 6.60 Hz, 3 H) 1.32 (d, J = 5.87 Hz , 3 H) ¹³ C NMR (100 MHz, CDCl ₃ )? 170.80 165.99 165.89 165.60 165.59 165.27 165.16 133.38 133.29 133.17 132.99 132.91 132.76 130.00 129.87 129.81 129.77 129.71 129.65 129.49 129.46 129.44 129.39 128.50 128.45 128.42 128.31 128.19 128.08 100.13 99.76 91.36 81.02 79.02 73.13 72.32 72.05 71.97 71.43 69.58 69.38 67.78 67.72 67.20 21.32 18.69 17.66

2,3,4,6-O-benzoyl- [beta] -D- Glucopyranosyl - (1 → 3) - [2,3,4,6-O-benzoyl- 硫 -D-glucopyranosyl- (1 → 4)] - 2-O- Acetyl -α-L-rhamphyranoside (20c)

White solid, (α: β = 7: 1) 1 H NMR (400 MHz, CDCl 3) δ 7.21 - 8.36 (m, 40 H) 5.75 (t, J = 8.80 Hz, 1 H) 5.59 (t, J = 8.07 Hz, 1H) 5.37-5.51 (m, 4H) 5.21 (br.s., 1H) 5.04 (br.s, 1H) 4.62 (d, J = 7.34 Hz, 1H) 4.56 J = 7.34 Hz, 1H) 4.42 (d, J = 9.54 Hz, 2H) 4.19 (d, J = 11.74 Hz, 2H) 4.11 (d, J = 9.54 Hz, 1H) 3.91 ., 1 H) 3.60 (t , J = 9.17 Hz, 1 H) 3.27 (br.s., 1 H) 2.57 (d, J = 5.14Hz, 2 H) 2.15 (s, 3 H) 1.17 - 1.28 ( m, 3 H) ¹³ C NMR (100 MHz, CDCl ₃ )? 170.31 166.18 166.00 165.88 165.87 165.19 165.06 164.91 164.58 133.69 133.63 133.38 133.26 133.22 130.16 130.09 129.95 129.86 129.78 129.69 129.61 129.56 129.02 128.88 128.55 128.51 128.45 100.47 100.20 92.16 77.09 74.63 72.87 72.69 72.61 72.55 72.17 72.09 71.16 69.54 69.39 66.73 62.49 62.39 21.01 17.82

Example 12. Preparation of compounds 21a to 21g

Compound 15a to 15d and 20a to 20c were converted to CCl ₃ CN and a methylene chloride solution using the DBU, stirred to 0 ℃, concentration, separation acetamido imidate of 21a to 74 to 88% yield of 21g with trichloroacetic. These promoters were used in the synthesis of 22a to 22g without separation immediately upon formation.

Example 13. Preparation of compounds 22a-22g

The above compounds 21a to 21g were glycosylated with compound 8 to obtain 22a to 22g of four saccharides completely protected. As an example, TMSOTf (0.05 mmol) was added at -78 ° C to a solution of 21a-21g (0.25 mmol) and hederagenin 8 (0.25 mmol) in methylene chloride. After stirring for 1 hour, the mixture was neutralized with triethyl amine, and then concentrated and separated to obtain 22 to 22 g of a 73 to 82% yield.

2-O-benzoyl-hederagenin-3-O-2,3,4-O-benzoyl- alpha -L-arabinopyranosyl- (1 → 4) 3-O-benzoyl- [alpha] -L-rhamphyranoside (22a)

White _{solid, R f = 0.43 (n-} Hexane / EtOAc, 2: 1, v / v) [α] D + 45 ° (c 0.1, CHCl 3) 1 H NMR (400 MHz, CDCl 3) δ 7.93 - 7.99 (m, 4 H) 7.78 - 7.86 (m, 4 H) 7.12 - 7.70 (m, 32H) 5.64 (br.s., 2 H) 5.58 (br.s., 1 H) 5.52 (d, J = 8.80 Hz, 1 H) 5.39 (d , J = 8.80 Hz, 1 H) 5.26 (br.s., 1 H) 5.04 (d, J = 5.14 Hz, 1 H) 4.98 (br.s., 1 H) 4.24 - 4.37 (m, 2 H) 4.04 - 4.17 (m, 3 H) 3.91 (d, J = 13.20 Hz, 1 H) 3.62 (t, J = 7.34 Hz, 1 H) 2.87 (d, J = 12.47 Hz, (Br.s., 3 H) 0.94 (br.s., 3 H) 0.94 (br.s., 3 H) 0.95 0.87 (br.s., 3 H) 0.85 - 2.03 (m, 22 H) 0.39 (s, 3 H) 13 C NMR (100 MHz, CDCl 3) δ 176.66 165.93 165.80 165.60 165.29 165.20 165.02 143.78 135.89 133.55 133.41 133.28 133.22 133.14 132.85 132.09 130.62 130.04 129.98 129.95 129.87 129.71 129.66 129.63 129.09 129.00 128.65 128.50 128.43 127.67 127.63 122.39 101.05 99.8982.96 76.89 72.87 70.99 70.93 70.04 68.52 67.42 65.69 62.99 48.11 48.07 46.40 42.58 41.98 41.84 39.37 38.53 36.61 34.14 33.20 32.63 32.49 30.85 27.55 27.23 25.33 25.08 23.65 23.54 19.46 18.27 18.22 17.18 15.88 13.05 IR v _max cm ^-1 (KBr) 2935.24 2864.23 1725.52 1602.56 1455.72 1384.78 1262.35 1094.15; MALDI-TOF-MS m / z 1635.4953 [M + Na] ⁺ (Calcd for C ₉₉ H ₁₀₈ O ₁₈ SiNa _, found: 1635.7203)

