(3S,6R,1'S,2'R,3'S)-3-(1,4-dihydroxy-2,3-isopropylidenedioxybutyl)-2,5-diethoxy-3,6-dihydro-6-isopropylpyrazine | 460718-35-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (3S,6R,1'S,2'R,3'S)-3-(1,4-dihydroxy-2,3-isopropylidenedioxybutyl)-2,5-diethoxy-3,6-dihydro-6-isopropylpyrazine
• 英文别名: (S)-[(2S,5R)-3,6-diethoxy-5-propan-2-yl-2,5-dihydropyrazin-2-yl]-[(4R,5S)-5-(hydroxymethyl)-2,2-dimethyl-1,3-dioxolan-4-yl]methanol
• CAS: 460718-35-8
• 化学式: C₁₈H₃₂N₂O₆
• 分子量: 372.462
• InChiKey: HUPAGQXBAAHIGM-AICCOOGYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  26
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  102
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (3S,6R,1'S,2'R,3'S)-3-(1,4-dihydroxy-2,3-isopropylidenedioxybutyl)-2,5-diethoxy-3,6-dihydro-6-isopropylpyrazine 在 palladium on activated charcoal 盐酸 、 氢气 、 三乙基硼氢化锂 、 2-碘酰基苯甲酸 作用下， 以 四氢呋喃 、 乙醇 、 二甲基亚砜 为溶剂， 反应 35.0h， 生成 (2R,3S,4S,5S)-3,4,5-trihydroxy-2-hydroxymethyl piperidine
  参考文献：
  名称：

  Access to iminosugars by aldol additions of metalated bis-lactim ethers to l-erythrose derivatives

  摘要：

  Aldol additions of metalated bis-lactim ethers derived from cyclo-[Gly-D-Val] 3A-E* to mismatched L-erythrose-derivatives 4a and 4b have been studied. Reactions of titanium(IV) and tin(II) azaenolates with the lactol derivative 4b allow direct and moderate (syn,syn)- or highly (anti,anti)-selective access to polyhydroxy amino acids that have been efficiently transformed into 1-deoxy-D-gulonojirimycin or 1-deoxy-D-allonojirimycin. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00189-1
• 作为产物：
  描述：

  (4S,5S)-5-[(benzyloxy)methyl]-2,2-dimethyl-1,3-dioxolane-4-carbaldehyde 在 palladium on activated charcoal 氢气 、 zinc(II) chloride 作用下， 以 四氢呋喃 为溶剂， 反应 8.0h， 生成 (3S,6R,1'S,2'R,3'S)-3-(1,4-dihydroxy-2,3-isopropylidenedioxybutyl)-2,5-diethoxy-3,6-dihydro-6-isopropylpyrazine
  参考文献：
  名称：

  Access to iminosugars by aldol additions of metalated bis-lactim ethers to l-erythrose derivatives

  摘要：

  Aldol additions of metalated bis-lactim ethers derived from cyclo-[Gly-D-Val] 3A-E* to mismatched L-erythrose-derivatives 4a and 4b have been studied. Reactions of titanium(IV) and tin(II) azaenolates with the lactol derivative 4b allow direct and moderate (syn,syn)- or highly (anti,anti)-selective access to polyhydroxy amino acids that have been efficiently transformed into 1-deoxy-D-gulonojirimycin or 1-deoxy-D-allonojirimycin. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00189-1

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
• Access to iminosugars by aldol additions of metalated bis-lactim ethers to l-erythrose derivatives
  作者：Marı́a Ruiz、Vicente Ojea、Tania M. Ruanova、José M. Quintela

  DOI：10.1016/s0957-4166(02)00189-1

  日期：2002.5

  Aldol additions of metalated bis-lactim ethers derived from cyclo-[Gly-D-Val] 3A-E* to mismatched L-erythrose-derivatives 4a and 4b have been studied. Reactions of titanium(IV) and tin(II) azaenolates with the lactol derivative 4b allow direct and moderate (syn,syn)- or highly (anti,anti)-selective access to polyhydroxy amino acids that have been efficiently transformed into 1-deoxy-D-gulonojirimycin or 1-deoxy-D-allonojirimycin. (C) 2002 Elsevier Science Ltd. All rights reserved.