Total synthesis of astrosterioside A, an anti-inflammatory asterosaponin

Dai, Yuanwei; Yu, Biao

doi:10.1039/c5cc04734j

Cited by 21 publications

(16 citation statements)

References 30 publications

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“…The preparation of trisaccharide donor 2 was straightforward and employed three readily available monosaccharide derivatives (i.e., 9 , 10 , and 11 ) as building blocks (Scheme ). Thus, the coupling of perbenzoyl rhamnosyl N ‐phenyltrifluoroacetimidate 9 with allyl 2,3,6‐tri‐ O ‐benzoylglucoside 10 proceeded smoothly in the presence of trimethylsilyl trifluoromethanesulfonate (TMSOTf, 0.4 equiv) and 4 Å molecular sieves (MS) in CH 2 Cl 2 at room temperature to lead to disaccharide 12 in 90 % yield .…”

Section: Resultsmentioning

confidence: 99%

A Convergent Synthesis of the Triterpene Saponin Asiaticoside

et al. 2017

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Asiaticoside (1), namely,2 a,3b,23-trihydroxy-urs-12-en-28-oic-O-a-l-rhamnopyranosyl-(1!4)-b-d-glucopyranosyl-(1!6)-b-d-glucopyranoside,t he major activeb iomarker of the traditional medicinal plant Centella asiatica,h as been synthesized for the first time. The strategy features alate-stage gold(I)-catalyzed glycosidic condensation of atriterpenoid acid and at risaccharide ortho-hexynylbenzoate. The overall preparation required at otal 31 steps with the longest linear sequence occurring over 14 steps in a6 % overall yield and startingf rom ursolic acid (3b-hydroxy-urs-12-en-28-oic acid). IntroductionCentella asiatica (L.) Urban, the synonym of which is Hydrocotyle asiatica L. and also knowna sg otu kola or Indianp ennywort, grows widely in tropical regions. It hasb een used since prehistoric times as ac ure-all, but most prominently it has been used fort he treatmento fd ermatoses and skin lesions such as excoriations, burns, and hypertrophic scars.[1] The major active biomarker of C. asiatica hasb een identified as an ursane-type triterpene glycoside, namely,a siaticoside (1). [2] Indeed, it has been reported that asiaticoside can stimulate collagen synthesis, [3] possibly through activation of the Smad pathway [3a] or the inhibition of glycogen phosphorylase.[4a] Asiaticoside( 1)i so ne of the earliestc haracterized saponins, [2a] and its structure was unambiguously established in 1987 by Xray diffraction as 2a,3b,23-trihydroxy-urs-12-en-28-[2b] Although analogues,m ostly derivatized from the aglycone,h ave been synthesized for structureactivity relationship studies, [4] the total synthesis of asiaticoside has not been realized.I nl ine with our prolonged interest in the chemical synthesis of saponins for biological studies, [5] we embarked on the preparation of asiaticoside( 1), and we herein reporti ts first total synthesis. Results and DiscussionAsiaticoside (1)c onsists of 2a,3b,23-trihydroxy-urs-12-en-28-oic acid (i.e.,a siatic acid) as an aglycone with ag lycan moiety attached at the ester linkage at C28. The convergent synthesis calls for the condensation of an asiatic acid derivativewith atrisaccharide donor, [5] such as the condensation between 3 and 2 ( Figure 1). Fortunately,t he linear trisaccharide allows for the installation of ap articipating group (i.e.,abenzoyl group) at C2 of the first glucose unit to ensure the required b-selective glycosylation.I nl ine with our current practice regarding gold(I)-catalyzed glycosylations with glycosyl ortho-alkynylbenzoates as donors, [6] perbenzoyl trisaccharide n-hexynylbenzoate 2 was envisioned asareliable donor.A siatic acid derivative 3 could be synthesized from commerciallya vailableu rsolic acid (4), throught he introduction of the 23-and 2a-hydroxy groups. [7] Given the robustness of the triterpenoid 28-ester linkage, we employed acetyl and benzoyl groups as permanent protecting groups,w hich couldb eg lobally removed without the hydrolysis of this typical triterpene glycosidic linkage. [5] We commencedt he synthesis by ...