-2-O-benzoyl-hederagenin-3-O-2,3,4-O-benzoyl- alpha -L-rhamnopyranosyl- (1 → 4) -2,3 -O-benzoyl- [alpha] -L-rhamphyranoside (22b)

White _{solid, R f = 0.67 (n-} Hexane / EtOAc, 2: 1, v / v) [α] D + 151 ° (c 0.1, CHCl 3) 1 H NMR (400 MHz, CDCl 3) δ7.05 - 8.05 (m, 40 H) 5.75 - 5.84 (m, 2 H) 5.64 - 5.68 (m, 1 H) 5.58 (t, J = 9.95 Hz, 1 H) 5.47 (dd, J = 3.24, 1.66 Hz, 1 H ) 5.36 (s, 1H) 5.28 (br.s., 1H) 5.06 (s, 1H) 4.20-4.42 (m, 4H) 4.11 (t, J = 9.40 Hz, 1H) 3.64-3.75 m, 1 H) 2.88 (d , J = 12.95 Hz, 1 H) 0.81 - 2.00 (m, 22 H) 1.51 (d, J = 6.00 Hz, 3 H) 1.37 (d, J = 6.32 Hz, 3 H) 1.14 (s, 9 H) 1.02 (s, 3 H) 1.01 (s, 3 H) 1.00 (s, 3 H) 0.94 (s, 3 H) 0.91 (s, 3 H) 0.41 (s, 3 H) 13 _{C NMR (100 MHz, CDCl 3} ) δ176.67 165.97 165.82 165.35 165.26 164.47 143.76 135.88 133.48 133.32 133.11 132.86 132.12 132.03 130.62 130.04 129.90 129.85 129.76 129.64 129.48 129.24 129.15 128.52 128.43 128.38128.26 128.18 127.67 127.62 122.36 99.65 99.48 83.13 78.77 72.76 71.71 71.16 70.68 69.47 67.99 67.00 65.78 48.12 48.04 42.65 41.95 41.79 39.33 38.48 36.87 36.61 34.10 33.20 32.63 32.47 30.84 27.54 27.21 25.33 25.11 23.63 23.49 19.44 18.42 18.29 17.65 17.13 15.89 13.17 IR v _max cm ^-1 (KBr) 2934.45 2863.67 1724.30 1602.57 1454.67 1384.28 1263.98 1093.63; MALDI-TOF-MS m / z 1649.6750 [M + Na] + (Calcd for C 100 H 110 O 18 SiNa, found: 1649.7359)

2-O-benzoyl-hederagenin-3-O-2,3,4,6-O-benzoyl- beta -D-glucopyranosyl- (1 → 4) -2 , 3-O-benzoyl- alpha -L-rhamphyranoside (22c)

