- Chemical intertransformations of diverse bisdesmosidic furostanol saponins
-
An effective synthetic route towards four types of bisdesmosidic furostanol saponin was developed and 36 derivatives were designed and synthesized for antitumor investigation. The chemical intertransformations of these furostanol structures were discussed
- Zhao, Dong-Mei,Liu, Yang,Liu, Yong-Xiang,Zheng, Li-Gang,Yan, Mao-Cai,Cheng, Mao-Sheng
-
-
Read Online
- Synthesis and structural characterization of an oxaziridine derived from 6-azadiosgenin
-
The synthesis of the first spirostanic oxaziridine 18 derived from diosgenin (9) is described, this novel compound is very interesting due to its potential utility in oxaziridine chemistry. Compound 18 was obtained through formation of the 5,6-secoteroid intermediate 12, which after four steps provided 6-azasteroid 16. Notably, depending on the reaction conditions used to carry out the cyclization of the isocyanate 15 to 6-azadiosgenin 16, formation of 16, as the main product, or of 6-azadiene 17 can be favored. Moreover, a mechanistic proposal for the formation of compound 16is discussed. The structures of the products were established by 1D and 2D NMR analysis and in the case of epoxy compound 11a, its structure with α orientation was confirmed by analysis X-ray.
- García-Merinos, J. Pablo,López, Yliana,Pérez-Gómez, Cristhian O.,Ramírez-Díaz, Martha I.,Santillan, Rosa,Vazquez-Chavez, Josué,Yepéz, Rebeca,del Río, Rosa E.
-
-
- Stereoselective Synthesis of (-)-Verazine and Congeners via a Cascade Ring-Switching Process of Furostan-26-acid
-
An efficient synthetic strategy for three natural seco-type cholestane alkaloids isolated from the Veratrum plants, based on commercially available naturally occurring and abundant (-)-diosgenin (1), as exemplified in the concise asymmetric synthesis of (-)-verazine (4), (-)-veramiline (5) (proposed structure), and its 22-epimer, (-)-oblonginine (6), is presented. This work highlights the application of a cascade ring-switching process of (-)-diosgenin to achieve the E-ring opening and construction of chiral six-membered lactone challenges in seco-type cholestane alkaloid synthesis. This approach enables the synthesis of related natural and nature-like novel cholestane alkaloids, opening up opportunities for more extensive exploration of cholestane alkaloid biology.
- Chen, Fen-Er,Shi, Yong,Tang, Pei,Tian, Wei-Sheng,Wang, Yun,Zhuang, Chunlin
-
supporting information
(2020/04/02)
-
- New selenosteroids as antiproliferative agents
-
Starting from natural steroids (diosgenin, hecogenin, smilagenin, estrone), we have prepared a wide panel of selenoderivatives, including benzoselenazolones, selenosemicarbazones, isoselenocyanates, selenoureas, selenocyanates and diselenides, with the aim of developing new families of potential chemotherapeutic agents. The modification of the organoselenium moieties, and their position on the steroid provided valuable information concerning the antiproliferative activities. Among all the families accessed herein, the best profile was achieved for selenoureas on the A ring of estrone, which exhibited GI50 values in the range 2.0-4.1 μM for all the tested tumor cell lines, with increased potency compared with commonly used chemotherapeutic agents, like 5-fluorouracil and cisplatin. Cell cycle analysis revealed that selenoureas induced accumulation of cells in the G1 phase of the cell cycle in the breast cancer cell lines HBL-100 and T-47D; therefore, a different mechanism than cisplatin, that induces cell cycle accumulation in the S phase as a result of DNA damage, must be involved. In the rest of the tumor cells, a slight increase of the S compartment was observed. Moreover, selenosteoids turned out to be excellent glutathione peroxidase (GPx) mimics for the catalytic removal of deleterious H2O2 (t1/2 8.0-22.5 min) and alkyl peroxides (t1/2 23.0-38.9 min) when used in substoichiometric amounts (1% molar ratio), thus providing a valuable tool for reducing the intrinsic oxidative stress in tumor progression.
- Fuentes-Aguilar, Alma,Romero-Hernández, Laura L.,Arenas-González, Ailed,Merino-Montiel, Penélope,Montiel-Smith, Sara,Meza-Reyes, Socorro,Vega-Báez, José Luis,Plata, Gabriela B.,Padrón, José M.,López, óscar,Fernández-Bola?os, José G.
-
p. 5041 - 5054
(2017/07/11)
-
- An efficient and recyclable catalyst for the cleavage of tert-butyldiphenylsilyl ethers
-
An efficient, chemoselective, and environment-friendly method for the deprotection of tert-butyldiphenylsilyl ethers mediated by triflic acid supported on silica gel is reported. A wide range of tert-butyldiphenylsilyl ethers derived from carbohydrate and saponin residues can be smoothly cleaved in the presence of various types of other protecting groups in good to excellent yields in acetonitrile. This heterogeneous reaction does not require aqueous workup, and the supported catalyst can be readily recycled.
- Yan, Shiqiang,Ding, Ning,Zhang, Wei,Wang, Peng,Li, Yingxia,Li, Ming
-
experimental part
p. 6 - 20
(2012/07/13)
-
- Synthesis of Dihydrodiosgenin Glycosides as Mimetics of Bidesmosidic Steroidal Saponins
-
The focus of this work is the synthesis of bidesmosidic saponin mimetics. Therefore, dihydrodiosgenin derivatives, which differ from the natural compounds by reduction of the 22-(hemi) acetal were used as glycosyl acceptors. In preliminary studies, the dihydrodiosgenin glycosides 16, 17 and 19, as well as trisaccharide 22, were synthesized. The acceptors 10 and 14 were subjected to DMTST-mediated glucosylation for the synthesis of the chacotriose-substituted compound 3. For a selective 2,4-di-rhamnosylation of the dihydrodiosgenin glucopyranoside, differentiation of the glucose OH groups was achieved by selective benzoylation with 1-(benzoyloxy)benzotriazole. Reaction of the 3,6-di-O-benzoate 32 with the perbenzoylated ethyl thiorhamnopyranoside donor 15 gave the 2,4-di-rhamnosylated compound 33, together with the mono-rhamnosylated derivative. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.
- Suhr, Rene,Lahmann, Martina,Oscarson, Stefan,Thiem, Joachim
-
p. 4003 - 4011
(2007/10/03)
-
- Total synthesis of methyl protodioscin: A potent agent with antitumor activity
-
Methyl protodioscin (1), otherwise known as 3-O-[α-L-rhamnopyranosyl-(1→2)-{α-L-rhamnopyranosyl- (1→4)}-β-D-glucopyranosyl]-26-O-[β-D-glucopyranosyl]-22- methoxy-25(R)-furost-5-ene-3β,26-diol, has been synthesized for the first time from diosgenin through nine steps in an overall yield of 7.8%.
- Cheng, Mao S.,Wang, Qian L.,Tian, Quan,Song, Hong Y.,Liu, Yong X.,Li, Qiang,Xu, Xin,Miao, Hong D.,Yao, Xin S.,Yang, Zhen
-
p. 3658 - 3662
(2007/10/03)
-
- The first synthetic route to furostan saponins
-
26-O-β-D-Glucopyranosyl-22-methoxy-25(R)-furost-5-en-3β-ol 3-O-β-D-glucopyranoside is synthesized from diosgenin in 11 steps and 26% overall yield. The present synthetic route represents the first one to furostan saponins.
- Yu, Biao,Liao, Jianchun,Zhang, Jianbo,Hui, Yongzheng
-
-