per-O-TBS-D-Galf | 1130007-82-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: per-O-TBS-D-Galf
• 英文别名: per-O-tert-butyldimethylsilyl-D-Galf；1,2,3,5,6-penta-O-tert-butyldimethylsilyl-β-D-galactofuranose；per-O-TBS-β-D-galactofuranose；TBDMS(-2)[TBDMS(-3)][TBDMS(-5)][TBDMS(-6)]Galf(b)-O-TBDMS；[(2S,3S,4R,5S)-2-[(1R)-1,2-bis[[tert-butyl(dimethyl)silyl]oxy]ethyl]-4,5-bis[[tert-butyl(dimethyl)silyl]oxy]oxolan-3-yl]oxy-tert-butyl-dimethylsilane
• CAS: 1130007-82-7
• 化学式: C₃₆H₈₂O₆Si₅
• 分子量: 751.471
• InChiKey: QTPLRDYSRLDYJS-NBCLCUQJSA-N

物化性质

• 熔点：
  109.4-109.6 °C
• 沸点：
  577.0±50.0 °C(Predicted)
• 密度：
  0.92±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  11.93
• 重原子数：
  47
• 可旋转键数：
  17
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  55.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  per-O-TBS-D-Galf 在 碘代三甲硅烷 作用下， 以 二氯甲烷 为溶剂， 生成 TBDMS(-2)[TBDMS(-3)][TBDMS(-5)][TBDMS(-6)]b-Galf1I
  参考文献：
  名称：

  Collinsella aerofaciens 产生 pH 响应性脂质免疫原

  摘要：

  人类肠道微生物群的一些成员深刻地影响宿主的生理、健康和治疗反应，但负责的分子和机制在很大程度上尚不清楚。作为鉴定肠道微生物产生的免疫调节剂项目的一部分，我们分析了产气柯林斯菌（Collinsella aerofaciens）的代谢组，这是一种在众多关联研究中占有重要地位的放线菌。这些关联通常是产气梭菌与促炎症反应和不良结果呈正相关，但与 PD-1/PD-L1 癌症免疫治疗的有利反应的关联是一个值得注意的例外。使用树突状细胞 (mBMDC) 和细胞因子读数进行表型测定引导筛选，鉴定出活性化合物，其结构特征为具有带有缩醛的 β-呋喃半乳糖头基的溶血甘油脂 (CaLGL-1, 1 )。通过全合成确认了结构归属。对tlr2 –/– 、 tlr4 –/–和 wt mBMDC 的检测揭示了 TLR2 依赖性信号传导。 CaLGL-1 是通过在低 pH 环境下将细菌生物合成的缩醛磷脂 (CaPlsM, 3

  DOI：

  10.1021/jacs.3c00250
• 作为产物：
  描述：

  D-吡喃葡萄糖 、 叔丁基二甲基氯硅烷 在 咪唑 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 per-O-TBS-D-Galf
  参考文献：
  名称：

  Collinsella aerofaciens 产生 pH 响应性脂质免疫原

  摘要：

  人类肠道微生物群的一些成员深刻地影响宿主的生理、健康和治疗反应，但负责的分子和机制在很大程度上尚不清楚。作为鉴定肠道微生物产生的免疫调节剂项目的一部分，我们分析了产气柯林斯菌（Collinsella aerofaciens）的代谢组，这是一种在众多关联研究中占有重要地位的放线菌。这些关联通常是产气梭菌与促炎症反应和不良结果呈正相关，但与 PD-1/PD-L1 癌症免疫治疗的有利反应的关联是一个值得注意的例外。使用树突状细胞 (mBMDC) 和细胞因子读数进行表型测定引导筛选，鉴定出活性化合物，其结构特征为具有带有缩醛的 β-呋喃半乳糖头基的溶血甘油脂 (CaLGL-1, 1 )。通过全合成确认了结构归属。对tlr2 –/– 、 tlr4 –/–和 wt mBMDC 的检测揭示了 TLR2 依赖性信号传导。 CaLGL-1 是通过在低 pH 环境下将细菌生物合成的缩醛磷脂 (CaPlsM, 3

  DOI：

  10.1021/jacs.3c00250

文献信息

• Two-Step Synthesis of Per-<i>O</i>-acetylfuranoses: Optimization and Rationalization
  作者：Rémy Dureau、Laurent Legentil、Richard Daniellou、Vincent Ferrières

  DOI：10.1021/jo201913f

  日期：2012.2.3

  A simple two-step procedure yielding peracetylated furanoses directly from free aldoses was implemented. Key steps of the method are (i) highly selective formation of per-O-(tert-butyldimethylsilyl)furanoses and (ii) their clean conversion into acetyl ones without isomerization. This approach was easily applied to galactose and structurally related carbohydrates such as arabinose, fucose, methyl galacturonate