White _{solid, R f = 0.37 (n-} Hexane / EtOAc, 2: 1, v / v) [α] D + 45 ° (c 0.1, CHCl 3) 1 H NMR (400 MHz, CDCl 3) δ 8.04 (d , J = 8.07 Hz, 2 H ) 7.96 (d, J = 7.34 Hz, 2 H) 7.89 (d, J = 7.34 Hz, 4 H) 7.02 - 7.78 (m, 37 H) 5.75 (t, J = 9.54 Hz (M, 2 H) 5.10 (d, J = 8.07 Hz, 1 H) 4.95 (s, 1 H) 5.63 (t, J = 9.54 Hz, , 1 H) 4.76 (d, J = 11.74 Hz, 1 H) 4.46 (dd, J = 11.00, 4.40 Hz, 1 H) 4.24 (t, J = 11.74 Hz, 2 H) 4.11 (d, J = 11.00 Hz , 2 H) 4.02 (t, J = 9.17 Hz, 1 H) 3.55 - 3.65 (m, 1 H) 2.87 (d, J = 13.20 Hz, 1 H) 1.40 (d, J = 5.14 Hz, 3 H) 1.13 (s, 9H) 0.97 (br.s., 3 H) 0.94 (br.s, 6 H) 0.89 (br.s., 3 H) 0.87 (br.s., 3 H) 0.84-1.96 m, 22 H) 0.38 (s, 3 H) ¹³ C NMR (100 MHz, CDCl ₃ ) δ 176.67 166.23 165.93 165.80 165.39 165.35 165.14 164.93 143.75 135.91 133.60 133.32 133.20 132.99 132.84 132.19 132.09 130.65 130.06 129.96 129.84 129.77 129.74 129.63 129.58 128.87 128.59 128.54 128.48 128.43 128.37 128.26 127.67 127.63 122.46 101.44 99.98 83.11 77.81 73.07 7 2.42 72.12 71.96 71.00 69.91 67.37 65.73 63.14 48.14 48.07 46.40 42.57 41.96 41.86 39.37 38.53 36.60 34.15 33.21 32.63 32.51 30.86 27.55 27.24 25.33 25.11 23.65 23.54 19.46 18.26 18.04 17.17 15.87 13.09 IR v _max cm ^-1 (KBr) 2936.73 2863.37 1728.42 1602.57 1453.65 1383.89 1263.56 1093.79; MALDI-TOF-MS m / z 1769.5055 [M + Na] ⁺ (Calcd for C ₁₀₇ H ₁₁₄ O ₂₀ SiNa _, found: 1769.7570)

2-O-benzoyl-hederagenin-3-O-2,3,4,6-O-benzoyl- alpha -D-mannopyranosyl- (1 → 4) -2 , 3-O-benzoyl- [alpha] -L-rhamopyranoside (22d)

White _{solid, R f = 0.44 (n-} Hexane / EtOAc, 2: 1, v / v) [α] D + 66 ° (c 0.1, CHCl 3) 1 H NMR (400 MHz, CDCl 3) δ 7.21 - 8.04 (m, 45 H) 6.13 ( t, J = 10.27 Hz, 1 H) 5.85 (d, J = 8.80 Hz, 1 H) 5.79 (d, J = 10.27 Hz, 1 H) 5.66 (br.s., 2 H) 5.32 (br.s., 1 H) 5.28 (br.s., 1 H) 5.05 (br.s., 1 H) 4.19-4.40 (m, 3 H) 4.02 - 4.14 (m, 3.61 (m, 2H) 2.89 (d, J = 12.47 Hz, 1H) 1.55 (d, J = 5.14 Hz, 9 H) 0.94 (s, 3 H) 0.91 (s, 3 H) 0.87 - 2.05 (m, 22 H) 0.42 (s, 3 H) ¹³ C NMR (100 MHz, CDCl ₃ ) δ 176.70 166.03 165.92 165.82 165.74 165.37 165.25 143.75 135.92 133.63 133.49 133.40 132.97 132.91 132.21 132.11 130.64 130.08 129.96 129.89 129.74 129.68 129.30 129.14 129.04 128.72 128.67 128.48 127.69 127.65 122.47 99.72 99.05 83.33 80.45 71.30 70.83 70.01 69.36 68.02 66.01 65.80 61.09 48.23 48.16 48.09 42.68 42.00 41.87 39.41 38.54 36.68 34.16 33.22 32.70 32.54 30.87 27.56 27.25 25.38 25.13 23.69 23.59 19.47 18.22 17.23 15.93 13.20 IR v _max cm ^-1 (KBr) 2 935.67 2863.98 1724.50 1601.47 1452.92 1384.94 1263.53 1094.27; MALDI-TOF-MS m / z 1769.2527 [M + Na] ⁺ (Calcd for C ₁₀₇ H ₁₁₄ O ₂₀ Si Na _, found: 1769.7570)

3-O-2,3,4-O-benzoyl-? -L-arabinopyranosyl- (1? 3) -? 2-O-benzyl-hederagenin- , 2-O-benzoyl- alpha -L-rhamopyranoside (22e), 3, 4,6-O-benzoyl- beta -D-glucopyranosyl-

