(3S,6R,1'S,2'S,3'S)-3-[4-tert-butyldiphenylsilyloxy-1-hydroxy-2,3-isopropylidenedioxybutyl]-2,5-diethoxy-3,6-dihydro-6-isopropylpyrazine | 221564-60-9

• 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'S,3'S)-3-[4-tert-butyldiphenylsilyloxy-1-hydroxy-2,3-isopropylidenedioxybutyl]-2,5-diethoxy-3,6-dihydro-6-isopropylpyrazine
• 英文别名: (S)-[(4S,5S)-5-[[tert-butyl(diphenyl)silyl]oxymethyl]-2,2-dimethyl-1,3-dioxolan-4-yl]-[(2S,5R)-3,6-diethoxy-5-propan-2-yl-2,5-dihydropyrazin-2-yl]methanol
• CAS: 221564-60-9
• 化学式: C₃₄H₅₀N₂O₆Si
• 分子量: 610.866
• InChiKey: AAXVKHPBRSRUEA-PBIKNJLJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.72
• 重原子数：
  43
• 可旋转键数：
  13
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  91.1
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (3S,6R,1'S,2'S,3'S)-3-[4-tert-butyldiphenylsilyloxy-1-hydroxy-2,3-isopropylidenedioxybutyl]-2,5-diethoxy-3,6-dihydro-6-isopropylpyrazine 在 四丁基氟化铵 、 四丁基碘化铵 、 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 28.0h， 生成 (3S,6R,1'S,2'S,3'S)-3-(1-benzyloxy-4-hydroxy-2,3-isopropylidenedioxybutyl)-2,5-diethoxy-3,6-dihydro-6-isopropylpyrazine
  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：

  4-O-(tert-butyldiphenylsilyl)-2,3-O-isopropylidene-L-threose 、 lithium;(2R)-3,6-diethoxy-2-propan-2-yl-2,5-dihydropyrazin-5-ide 在 tin(ll) chloride 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以79%的产率得到(3S,6R,1'S,2'S,3'S)-3-[4-tert-butyldiphenylsilyloxy-1-hydroxy-2,3-isopropylidenedioxybutyl]-2,5-diethoxy-3,6-dihydro-6-isopropylpyrazine
  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.