3,4,6-tri-O-benzyl-α-D-arabino-hexopyranose-2-ulosyl bromide | 158818-92-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3,4,6-tri-O-benzyl-α-D-arabino-hexopyranose-2-ulosyl bromide
• 英文别名: 3,4,6-tri-O-benzyl-4α-D-arabino-hexopyranos-2-ulosyl bromide；3,4,6-tri-O-benzyl-α-D-arabino-hexopyranos-2-ulosyl bromide；ulosyl bromide；(2R,4S,5R,6R)-2-bromo-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-3-one
• CAS: 158818-92-9
• 化学式: C₂₇H₂₇BrO₅
• 分子量: 511.412
• InChiKey: JVFLEQGZFBLKRO-WSEBHVOGSA-N

物化性质

• 沸点：
  603.2±55.0 °C(Predicted)
• 密度：
  1.36±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  33
• 可旋转键数：
  10
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  3,4,6-tri-O-benzyl-α-D-arabino-hexopyranose-2-ulosyl bromide 在 Ag(zeolite) 、 L-Selectride 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 16.0h， 生成 allyl (3,4,6-tri-O-benzyl-β-D-mannopyranosyl)-(1->2)-3,4,6-tri-O-benzyl-β-D-mannopyranoside
  参考文献：
  名称：

  Synthesis of a β1,2-Mannopyranosyl Tetrasaccharide Found in the Phosphomannan Antigen of Candida albicans

  摘要：

  [GRAPHICS]The synthesis of a portion of the challenging beta 1,2-mannosyl polymer found in the cell walls of Candida albicans was undertaken to develop a conjugate vaccine against C. albicans and to facilitate NMR conformational studies of this unique polysaccharide. The novel approach to the synthesis of tetrasaccharide 1 employed the modified ulosyl bromide 11 as the glycosyl donor which provided high diastereoselectivity. A participating solvent as well as p-chlorobenzyl protection facilitated the new approach.

  DOI：

  10.1021/ol0061743
• 作为产物：
  描述：

  3,4,6-tri-O-acetyl-1,2-O-(S)-(1-ethoxyethylidene)-α-D-glucopyranose 在 氢氧化钾 、 N-溴代丁二酰亚胺(NBS) 、 3 A molecular sieve 、 氢溴酸 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 sodium iodide 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 溶剂黄146 为溶剂， 反应 4.53h， 生成 3,4,6-tri-O-benzyl-α-D-arabino-hexopyranose-2-ulosyl bromide
  参考文献：
  名称：

  3,4,6-Tri-O-benzyl-.alpha.-D-arabino-hexopyranos-2-ulosyl Bromide: A Versatile Glycosyl Donor for the Efficient Generation of .beta.-D-Mannopyranosidic Linkages

  摘要：

  An expedient four-step sequence is described for the conversion of acetobromoglucose into the title 2-oxohexosyl (''ulosyl'') bromide 4. Due to its O-benzyl protection, 4 is considerably more reactive than its acylated analogs 1-3: Ag2CO3-promoted glycosidations with 2-propanol, diacetone-galactose, and methyl 2,3-O-isopropylidene-alpha-L-rhamnoside are complete within minutes and, in addition, are endowed with beta-specificity. This renders ulosyl bromide 4 a most propitious, indirect beta-D-mannosyl donor, inasmuch as the borohydride reduction of the beta-D-glycosiduloses formed (14-16 --> 19, 21, and 22) proceeds with manno selectivities of >20:1. Comparative evaluation of the manno/gluco ratios obtained in all 21 beta-D-arabino hexosidulose reductions (Table 1) reveals the 3-O-blocking group to have a pronounced effect on the outcome: >20:1 in cases with a 3-O-benzyl group versus only 2:1 to 3:1 in the presence of 3-O-acyl functions.

  DOI：

  10.1021/jo00101a035

文献信息

• Synthesis of 2-hydroxy-6-{[(16R)-β-δ-mannopyransyloxy]heptadecyl}benzoic acid, a fungal metabolite with GABAA ion channel receptor inhibiting properties
  作者：Alois Fürstner、Ingo Konetzki

  DOI：10.1016/s0040-4020(96)00950-7

  日期：1996.11

  An expeditious total synthesis of the physiologically active fungal metabolite 1 is described. The stereoselective formation of its β-δ-mannopyranosidic linkage is achieved in two steps upon reaction of the hexopyranos-2-ulosyl bromide 15 with the glycosyl acceptor 13, followed by reduction of the resulting β-δ-glycos-2-uloside 16. Alcohol 13 was efficiently prepared via a Suzuki reaction of the aryltriflate