White _{solid, R f = 0.37 (n-} Hexane / EtOAc, 2: 1, v / v) [α] + 69.3 ° (c 0.1, CHCl 3) 1 H NMR (400 MHz, CDCl 3) δ7.22 - 8.31 (m, 2H), 5.71 (s, 1H), 5.71 (s, 1H) 4.66 (d, J = 7.58 Hz , 1 H) 4.52 (d, J = 7.11 Hz, 1 H) 4.42 (dd, J = 12.00, 2.84 Hz, 1 H) 4.26 (d, J = 11.22 Hz, 1 H) 4.14 (dd, J = 12.16, 4.42 Hz, 1 H) 3.75 - 4.03 (m, 4 H) 3.52 - 3.65 (m, 2 H) 2.80 - 2.92 (m, 1 H) 2.46 - 2.59 (m, 2 H) (S, 3 H) 1.19 (d, J = 6.16 Hz, 3 H) 1.12 (s, 10 H) 1.06 - 1.98 H) 0.80 (s, 3 H) 0.36 (s, 3 H) ¹³ C NMR (100 MHz, CDCl ₃ )? 176.68 169.79 165.97 16589 165.85 165.65 165.21 165.13 164.82 143.67 135.86 134.11 133.65 133.43 133.28 132.92 132.13 132.03 130.45 130.32 130.03 129.90 129.83 129.79 129.72 129.57 129.48 129.38 129.07 129.00 128.83 128.58 128.52 12845 127.65 127.60 122.38 100.60 100.15 99.89 82.32 77.42 74.25 72.85 72.67 72.35 71.15 71.06 70.36 69.35 68.37 66.90 65.70 63.52 62.31 48.06 48.02 42.36 41.90 41.80 39.29 36.51 34.07 33.18 30.83 29.82 27.48 27.19 25.25 24.88 23.60 21.08 19.43 17.59 17.10 15.80 12.97 IR v _max cm ^-1 (KBr) 2936.88 2864.62 1724.58 1602.93 1454.56 1382.89 1262.36 1093.59; MALDI-TOF-MS m / z 2047.1436 [M + Na] ⁺ (Calcd for C ₁₂₁ H ₁₂₈ O ₂₆ Si Na _, found: 2047.8361)

28-O-t- Butyl diphenylsilyl -23-O- Benzoyl - Hederagenin -3-O-2,3,4-O- Benzoyl -α-L- Laminopyranosyl - (1- > 3) - [2,3,4-O- Benzoyl -α-L- Laminopyranosyl - (1- > 4)] - 2-O- Benzoyl -α-L-rhamphyranoside (22f)

White _{solid, R f = 0.41 (n-} Hexane / EtOAc, 2: 1, v / v) [α] D + 109 ° (c 0.1, CHCl 3) 1 H NMR (400 MHz, CDCl 3) δ7.86 - 8.05 (m, 10 H) 7.76 (d, J = 7.34 Hz, 2 H) 7.08 - 7.70 (m, 33 H) 5.89 - 6.02 1H, J = 9.90 Hz, 1H) 5.62 (t, J = 9.54 Hz, 1H) 5.56 (br.s, 1H) 4.93 (br.s., 1H) 4.27-4.40 (m, 3H) 4.13-4.21 (m, 1H) 4.00-4.11 (m, 2H) 3.91 (t, J = 9.17 Hz, 1H) 3.67 (br.s., 1 H) 2.87 (d, J = 11.74 Hz, 1 H) 2.19 (br.s., 3 H) 1.46 (d, J = 4.40 Hz, 3 H) 1.39 (d, J = 5.14 Hz, 3 H) 1.29 ( d, J = 5.87 Hz, 3 H) 1.13 (s, 9 H) 0.98 (s, 6 H) 0.94 (s, 3 H) 0.93 (s, 3 H) 0.91 (s, 3 H) 0.85-1.97 (m, 22 H) 0.40 (s, 3 H) ¹³ C NMR (100 MHz, CDCl ₃ )? 176.69 170.32 165.95 165.89 165.62 165.57 165.33 165.17 143.77 135.87 133.38 133.26 133.16 133.00 132.92 132.87 132.77 132.15 130.61 130.05 129.86 129.75 129.65 129.55 128.50 128.45 128.34 128.23 128.11 127.66 127.62 122.36 100.14 99.70 98.76 82.64 80.72 79.22 72.66 72.25 72.1 2 71.91 71.38 69.57 69.46 67.82 67.76 67.58 65.79 48.17 48.11 48.06 42.49 41.96 41.82 39.36 38.50 36.65 34.12 33.19 32.62 32.49 30.83 27.53 27.21 25.33 25.02 24.00 23.64 23.54 21.24 19.44 18.57 17.69 17.65 17.17 15.88 13.17 IR v _max cm ^-1 (KBr) 2932.25 2863.57 1724.56 1603.57 1451.56 1382.67 1263.84 1093.23; MALDI-TOF-MS m / z 1941.7015 [M + Na] + (Calcd for C 115 H 126 O 24 SiNa, found: 1941.8306)

