3,4,6-Triacetyl-β-aethylthio-D-glucopyranosid | 98179-07-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3,4,6-Triacetyl-β-aethylthio-D-glucopyranosid
• 英文别名: ethyl 3,4,6-tri-O-acetyl-1-thio-β-D-glucopyranoside；[(2R,3R,4R,5R,6S)-3,4-diacetyloxy-6-ethylsulfanyl-5-hydroxyoxan-2-yl]methyl acetate
• CAS: 98179-07-8
• 化学式: C₁₄H₂₂O₈S
• 分子量: 350.39
• InChiKey: IZPREHBCZUSXSQ-KSTCHIGDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  23
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  134
• 氢给体数：
  1
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  3,4,6-Triacetyl-β-aethylthio-D-glucopyranosid 在 4 A molecular sieve 、 三氟化硼乙醚 、 sodium methylate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 2.75h， 生成 ethyl 1-thio-2-O-β-D-xylopyranosyl-β-D-glucopyranoside
  参考文献：
  名称：

  Highly β-Selective and Direct Formation of 2-O-Glycosylated Glucosides by Ring Restriction into Twist-Boat

  摘要：

  Three disaccharide donors, ethyl 2- O- ( 2,3,4- tris- O- tert- butyldimethylsilyl-beta- (D)- xylopyranosyl)- 3,4,6- tris- O- tert- butyldimethylsilyl- 1- thio-beta- (D)- glucopyranoside, ethyl 2- O- ( 2,3,4- tris- O- tert- butyldimethylsilyl- alpha- (L)- rhamnopyranosyl)- 3,4,6- tris- O- tert- butyldimethylsilyl- 1- thio-beta- (D)- glucopyranoside, and ethyl 2- O( 2,3,4,6- tetrakis- O- tert- butyldimethylsilyl-beta- (D)- glucopyranosyl)- 3,4,6- tris- O- tert- butyldimethylsilyl- 1- thio-(beta)- (D)- glucopyranoside, produced a highly beta- selective glycosidation up to alpha/beta = 2/ 98 using MeOTf as the activator and 2,6- lutidine as an additive. The ring conformations of the glucose part in these disaccharide donors were all restricted to S-3(1), and the conformation would lead to the stereoselectivity.

  DOI：

  10.1021/ol070720b

文献信息

• β-Selective Glycosylation Using Axial-Rich and 2-<i>O</i>-Rhamnosylated Glucosyl Donors Controlled by the Protecting Pattern of the Second Sugar
  作者：Masafumi Bando、Yuri Kawasaki、Osamu Nagata、Yasunori Okada、Daiki Ikuta、Kazutada Ikeuchi、Hidetoshi Yamada

  DOI：10.1248/cpb.c20-00733

  日期：2021.1.1

  Herein, we describe two counterexamples of the previously reported β/α-selectivity of 96/4 for glycosylation using ethyl 2-O-[2,3,4-tris-O-tert-butyldimethylsilyl (TBS)-α-L-rhamnopyranosyl]-3,4,6-tris-O-TBS-thio-β-D-glucopyranoside as the glycosyl donor. Furthermore, we investigated the effects of protecting group on the rhamnose moieties in the glycosylation with cholestanol and revealed that β-selectivity originated from the two TBS groups at the 3-O and 4-O positions of rhamnose. In contrast, the TBS group at the 2-O position of rhamnose hampered the β-selectivity. Finally, the β/α-selectivity during the glycosylation was enhanced to ≥99/1. The results obtained herein suggest that the protecting groups on the sugar connected to the 2-O of a glycosyl donor with axial-rich conformation can control the stereoselectivity of glycosylation.

  本文描述了先前报道的β/α-选择性为96/4的两个反例，使用乙基2-O-[2,3,4-三-O-叔丁基二甲基硅基(TBS)-α-L-鼠李糖吡喃糖苷]-3,4,6-三-O-TBS-硫代-β-D-葡萄糖吡喃糖苷作为糖基供体进行糖基化。此外，我们研究了胆固醇醇糖基化中鼠李糖部分保护基的影响，并揭示了β-选择性源于鼠李糖的3-O和4-O位置上的两个TBS基团。相比之下，鼠李糖2-O位置上的TBS基团阻碍了β-选择性。最终，糖基化过程中的β/α-选择性提高至≥99/1。本文获得的结果表明，与轴向富集构象的糖基供体的2-O相连的糖上的保护基可以控制糖基化的立体选择性。
• Synthesis of stryphnoside A, a triterpene saponin isolated from the pericarps of Stryphnodendron fissuratum
  作者：Xun Lv、Shouyi Yu、Jing Wang、Yuguo Du

  DOI：10.1016/j.carres.2011.06.006

  日期：2011.9

  Stryphnoside A, alpha-L-rhamnopyranosyl 3 beta-O-[alpha-L-arabinopyranosyl-(1 -> 4)-beta-D-xylopyranosyl-(1 -> 2)-beta-D-glucopyranosyl]-2 alpha-hydroxyolean-12-en-28-oate, has been synthesized in 11 steps in 15% overall yield starting from the naturally abundant oleanolic acid. Condensation of a partially protected glucopyranosyl donor and 2 alpha, 3 beta-dihydroxyolean-12-en-28-oic acid derivative using inverse glycosylation procedure has significantly simplified the target saponin synthesis. Stryphnoside A exhibited weak cytotoxic activities against tumor cells HeLa, A549, and HepG2 with IC50 at mM level. (C) 2011 Elsevier Ltd. All rights reserved.