methyl 3,6-dideoxy-4-O-methyl-3-C-methyl-3-nitro-2-O-pivaloyl-α-L-glucopyranoside | 135593-66-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 3,6-dideoxy-4-O-methyl-3-C-methyl-3-nitro-2-O-pivaloyl-α-L-glucopyranoside
• 英文别名: [(2R,3S,4R,5R,6S)-2,5-dimethoxy-4,6-dimethyl-4-nitrooxan-3-yl] 2,2-dimethylpropanoate
• CAS: 135593-66-7
• 化学式: C₁₄H₂₅NO₇
• 分子量: 319.355
• InChiKey: BGEMRVGYHNLELT-PDNLZKNQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  99.8
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  methyl 3,6-dideoxy-4-O-methyl-3-C-methyl-3-nitro-2-O-pivaloyl-α-L-glucopyranoside 在 二乙胺基三氟化硫 、 四丁基氢氧化铵 作用下， 以 1,4-二氧六环 、 二氯甲烷 、 水 为溶剂， 反应 2.5h， 生成 (1R)-2,5-anhydro-3,6-dideoxy-1-fluoro-3-C-methyl-1,4-di-O-methyl-3-nitro-α-L-mannitol
  参考文献：
  名称：

  Novel rearrangement reactions in the fluorination of methyl 3-C-methyl-3-nitro-α-l-hexopyranosides by the DAST reagent

  摘要：

  A simple method for the preparation of 1-fluoro- and/or 5-fluoro-3-branched-chain sugar derivatives by reaction of DAST with methyl 3-C-methyl-3-nitro-alpha-L-hexopyranosides is described. The reaction involves rearrangement with or without ring contraction, depending on the 1,2 relative configuration and the presence of a free OH group at C-4 in the substrate. A new, useful aldehydo-sugar ramified at 0-3 is easily accessible in good yield by the route reported here. (C) 1997, Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4039(96)02479-3
• 作为产物：
  描述：

  三甲基乙酰氯 在 吡啶 、 silver(l) oxide 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 生成 methyl 3,6-dideoxy-4-O-methyl-3-C-methyl-3-nitro-2-O-pivaloyl-α-L-glucopyranoside
  参考文献：
  名称：

  改进的过氧化亚硝酶的合成

  摘要：

  摘要由甲基2合成了Everninomicin寡糖抗生素的成分Evernitrose（13，2,3,6-trideoxy-3-C -methyl-4-O -methyl-3-nitrol-arabino-hexopyranose）。 4-二-O-乙酰基-3,6-二脱氧-3-C-甲基-3-硝基-α-1-葡萄糖-己基吡喃糖苷（2）的克含量为16％，避免了色谱分离。通过对甲基α-1-鼠李糖吡喃糖苷（1）进行二醛-硝基乙烷环化而获得的二乙酸硝基酯2依次进行氢解，N-乙酰化，区域选择性2-O-多羟基化和4-O-甲基化，得到甲基3-乙酰氨基-3，6-二脱氧-3-C-甲基-4-O-甲基-2-O-新戊酰基-α-1-吡喃葡萄糖苷（6）。在六甲基磷酸三酰胺和水的混合物中对酯6进行光脱氧（254 nm），得到3-乙酰氨基-2,3，6-三甲氧基-3-C-甲基-4-O-甲基-α-1-阿糖基己吡喃糖苷（8）。对8进行还原性脱保护得到甲基3-氨基-2

  DOI：

  10.1016/0008-6215(91)84048-j

文献信息

• Rearrangement reactions in the fluorination of 3-deoxy-3-C-methyl-3-nitro-hexopyranosides (and hexo-1-thiopyranosides) of the d- and l-series by the DAST reagent
  作者：Pastora Borrachero、Francisca Cabrera-Escribano、Ana T Carmona、Manuel Gómez-Guillén

  DOI：10.1016/s0957-4166(00)00252-4

  日期：2000.7

  Fluorination of diverse 3-deoxy-3-C-methyl-3-nitro-hexopyranosides and hexo-1-thiopyranosides of the D- and L-series by the DAST reagent was studied in order to establish, on this 3-branched-chain sugar domain, the influence of the stereochemical relationship of the substituents at positions 1 and 2, as well as the protection of the HO-4, on the kinds of rearrangement reaction promoted by this fluorinating agent. Three classes of pyranosidic substrate were employed. (a) 1,2-trans configured, irrespective of whether HO-4 is protected or not: (b) 4-O-protected 1,2-cis configured; and (c) 4-O-unprotected 1,2-cis configured. They were prepared starting from simple glycosides through routes involving a Baer reaction and subsequent transformations by known methodology. All the substrates of class a essayed underwent, on treatment with DAST at room or higher temperatures, a rearrangement involving a 1,2-shift to give both the anomeric 2-inverted pyranosyl fluorides (or, for the l-thioglycosides, only the a fluoride). Substrates of class b led, through a mechanism similar to that proposed for transformations of related substrates, to ring-contracted 2,5-anhydro-1-fluoro-1-O-methyl- (or 1-deoxy-1-phenylthio-)hexitol derivatives (sometimes as 1-epimers), which are precursors of 2,5-anhydro-aldehydo-sugars. Substrates of class c led to 4,5-anhydro-1-fluoro-1-O-methylalditol derivatives in all cases, together with a ring-contracted 5-fluoro-hexofuranoside ill only one case; a rationalisation for their formation is proposed. (C) 2000 Elsevier Science Ltd. All rights reserved.
• JUTTEN, PETER;SCHARF, HANS-DIETER, CARBOHYDR. RES., 212,(1991) C. 93-108
  作者：JUTTEN, PETER、SCHARF, HANS-DIETER

  DOI：——

  日期：——