28-O-t-butyldiphenylsilyl-23-O-benzoyl-hederagenin-3-O-2,3,4,6-O-benzoyl- Glucopyranosyl - (1? 3) - [2,3,4,6-O-benzoyl-? -D- Glucopyranosyl - (1 → 4)] - 2-O-benzoyl- alpha -L-rhamphyranoside (22 g)

White _{solid, R f = 0.3 (n-} Hexane / EtOAc, 2: 1, v / v) [α] D + 66.7 ° (c 0.1, CHCl 3) 1 H NMR (400 MHz, CDCl 3) δ 8.30 (d , J = 6.60 Hz, 2 H ) 8.23 (d, J = 7.34 Hz, 2 H) 7.23 - 8.01 (m, 51 H) 5.73 (t, J = 9.54 Hz, 1 H) 5.64 (t, J = 9.54 Hz J = 7.34 Hz, 1H), 4.60 (d, J = 7.8 Hz, 1H) 6.60 Hz, 1 H) 4.43 ( d, J = 11.74 Hz, 1H) 4.25 - 4.30 (m, 1 H) 4.13 - 4.21 (m, 2 H) 4.02 - 4.12 (m, 1 H) 3.85 (d, J = 11.74 Hz, 1 H) 3.76 - 3.83 (m, 1 H) 3.60 (t, J = 9.17 Hz, 1 H) 3.48 (t, J = 7.34 Hz, 1 H) 2.86 (d, J = 12.47 Hz, 1 H ) 2.58 (d, J = 5.87 Hz, 1H) 2.49 (d, J = 7.34 Hz, 1H) 2.12 H) 0.93 (s, 6 H ) 0.89 (s, 3 H) 0.78 (s, 3 H) 0.75 - 1.95 (m, 22 H) 0.57 (s, 3 H) 0.35 (s, 3 H) 13 C NMR ( 100 MHz, CDCl 3) 176.65 169.92 166.07 165.93 165.84 165.63 165.23 165.03 164.97 164.45 143.74 135.87 133.83 133.68 133.61 133.52 133.41 133.28 133.20 132.81 130.57 130.19 130.07 130.00 129.95 129.83 129.71 129.60 128. 58 128.41 127.65 127.61 122.38 100.31 100.20 100.05 82.34 77.32 74.04 72.93 72.85 72.71 72.40 72.38 72.09 71.28 69.42 69.39 67.01 65.41 62.46 62.39 48.05 48.01 47.92 46.36 42.36 41.92 41.80 39.29 38.43 36.46 34.14 33.18 32.53 32.49 30.82 27.51 27.21 25.25 25.10 23.62 23.48 21.02 19.44 18.13 17.55 17.13 15.68 12.57 IR v _max cm ^-1 (KBr) 2931.56 2864.78 1724.57 1604.71 1453.47 1384.48 1262.36 1092.79; MALDI-TOF-MS m / z 2181.9798 [M + Na] ⁺ (Calcd for C ₁₂₉ H ₁₃₄ O ₂₈ Si Na _, found: 2181.8729)

Example 14. Preparation of compounds 23a-23g

TBAF and potassium t-butoxide were used to deprotect TBDPS and benzoyl groups in 22a to 22g to prepare 23a to 23g of a saponin derivative having a rhamnose-core. TBAF (0.08 mmol) was added to a solution of compound 22a-22g (0.04 mmol) in THF (3 mL) and stirred. After the reaction, potassium t-butoxide was added, and the mixture was stirred for 24 hours. Amberlite acid resin was added to neutralize the mixture to pH 7, and the mixture was concentrated and separated to obtain 23a to 23g in 78-84% yield.

Hederagenin 3-O- [alpha] -L- Arabinopyranosyl - (1 → 4) -α-L- Rhamnopyranoside (23a)

White _{solid, R f = 0.58 (CHCl 3} / MeOH / H 2 O, 20: 10: 1, v / v / v) [α] D + 31.5 ° (c 0.05, MeOH) 1 H NMR (400 MHz, Pyr ) [delta] 5.63 (br.s., 1H) 5.48 (br.s., 1H) 5.08 (d, J = 4.40 Hz, 1H) 4.62 (br.s. , 2 H) 4.28 - 4.37 ( m, 2 H) 4.22 - 4.28 (m, 2 H) 4.08 - 4.19 (m, 2 H) 3.72 (d, J = 9.54 Hz, 1 H) 3.61 (d, J = 11.74 Hz, 2 H) 3.29 (d , J = 13.20 Hz, 1 H) 0.90 - 2.21 (m, 22 H) 1.45 (d, J = 4.40 Hz, 3 H) 1.22 (s, 3 H) 1.04 (s, 3 H) 1.01 (s, 3 H) 0.95 (br.s., 6 H) 0.74 (s, 3 H) ¹³ C NMR (100 MHz, Pyr)? 180.64 145.29 123.01 107.66 104.14 85.34 81.55 75.62 74.47 73.51 72.52 70.18 68.35 68.08 64.57 48.52 74.53 47.08 46.86 43.77 42.58 42.41 40.19 39.01 37.30 34.66 33.72 33.66 33.24 31.40 28.79 26.62 26.01 24.65 24.30 24.24 24.12 20.52 18.85 18.61 17.89 16.48 13.99 IR v _max cm ^-1 (KBr) 3435.51 2934.33 1702.51 1635.81 1454.56 1383.78 1263.99 1073.21; MALDI-TOF-MS m / z 773.5143 [M + Na] + (Calcd for C 41 H 66 O 12 Na, found: 773.4452)