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Section: Resultsmentioning

confidence: 99%

A Convergent Synthesis of the Triterpene Saponin Asiaticoside

et al. 2017

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“…Next, we turned our attention to the synthesis of tetrasaccharide 2 . Diarabinan N -phenyl trifluoroacetimidate donor 8 was prepared in six steps starting from the arabinose donor 11 [ 29 ] similar to previous work by Varrot and coworkers [ 30 ] ( Scheme 7 ).…”

Section: Resultsmentioning

confidence: 99%

Synthesis of Two Tetrasaccharide Pentenyl Glycosides Related to the Pectic Rhamnogalacturonan I Polysaccharide

et al. 2018

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The synthesis of two protected tetrasaccharide pentenyl glycosides with diarabinan and digalactan branching related to the pectic polysaccharide rhamnogalacturonan I is reported. The strategy relies on the coupling of N-phenyl trifluoroacetimidate disaccharide donors to a common rhamnosyl acceptor. The resulting trisaccharide thioglycosides were finally coupled to an n-pentenyl galactoside acceptor to access the two protected branched tetrasaccharides.

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“…[6] Với cấu trúc hóa học độc đáo và hoạt tính sinh học tiềm năng, hợp chất 23 đã được các nhà khoa học trên thế giới nghiên cứu tổng hợp toàn phần. [11] Ngoài ra, hợp chất 27 thể hiện hoạt tính mạnh trên cả ba dòng tế bào ung thư thử nghiệm là HL-60 (ung thư máu cấp tính), PC-3 (tuyến tiền liệt) và SNU-C5 (ruột) với giá trị IC 50 trong khoảng từ 4,31 đến 6,99 μM. Nghiên cứu tiếp theo cho thấy cặn chiết MeOH loài sao biển A. monacanthus và hợp chất 27 kích thích quá trình chết theo chương trình (apoptosis) ở tế bào HL-60 được xác nhận bởi sự gia tăng các thể apoptosis ở các tế bào được xử lý khi nhuộm với thuốc nhuộm Hoechst 33342 và thông qua việc điều tiết giảm con đường ERK 1/2 và C-myc ở tế bào HL-60, PC-3 và SNU-C5.…”

Section: Nhóm Chất Saponinunclassified

Điểm lại các nghiên cứu hóa học và hoạt tính sinh học một số loài sinh vật biển Việt Nam trong giai đoạn 2013‐2017

Cường¹,

Nhiệm²,

Thành³

et al. 2018

Vietnam Journal of Chemistry

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Điểm lại các nghiên cứu hóa học và hoạt tính sinh học một số loài sinh vật biển Việt Nam trong giai đoạn AbstractThis paper reviews the investigations on marine natural products in Vietnam published in period of 2013-2017 from sponges, corals, echinoderms, mollusks, and microorganisms. About 415 compounds were isolated and structure elucidated including 33 saponins (15 new compounds), 143 steroids (30 new compounds), 38 steroid glycosides (20 new compounds), 33 diterpenes (20 new compounds), 53 sesquiterpenes (27 new compounds), 12 cyclopeptides, 7 pyrrole and furan oligoglycosides (6 new compounds), 10 biscembranoids (2 new compounds), 15 triterpenes (14 new compounds), and 71 other compounds (8 new compounds). Many compounds have unique structures and exhibited potential biological effects including cytotoxic, anti-inflammatory, and anti-microbial activities.

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Total synthesis of astrosterioside A, an anti-inflammatory asterosaponin

Abstract: Astrosterioside A, a sulfated steroidal hexasaccharide isolated from starfish Astropecten monacanthus showing potent anti-inflammatory activity, was synthesized in a convergent linear sequence of 24 steps and in 6.8% overall yield from adrenosterone.

Cited by 21 publications

References 30 publications

A Convergent Synthesis of the Triterpene Saponin Asiaticoside

A Convergent Synthesis of the Triterpene Saponin Asiaticoside

Synthesis of Two Tetrasaccharide Pentenyl Glycosides Related to the Pectic Rhamnogalacturonan I Polysaccharide

Điểm lại các nghiên cứu hóa học và hoạt tính sinh học một số loài sinh vật biển Việt Nam trong giai đoạn 2013‐2017

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