  实现了一个简单的两步程序，直接从游离醛糖中产生过乙酰化呋喃糖酶。该方法的关键步骤是（i）高选择性形成过-O-（叔丁基二甲基甲硅烷基）呋喃糖和（ii）在不异构化的情况下将其干净地转化为乙酰基。这种方法很容易应用于半乳糖和与结构相关的碳水化合物，例如阿拉伯糖，岩藻糖，半乳糖醛酸甲酯和N-乙酰半乳糖胺得到相应的过乙酰化目标。该方法的成功取决于至少三个参数的控制：（i）起始未保护糖的互变异构平衡，（ii）靶向呋喃糖酶和甲硅烷基化剂的空间位阻，最后，（iii）保护基相互转化期间的每个软亲核试剂。
• Expedient synthesis of 1,6-anhydro-α-D-galactofuranose, a useful intermediate for glycobiological tools
  作者：Luciana Baldoni、Carla Marino

  DOI：10.3762/bjoc.10.172

  日期：——

  A new and efficient three-step procedure for the synthesis of 1,6-anhydro-α-D-galactofuranose is described. The key step involves the formation of the galactofuranosyl iodide by treatment of per-O-TBS-D-Galf with TMSI, the selective 6-O-desilylation by an excess of TMSI, and the simultaneous nucleophilic attack of the 6-hydroxy group on the anomeric carbon, with the iodide as a good leaving group. This compound is a good precursor for building blocks for the construction of 1→6 linkages.

  描述了一种新的高效三步合成1,6-脱水α-D-半乳糖的方法。关键步骤涉及通过使用TMSI处理per-O-TBS-D-Gal f，形成半乳糖基碘化物，通过过量的TMSI进行选择性的6-O-脱硅基化，同时伴随着6-羟基团对缩醛糖基的核攻击，以碘化物作为良好的离去基团。该化合物是构建1→6键的构建块的良好前体。
• Synthesis of S- and C-galactofuranosides via a galactofuranosyl iodide. Isolable 1-galactofuranosylthiol derivative as a new glycosyl donor
  作者：Luciana Baldoni、Carla Marino

  DOI：10.1016/j.carres.2012.08.021

  日期：2012.11

  The use of the easily available persilylated derivative 1 for the synthesis of C- and S-Galf derivatives has been investigated. By anomeric iodination of 1 with TMSI, followed by in situ coupling with C-and S-nucleophiles under very mild conditions and in the absence of promoters, derivatives with value as glycomimetics or as precursors of glycobiological tools were synthesized. Among them, the synthesis of the isolable 1-galactofuranosylthiol 15 is remarkable, as it paves the way for alternative approaches for S-galactofuranosyl derivatives. (C) 2012 Elsevier Ltd. All rights reserved.
• Facile Synthesis of per-<i>O-tert</i>-Butyldimethylsilyl-β-<scp>d</scp>-galactofuranose and Efficient Glycosylation via the Galactofuranosyl Iodide
  作者：Luciana Baldoni、Carla Marino

  DOI：10.1021/jo8025274

  日期：2009.3.6

  The synthesis of crystalline per-O-TBS-beta-D-galactofuranose (4 beta) as a new precursor of D-Galf units is described. Anomeric iodination by reaction with TMSI followed by in situ coupling with simple alcohols and a wide variety of glycosyl acceptors, in the absence of a promoter, was employed as a new efficient glycosylation method for the assembly Of D-galactofuranosyl moieties with high beta-stereoselectivity. Under the mild conditions of this reaction labile protective groups, like acetals, and furanosyl linkages are preserved.
• Synthesis and conformational analysis of 1,2-cis fused bicyclic α-d-galactofuranosyl thiocarbamate from per-O-tert-butyldimethylsilyl-β-d-galactofuranosyl isothiocyanate
  作者：Luciana Baldoni、Carlos A. Stortz、Carla Marino

  DOI：10.1016/j.carres.2010.11.013

  日期：2011.2

  Per-O-tert-butyldimethylsilyl-alpha,beta-D-galactofuranosyl isothiocyanate (4) was synthesized by the reaction of per-O-TBS-beta-D-galactofuranose (1) with KSCN, promoted by TMSI. Upon O-desilylation (1,2-dideoxy-alpha-D-galactofuranoso)[1,2d]-1,3-oxazolidine-2-thione (6), the cis-fused bicyclic thiocarbamate was obtained as the only product. Conformational analysis, aided by molecular modelling, showed two stable twist forms (T-3(4) and T-4(o)) for the five-membered sugar ring in 6. In aqueous solution, the equilibrium favours the first conformation (3:1 ratio). On the other hand, this ratio decreases for less polar solvents. (C) 2010 Elsevier Ltd. All rights reserved.