(1 → 4) -α-L-rhamnopyranoside (23b) is a compound of formula

White _{solid, R f = 0.6 (CHCl 3} / MeOH / H 2 O, 20: 10: 1, v / v / v) [α] D -14.6 ° (c 0.05, MeOH) 1 H NMR (400 MHz, Pyr ) [delta] 6.30 (s, 1H) 5.62 (s, 1H) 5.49 (br.s, 1H) 4.91 (br.s, 1H) 4.50-4.59 , 4 H) 4.17 (dd, J = 11.74, 4.40 Hz, 1 H) 3.71 (d, J = 11.00 Hz, 1 H) 3.62 (d, J = 11.00 Hz, 1 H) 3.30 (d, J = 11.00 Hz , 1 H) 1.63 (d, J = 5.87 Hz, 3 H) 1.61 (d, J = 6.60 Hz, 3 H) 1.04 (s, 3 H) 1.01 (s, 3 H) 0.96 (s, 3 H) 0.94 (br.s., 6 H) 0.88-2.21 (m, 22 H) 0.76 (s, 3 H) ¹³ C NMR (100 MHz, Pyr)? 180.71 145.32 123.00 104.21 103.62 81.65 80.71 74.46 74.03 73.41 73.16 70.82 68.31 64.61 48.54 47.55 47.10 46.88 43.79 42.59 42.43 40.19 39.06 37.32 34.68 33.72 33.68 33.24 31.41 28.80 26.63 26.05 24.64 24.32 24.24 24.13 20.51 19.36 18.98 18.62 17.90 16.49 14.27 13.98 IR v _max cm ^-1 (KBr) 3433.23 2931.98 1701.69 1637.93 1459.54 1384.12 1264.63 1075.18; MALDI-TOF-MS m / z 787.5653 [M + Na] + (Calcd for C 42 H 68 O 12 Na, found: 787.4608)

(1 → 4) -α-L-rhamnopyranoside (23c) was prepared by the same procedure as in Example 1,

_{white solid, R f = 0.48 (} CHCl 3 / MeOH / H 2 O, 20: 10: 1, v / v / v) [α] D -7 ° (c 0.1, MeOH) 1 H NMR (400 MHz, Pyr ): 5.57 (s, 1H) 5.48 (s, 1H) 5.23 (d, J = 5.13 Hz, 1H) 4.58 (br.s, 2H) 4.09-4.47 (d, J = 12.47 Hz, 1H) 1.28 (d, J = 12.47 Hz, 3 H) 1.21 (br.s., 3 H) 1.04 (s, 3 H) 1.01 (s, 3 H) 0.96 (s, 3 H) 0.94 (s, 3 H) 0.90 - 2.22 (m, 22 H) 0.76 (s, 3 H) 13 C NMR (100 MHz , Pyr) [delta] 180.68 145.29 123.00 107.20 103.95 85.77 81.44 79.02 78.92 76.94 73.28 72.45 71.91 68.49 64.63 63.07 48.52 47.54 47.09 46.85 43.75 42.58 42.41 40.18 37.29 34.67 33.72 33.66 33.23 31.41 28.79 26.62 25.98 24.57 24.30 24.24 24.11 20.49 18.80 18.62 17.89 16.47 14.01 IR v _max cm ^-1 (KBr) 3432.35 2931.89 1702.32 1636.79 1458.11 1385.31 1263.95 1074.81; MALDI-TOF-MS m / z 803.1849 [M + Na] ⁺ (Calcd for C ₄₂ H ₆₈ O ₁₃ Na _, found: 803.4558)

(1 → 4) -α-L-rhamnopyranoside (23d).