  描述了生理活性真菌代谢物1的快速全合成。六吡喃-2-溴代糖基溴化物15与糖基受体13反应，然后还原所得的β-δ-甘露糖-2-基糖苷16，可通过两个步骤实现其β-δ-甘露吡喃型硅键的立体选择性形成。通过芳基三氟甲磺酸酯11与9-烷基-9-BBN衍生物10的Suzuki反应有效地制备了醇13。
• 1,2-Annulated Sugars: Synthesis of Polyhydroxylated 2,10-Dioxadecalins with β-<i>manno</i>Configuration
  作者：Daniel Borowski、Tobias Zweiböhmer、Thomas Ziegler

  DOI：10.1002/ejoc.201601050

  日期：2016.11

  interesting 1,2‐pyran‐annulated β‐mannosides (dioxadecalins) are presented. Key steps include 2‐uloside vinylation, alkene metathesis and diastereoselective syn/anti‐dihydroxylation. Similar bicyclic sugar‐derived compounds have been identified as glycosidase inhibitors.

  提出了合成结构上有趣的1,2-吡喃环化的β-甘露糖苷（二氧杂环丁烷）的策略。关键步骤包括2-uloside乙烯基化，烯烃复分解和非对映选择性的syn / anti -dihydroxylated 。相似的双环糖衍生化合物已被鉴定为糖苷酶抑制剂。
• Total Synthesis and Absolute Configuration of Simpotentin, a Potentiator of Amphotericin B Activity
  作者：Masaki Ohtawa、Eri Shimizu、Atsushi Saito、Sayuri Sakamoto、Ai Waki、Ariko Kondo、Akiho Yagi、Ryuji Uchida、Hiroshi Tomoda、Tohru Nagamitsu

  DOI：10.1021/acs.orglett.9b01945

  日期：2019.7.19

  potentiator of amphotericin B activity against Candida albicans, was achieved. Our research results enabled the access of all stereoisomers of 1 and the elucidation of the unknown absolute configuration of 1. Furthermore, one of the stereoisomers is a better amphotericin B potentiator than 1 and is an excellent lead compound for the development of a novel amphotericin B potentiator.

  实现了辛泊汀（1）的全合成，这是一种新的两性霉素B对白色念珠菌活性的增强剂。我们的研究结果使所有的立体异构体的访问1和未知绝对构型的阐明1。此外，立体异构体之一是比1更好的两性霉素B增效剂，并且是开发新型两性霉素B增效剂的极好的先导化合物。
• Practical Synthesis of .beta.-D-Xyl-(1.fwdarw.2)-.beta.-D-Man-(1.fwdarw.4)-.alpha.-D-Glc-OMe, a Trisaccharide Component of the Hyriopsis schlegelii Glycosphingolipid
  作者：Frieder W. Lichtenthaler、Thomas Schneider-Adams、Stefan Immel

  DOI：10.1021/jo00101a036

  日期：1994.11

  By employing the readily accessible (preceding paper in this issue) 3,4,6-tri-O-benzyl-alpha-D-arabino-hexosyl bromide (1) as an indirect, beta-specific mannosyl donor, a practical three-step synthesis was elaborated for methyl xylosyl-beta(1-->2)-mannosyl-beta(1-->4)-glucoside (11), a trisaccharide component of Hyriopsis schlegelii ceramide oligosaccharides. Key steps were the silver aluminosilicate-induced, beta-specific glycosidation of 1 with methyl 2,3,6-tri-O-benzyl-alpha-D-glucoside and the silver triflate-promoted beta-xylosylation with 2,3,4-tri-O-benzoyl-alpha-D-xylosyl bromide. The overall yield amounted to a satisfactory 47%.
• 3,4,6-Tri-O-benzyl-.alpha.-D-arabino-hexopyranos-2-ulosyl Bromide: A Versatile Glycosyl Donor for the Efficient Generation of .beta.-D-Mannopyranosidic Linkages
  作者：Frieder W. Lichtenthaler、Thomas Schneider-Adams

  DOI：10.1021/jo00101a035

  日期：1994.11

  An expedient four-step sequence is described for the conversion of acetobromoglucose into the title 2-oxohexosyl (''ulosyl'') bromide 4. Due to its O-benzyl protection, 4 is considerably more reactive than its acylated analogs 1-3: Ag2CO3-promoted glycosidations with 2-propanol, diacetone-galactose, and methyl 2,3-O-isopropylidene-alpha-L-rhamnoside are complete within minutes and, in addition, are endowed with beta-specificity. This renders ulosyl bromide 4 a most propitious, indirect beta-D-mannosyl donor, inasmuch as the borohydride reduction of the beta-D-glycosiduloses formed (14-16 --> 19, 21, and 22) proceeds with manno selectivities of >20:1. Comparative evaluation of the manno/gluco ratios obtained in all 21 beta-D-arabino hexosidulose reductions (Table 1) reveals the 3-O-blocking group to have a pronounced effect on the outcome: >20:1 in cases with a 3-O-benzyl group versus only 2:1 to 3:1 in the presence of 3-O-acyl functions.