3,6-di-O-benzoyl-2-(benzoyloximino)-4-O-(2,3,4,6-tetra-O-benzoyl-β-D-galactopyranosyl)-α-D-arabino-hexopyranosyl bromide | 97523-39-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 3,6-di-O-benzoyl-2-(benzoyloximino)-4-O-(2,3,4,6-tetra-O-benzoyl-β-D-galactopyranosyl)-α-D-arabino-hexopyranosyl bromide
• 英文别名: Hexa-O-benzoyl 2-<(benzoyloxy)imino>-2-deoxy-α-D-lactosulosyl bromide；Hexa-O-benzoyl 2-[(benzoyloxy)imino]-2-deoxy-α-D-lactosulosyl bromide
• CAS: 97523-39-2
• 化学式: C₆₁H₄₈BrNO₁₇
• 分子量: 1146.95
• InChiKey: BDXBAHNHFRJIHC-BWBBUERPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.05
• 重原子数：
  80.0
• 可旋转键数：
  18.0
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  224.15
• 氢给体数：
  0.0
• 氢受体数：
  18.0

反应信息

• 作为反应物：
  描述：

  3,6-di-O-benzoyl-2-(benzoyloximino)-4-O-(2,3,4,6-tetra-O-benzoyl-β-D-galactopyranosyl)-α-D-arabino-hexopyranosyl bromide 在 3 A molecular sieve 、 碘 、 silver carbonate 、 diborane(6) 作用下， 以 四氢呋喃 、 1,4-二氧六环 为溶剂， 反应 32.5h， 生成
  参考文献：
  名称：

  Disaccharide-derived 2-oxo- and 2-oximinoglycosyl bromides: novel, conveniently accessible building blocks for the expedient construction of oligosaccharides with .alpha.-D-glucosamine, .beta.-D-mannose, and .beta.-D-mannosamine as constituent sugars

  摘要：

  DOI：

  10.1021/jo00219a017
• 作为产物：
  描述：

  2,3,6-tri-O-benzoyl-4-O-(2,3,4,6-tetra-O-benzoyl-β-D-galactopyranosyl)-1,5-anhydro-D-arabino-hex-1-enitol 在 吡啶 、 N-溴代丁二酰亚胺(NBS) 、 盐酸羟胺 作用下， 以 四氯化碳 为溶剂， 反应 24.5h， 生成 3,6-di-O-benzoyl-2-(benzoyloximino)-4-O-(2,3,4,6-tetra-O-benzoyl-β-D-galactopyranosyl)-α-D-arabino-hexopyranosyl bromide
  参考文献：
  名称：

  Disaccharide-derived 2-oxo- and 2-oximinoglycosyl bromides: novel, conveniently accessible building blocks for the expedient construction of oligosaccharides with .alpha.-D-glucosamine, .beta.-D-mannose, and .beta.-D-mannosamine as constituent sugars

  摘要：

  DOI：

  10.1021/jo00219a017

文献信息

• A Novel, Readily Accessible Lactosaminyl Donor:<i>N</i>-Trichloroethoxycarbonyl-hexa-<i>O</i>-benzoyl-<i>β</i>-D-lactosaminyl Fluoride
  作者：Eisuke Kaji、Frieder W. Lichtenthaler、Yumiko Osa、Shonosuke Zen

  DOI：10.1246/bcsj.68.1172

  日期：1995.4

  A simple, preparatively satisfactory 10-step sequence is described for converting lactose into a novel, suitably blocked lactosaminyl donor: N-Trichloroethoxycarbonyl-β-d-lactosaminyl fluoride (5). The key intermediate in this conversion is the particularly well-accessible oxime of lactosulosyl bromide (52% for the 6 steps from lactose), which on α-glycosidation with p-methoxybenzyl alcohol, oxime reduction, N-protection by Troc chloride, and the anomeric fluorination yields 5 (37% for the 4 steps). The utility of 5 as an effective donor was proved by the β-selective glycosylation of the primary 6-OH of 1,2 : 3,4-di-O-isopropylidene-α-d-galactopyranose (14) and the 3-OH of methyl 2,4,6-tri-O-benzyl-β-d-galactopyranoside (16), both affording the respective trisaccharides 15 and 18 in high yields. The latter, when subjected to N-deprotection, N-acetylation, and de-O-acylation gave, in 42% yield based on donor 5, β-d-Gal-(1→4)-β-d-GlcNAc-(1→3)-β-d-Gal-(1→Me, a core trisaccharide unit of immunologically important carbohydrate antigens.

  本文描述了一种简单、制备令人满意的 10 步序列，用于将乳糖转化为一种新型的、适当封端的乳糖胺基供体：N-Trichloroethoxycarbonyl-β-d-lactosaminyl fluoride (5)。这种转化的关键中间体是特别容易获得的溴化乳糖基肟（从乳糖开始的 6 个步骤中占 52%），在与对甲氧基苄醇进行α-糖苷化、肟还原、三氯乙烷的 N 保护和异构体氟化后，可得到 5（4 个步骤中占 37%）。1,2 : 3,4-二-O-异亚丙基-α-d-吡喃半乳糖的初级 6-OH（14）和甲基 2,4,6-三-O-苄基-β-d-吡喃半乳糖苷的 3-OH（16）的β-选择性糖基化证明了 5 是一种有效的供体，两者都能以高产率得到相应的三糖 15 和 18。后者经过 N-脱保护、N-乙酰化和去 O-乙酰化后，以 42% 的产率（基于供体 5）得到了β-d-Gal-(1→4)-β-d-GlcNAc-(1→3)-β-d-Gal-(1→Me)，这是免疫学上重要的碳水化合物抗原的核心三糖单元。
• Lichtenthaler, Frieder W.; Kaji, Eisuke, Liebigs Annalen der Chemie, 1985, # 8, p. 1659 - 1668
  作者：Lichtenthaler, Frieder W.、Kaji, Eisuke

  DOI：——

  日期：——
• Kaji, Eisuke; Lichtenthaler, Frieder W., Journal of Carbohydrate Chemistry, 1995, vol. 14, # 6, p. 791 - 804
  作者：Kaji, Eisuke、Lichtenthaler, Frieder W.

  DOI：——

  日期：——
• Alternative Access to Lactosamine-derived Oxazoline via 2-Ulose Oxime as a Key Intermediate
  作者：Eisuke Kaji、Yumiko Osa、Naomi Shinohara、Chiho Yanagi、Masae Sekine、Takashi Nishino

  DOI：10.3987/com-04-s(p)28

  日期：——

  Lactosamine-derived oxazoline was synthesized via 2-ulose oxime as a key intermediate, in which substituent effects of the acyloxyimino group were investigated. On reduction of the oxime to amino group, p-chlorobenzoyloxime provided a good gluco : manno selectivity of 13 : 1. N-Acetyllactosaminyl chloride derived therefrom was readily converted into the oxazoline by AgOTf-promoted cyclization with an 84% yield.