White _{solid, R f = 0.44 (CHCl 3} / MeOH / H 2 O, 20: 10: 1, v / v / v) [α] D + 35 ° (c 0.05, MeOH) 1 H NMR (400 MHz, Pyr ) 5 5.58 (s, 1 H) 5.54 (s, 1 H) 5.48 (br s, 1 H) 4.92 (t, J = 6.97 Hz, 1 H) 4.58-4.71 . .s, 1 H) 4.33 - 4.45 (m, 2 H) 4.19 - 4.28 (m, 2 H) 4.12 - 4.18 (m, 1 H) 3.58 - 3.68 (m, 2 H) 3.29 (d, J = 10.27 Hz, 1 H) 1.42 (d , J = 5.14 Hz, 3 H) 1.21 (s, 3 H) 1.03 (s, 3 H) 1.00 (s, 3 H) 0.95 (s, 3 H) 0.93 (s, 3 H) 1.54 (m, 22 H ) 0.74 (s, 3 H) 13 C NMR (100 MHz, Pyr) δ 180.71 145.30 123.00 104.28 103.88 84.90 81.65 76.26 73.50 73.95 72.78 71.79 69.74 68.39 64.64 63.48 48.52 47.54 47.10 46.86 43.74 42.58 42.42 40.18 39.01 37.30 34.67 33.72 33.66 33.22 31.41 28.79 26.62 26.01 24.31 24.24 24.12 18.64 18.61 17.89 16.47 13.97 IR v _max cm ^-1 (KBr) 3434.31 2932.75 1702.33 1636.79 1458.17 1383.89 1265.54 1074.37; MALDI-TOF-MS m / z 803.1768 [M + Na] + (Calcd for C 42 H 68 O 13 Na, found: 803.4558)

(1 → 3) - [β-D-glucopyranosyl- (1 → 4)] - α-L-rhamnopyranoside (23e)

White _{solid, R f = 0.24 (CHCl 3} / MeOH / H 2 O, 20: 10: 1, v / v / v) [α] D -7.5 ° (c 0.1, MeOH) 1 H NMR (400 MHz, Pyr (d, J = 7.34 Hz, 1H) 5.49 (br.s., 1H) 5.25 (d, J = 8.07 Hz, 1H) 1 H) 4.62 - 4.67 (m , 1 H) 4.59 (t, J = 9.17 Hz, 1 H) 4.51 (t, J = 8.07 Hz, 1 H) 4.15 - 4.42 (m, 7 H) 4.11 (d, J = 8.80 Hz, 1H) 4.04 (t, J = 8.07 Hz, 1H) 3.72 (d, J = 11.00 Hz, 1H) 3.60-3.68 (m, 2H) 3.46-3.56 (d, J = 10.27 Hz, 1H) 1.73 (d, J = 6.60 Hz, 3H) 1.22 (s, 3H) 1.09-2.22 3 H) 0.97 (s, 3 H) 0.93 (s, 3 H) 0.81 (s, 3 H) ¹³ C NMR (100 MHz, Pyr)? 180.71 145.29 123.02 106.78 105.01 103.84 83.01 81.33 79.80 79.65 18.22 46.46 75.17 73.37 72.46 72.33 70.27 68.80 67.84 64.66 63.21 48.52 47.55 47.10 46.85 43.77 42.59 42.43 40.19 38.98 37.30 34.67 33.70 33.66 33.25 31.40 30.44 28.79 26.60 25.98 24.55 24.30 24.23 24.13 20.48 19.15 18.61 17.89 16.47 14.20 14.05 IR v _max cm ^-1 (KBr) 3435.32 2931.68 1701.41 1636.89 1459.14 1384.98 1264.45 1074.32; MALDI-TOF-MS m / z 935.5243 [M + Na] ⁺ (Calcd for C ₄₇ H ₇₆ O ₁₇ Na _, found: 935.4980)

(1) - [? -L-arabinopyranosyl- (1)] -? - L-rhamphyranoside (23f) Haderagenin 3-O- alpha -L arabinopyranosyl-

White _{solid, R f = 0.32 (CHCl 3} / MeOH / H 2 O, 20: 10: 1, v / v / v) [α] D -5.7 ° (c 0.05, MeOH) 1 H NMR (400 MHz, Pyr ) 5.95 (s, 1H) 5.74 (s, 1H) 5.55 (s, 1H) 5.49 (br.s. 4H) 4.25-4.40 (m, 4 H) 4.21 (dd, J ), 4.65 (d, J = = 12.10, 4.03 Hz, 1 H ) 3.69 - 3.80 (m, 2 H) 3.30 (d, J = 10.27 Hz, 1 H) 1.58 - 1.62 (m, 9 H) 1.21 (s, 3 H) 1.04 (s, 3 H) 1.01 (s, 3 H) 0.97 (s, 3 H) 0.93 (s, 3 H) 0.85 (s, 3 H) 0.80 - 2.21 (m, 22 H) 13 C NMR (100 MHz, Pyr) δ180 .79 145.32 122.99 105.14 104.28 104.04 82.36 81.82 79.76 74.30 74.06 73.24 73.15 72.99 72.61 71.01 70.59 68.91 64.73 48.54 47.55 47.1146.88 43.84 42.59 42.44 40.19 39.01 37.34 34.68 33.71 33.67 33.23 31.41 30.44 28.80 26.61 26.10 24.48 24.32 24.24 24.13 20.46 19.25 18.96 18.79 18.63 17.89 16.46 14.00 IR v _max cm ^-1 (KBr) 3433.13 2930.89 1702.53 1636.41 1459.13 1385.23 1263.77 1074.92; MALDI-TOF-MS m / z 933.6139 [M + Na] ⁺ (Calcd for C ₄₈ H ₇₈ O ₁₆ Na _, found: 933.5188)

