ethyl (2S,3S,4R,5S)-3-benzyloxy-4,5-isopropylidenedioxypipecolate | 221564-66-5

• 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: ethyl (2S,3S,4R,5S)-3-benzyloxy-4,5-isopropylidenedioxypipecolate
• 英文别名: ethyl (3aS,6S,7S,7aR)-2,2-dimethyl-7-phenylmethoxy-3a,4,5,6,7,7a-hexahydro-[1,3]dioxolo[4,5-c]pyridine-6-carboxylate
• CAS: 221564-66-5
• 化学式: C₁₈H₂₅NO₅
• 分子量: 335.4
• InChiKey: HAZPFTRGYCTNGT-JONQDZQNSA-N

物化性质

• 沸点：
  430.2±45.0 °C(Predicted)
• 密度：
  1.19±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  24
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.61
• 拓扑面积：
  66
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  ethyl (2S,3S,4R,5S)-3-benzyloxy-4,5-isopropylidenedioxypipecolate 在 palladium on activated charcoal 盐酸 、 氢气 、 三乙基硼氢化锂 作用下， 以 四氢呋喃 为溶剂， 反应 11.0h， 生成 米加司他
  参考文献：
  名称：

  Amino and hydroxy acid based diastereoselective synthesis of 1-deoxygalactostatin and its imino acid derivative

  摘要：

  1-Deoxygalactostatin (2) and (2S, 3S, 4R, 5S)-trihydroxypipecolic acid (15) have been synthesised from known building blocks derived from glycine, D-valine and L-tartaric acid (eight and seven steps, with 23% and 27% yield, respectively), via a syn-aldol reaction between 4-O-(tert-butyldiphenylsilyl)-2,-O-isopropylidene-L-threose (6) and the stannous salt of the Schollkopf's bislactim ether 7b. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(99)00107-0
• 作为产物：
  描述：

  (3S,6R,1'S,2'S,3'S)-3-(1-benzyloxy-4-hydroxy-2,3-isopropylidenedioxybutyl)-2,5-diethoxy-3,6-dihydro-6-isopropylpyrazine 在 盐酸 、 4-二甲氨基吡啶 、 三乙胺 作用下， 以 乙醇 、 二氯甲烷 、 二甲基亚砜 为溶剂， 反应 12.0h， 生成 ethyl (2S,3S,4R,5S)-3-benzyloxy-4,5-isopropylidenedioxypipecolate
  参考文献：
  名称：

  Amino and hydroxy acid based diastereoselective synthesis of 1-deoxygalactostatin and its imino acid derivative

  摘要：

  1-Deoxygalactostatin (2) and (2S, 3S, 4R, 5S)-trihydroxypipecolic acid (15) have been synthesised from known building blocks derived from glycine, D-valine and L-tartaric acid (eight and seven steps, with 23% and 27% yield, respectively), via a syn-aldol reaction between 4-O-(tert-butyldiphenylsilyl)-2,-O-isopropylidene-L-threose (6) and the stannous salt of the Schollkopf's bislactim ether 7b. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(99)00107-0

文献信息

• Diastereoselective Synthesis of Piperidine Imino Sugars Using Aldol Additions of Metalated Bislactim Ethers to Threose and Erythrose Acetonides
  作者：María Ruiz、Tania M. Ruanova、Olga Blanco、Fátima Núñez、Cristina Pato、Vicente Ojea

  DOI：10.1021/jo702601z

  日期：2008.3.1

  anti-selectivity for the mismatched ones may originate from (1) the intervention of solvated aggregates of tin(II) azaenolate and lithium chloride as the reactive species and (2) favored chair-like transition structures with a Cornforth-like conformation for the aldehyde moiety. DFT calculations indicate that aldol additions to erythrose acetonides proceed by an initial deprotonation, followed by coordination

  描述了从手性甘氨酸当量和4-碳构件合成1-脱氧-天冬酰胺的一般策略。非对映选择性醛醇缩合的金属化双lactimin醚添加到匹配和不匹配的赤藓糖或苏糖酸丙酮化物和分子内氮-烷基化（通过还原胺化或亲核取代）被用作关键步骤。研究了赤藓糖或苏糖醛丙酮化物中氮杂烯酸酯的金属抗衡离子和γ-烷氧基保护基的性质和醛醇加成的收率和不对称诱导的关系。借助密度泛函理论（DFT）计算已经合理化了氮杂锡（II）锡与羟醛加成的立体化学结果。按照理论计算与模型甘油丙酮化，高反式，顺式，反-selectivitity的配对和适度低反式，反，反错配的选择性可能源于（1）干预作为活性物质的氮杂锡（II）和氯化锂（II）的溶剂化团聚体；（2）醛基具有类似于Cornforth构象的椅子样过渡结构。DFT计算表明，向赤藓糖醇丙酮中添加羟醛的过程是先进行去质子化，然后将烷氧基衍生物与氮杂锡（II）配位，并通过周环过渡结构最终重组中间
• Amino and hydroxy acid based diastereoselective synthesis of 1-deoxygalactostatin and its imino acid derivative
  作者：María Ruiz、Tania M. Ruanova、Vicente Ojea、JoséM. Quintela

  DOI：10.1016/s0040-4039(99)00107-0

  日期：1999.3

  1-Deoxygalactostatin (2) and (2S, 3S, 4R, 5S)-trihydroxypipecolic acid (15) have been synthesised from known building blocks derived from glycine, D-valine and L-tartaric acid (eight and seven steps, with 23% and 27% yield, respectively), via a syn-aldol reaction between 4-O-(tert-butyldiphenylsilyl)-2,-O-isopropylidene-L-threose (6) and the stannous salt of the Schollkopf's bislactim ether 7b. (C) 1999 Elsevier Science Ltd. All rights reserved.