Methyl 5-acetamido-4,7,8,9-tetra-O-benzyl-2-bromo-2,3,5-trideoxy-3-phenylthio-D-erythro-β-L-gluco-2-nonulopyranosonate | 123284-43-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Methyl 5-acetamido-4,7,8,9-tetra-O-benzyl-2-bromo-2,3,5-trideoxy-3-phenylthio-D-erythro-β-L-gluco-2-nonulopyranosonate
• 英文别名: methyl (2S,3S,4R,5S,6R)-5-acetamido-2-bromo-4-phenylmethoxy-3-phenylsulfanyl-6-[(1S,2R)-1,2,3-tris(phenylmethoxy)propyl]oxane-2-carboxylate
• CAS: 123284-43-5
• 化学式: C₄₆H₄₈BrNO₈S
• 分子量: 854.859
• InChiKey: NITVWGOGQOEPSN-NYBQEGDLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.8
• 重原子数：
  57
• 可旋转键数：
  20
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  127
• 氢给体数：
  1
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  Methyl 5-acetamido-4,7,8,9-tetra-O-benzyl-2-bromo-2,3,5-trideoxy-3-phenylthio-D-erythro-β-L-gluco-2-nonulopyranosonate 、 methyl 5-acetamido-4,7,9-tri-O-benzyl-2,3-didehydro-3,5-dideoxy-D-glycero-D-galacto-2-nonulopyranosonate 在 4 A molecular sieve 、 氰化汞 、 mercury dibromide 作用下， 以 四氯化碳 为溶剂， 以64%的产率得到methyl O--(2->8)-5-acetamido-4,7,9-tri-O-benzyl-2,3-didehydro-3,5-dideoxy-D-glycero-D-galacto-2-nonulopyranosonate
  参考文献：
  名称：

  Studies Directed toward the Synthesis of Polysialogangliosides: The Regio- and Stereocontrolled Synthesis of Rationally Designed Fragments of the Tetrasialoganglioside GQ_1b⁺.

  摘要：

  The synthesis of suitably protected fragments of the tetrasialoganglioside GQ1b (I), i.e., 1 (alpha-NeuAc2 -->-8-alpha-NeuAc2 --> 3-beta-Gal1 --> 4Glc), 2 (alpha-NeuAc2 --> 8-alpha-NeuAc2 --> 3Gal), 3 (GalNAc), 4 (alpha-NeuAc2 --> 8NeuAc), 5 (beta-Gal1 -->- 3GalNAc), and 42 [beta-Gal1 --> 3-beta-GalNAc1 --> 4(alpha-NeuAc2 --> 3)beta-Gal --> 4Glc], is described. All are rationally designed so that the protecting groups can be regioselectively introduced and removed, as needed, before or after the stereoselective coupling of an appropriate pair of fragments. The syntheses of 1, 2, and 4 all feature stereoselective glycosylations by glycosyl donors that bear a C-3 thiophenoxy stereocontrolling auxiliary. Compound 3 was prepared from the D-glucosamine derivative 17 by way of a novel intramolecular nucleophilic displacement with inversion of configuration. Furthermore, model glycosylations of 4-hydroxygalactose derivatives, in which the thioglycoside 3 and the fluoride 40 served as glycosyl donors, were performed. The reaction of 3 with the glycosyl acceptor 30 gave the disaccharide 31 (GalNAc-beta-1 --> 4Gal), whereas that of 40 with 41 afforded the pentasaccharide 42.

  DOI：

  10.1021/jo00032a601

文献信息

• An efficient synthesis of ganglioside GM3: highly stereocontrolled glycosylations by use of auxiliaries
  作者：Masaaki Numata、Mamoru Sugimoto、Yukishige Ito、Tomoya Ogawa

  DOI：10.1016/0008-6215(90)80018-x

  日期：1990.8

  An efficiently stereocontrolled total synthesis of GM3 alpha-D-Neup5Ac-(2----3)-beta-D-Galp-(1----4)-beta-D-Glcp-(1----1) -Cer was achieved by employing both methyl 5-acetamido-4,7,8,9-tetra-O-benzyl-2-bromo-2,3,5-trideoxy-3- phenylthio-D-erythro-beta-L-gluco-2-nonulopyranosonate for the key sialylation step, and O-[methyl(5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-alpha -D-galacto-2

  GM3 alpha-D-Neup5Ac-（2 ---- 3）-β-D-Galp-（1 ---- 4）-beta-D-Glcp-（1 ---- 1）的立体立体合成）-Cer通过同时使用甲基5-乙酰氨基-4,7,8,9-四-O-苄基-2-溴-2,3,5-三苯氧基-3-苯硫基-D-赤型-β-L来实现-葡萄糖-2-壬基吡喃磺酸盐用于关键的唾液酸化步骤，以及O- [甲基（5-乙酰氨基-4,7,8,9-四-O-乙酰基-3,5-二脱氧-D-甘油-α-D-半乳糖-2-壬基吡喃糖基]]]-（2 ---- 3）-O-（2,4,6-tri-O-乙酰基-β-D-吡喃半乳糖基-（1 ---- 4）-3， 6-二-O-乙酰基-2-O-新戊酰-α-D-吡喃葡萄糖基三氯乙酰亚氨酸盐和氟化物与神经酰胺衍生物的关键偶联步骤，与我们之前进行的合成相比，这两个步骤均发生了明显变化和改进无需使用立体控制助剂，即可在4中获得GM3。从烯丙基O-（2
• Total synthesis of sialyl dimeric Lex
  作者：K. C. Nicolaou、C. W. Hummel、Y. Iwabuchi

  DOI：10.1021/ja00034a063

  日期：1992.4
• NUMATA, MASAAKI;SUGIMOTO, MAMORU;ITO, YUKISHIGE;OGAWA, TOMOYA, CARBOHYDR. RES., 203,(1990) N, C. 205-217
  作者：NUMATA, MASAAKI、SUGIMOTO, MAMORU、ITO, YUKISHIGE、OGAWA, TOMOYA

  DOI：——

  日期：——