(1 → 3) - [β-D-glucopyranosyl- (1 → 4)] - α-L-rhamphyranoside (23 g)

White _{solid, R f = 0.16 (CHCl 3} / MeOH / H 2 O, 20: 10: 1, v / v / v) [α] D 0 ° (c 0.1, MeOH) 1 H NMR (400 MHz, Pyr) δ 5.45 - 5.56 (m, 3 H) 5.39 (d, J = 8.07 Hz, 1 H) 4.86 (s, 1 H) 4.63 - 4.69 (m, 1 H) 4.57 (t, J = 9.17 Hz, 1 H) (M, 2H), 3.81 (br.s, 1H), 3.72 (d, 2H), 4.40-4.46 (m, 1H) J = 10.27 Hz, 1H) 3.54-3.66 (m, 2H) 3.28 (d, J = 11.00 Hz, 1H) 1.70 (d, J = 5.87 Hz, ) 1.02 (s, 3 H) 1.00 (s, 3 H) 0.96 (s, 3 H) 0.93 (s, 3 H) 0.81 (s, 3 H) 0.76 - 2.22 (m, 22 H) 13 C NMR (100 MHz, Pyr)? 180.77 145.29 123.00 105.88 105.08 103.6083.11 81.38 79.79 79.54 78.98 78.48 78.30 76.40 75.89 72.35 72.29 72.07 68.79 64.75 63.21 63.00 48.50 47.53 47.10 46.87 43.74 42.58 42.41 40.18 38.93 37.29 34.67 33.73 33.66 33.22 31.41 30.43 28.79 26.61 25.91 24.30 24.25 24.12 19.11 18.61 17.89 16.44 14.03 IR v _max cm ^-1 (KBr) 3433.56 2931.35 1701.69 1637.53 1459.83 1384.80 1264.31 1075.22; MALDI-TOF-MS m / z 965.7416 [M + Na] ⁺ (Calcd for C ₄₈ H ₇₈ O ₁₈ Na _, found: 965.5086)

Example 15. Anti-cancer effect experiment

The synthesized compounds 10a to 10i and 23a to 23g were tested in two kinds of cancer cell lines A-549 (lung cancer cell line) and MCF-7 (breast cancer cell line). The test results are shown in Table 1 below. As shown in Table 1, these novel PSD derivatives showed a strong lung cancer inhibitory effect with an IC50 value of 6.6 to 42.3 μM against lung cancer cell line A-549. However, most saponin derivatives tested did not show activity against MCF-7, a breast cancer cell line, except for compound 10i. Two types of saponin showed similar anti - lung cancer activity, and most disaccharide moiety saponins showed stronger anti - lung cancer activity. Among the disaccharide saponins, the anti-lung cancer activity of 10i was similar to the anti-lung cancer activity (5.9 μM) of full-tattylasaponin D (6.6 μM) and the anti-lung cancer activity more than 4 times stronger than the clinical drug Iressa ^® (26.08 μM) Respectively.

Table 1.

a = lung cancer cell line, b = breast cancer cell line.

While the present invention has been described with reference to exemplary embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. You will know. In addition, many modifications may be made to adapt a particular situation and material to the teachings of the invention without departing from the essential scope thereof. Accordingly, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention be construed as including all embodiments falling within the scope of the appended claims.

Claims

Heterangenin 3-O- alpha -D-mannopyranosyl- (1 → 3) -α-L-arabinopyranoside.

(1 → 3) -α-L-arabinopyranoside as an active ingredient. The present invention also provides a pharmaceutical composition for the treatment of lung cancer, comprising 3-O-α-D-mannopyranosyl-

(1 → 3) -α-L-arabinopyranoside as an active ingredient. The present invention also provides a pharmaceutical composition for the treatment of breast cancer, which comprises 3-O-α-D-mannopyranosyl-

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