(R)-2-<1-(N,N-dibenzylamino)-4-<(tert-butyldimethylsilyl)oxy>butyl> methanesulfonate | 152298-97-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (R)-2-<1-(N,N-dibenzylamino)-4-<(tert-butyldimethylsilyl)oxy>butyl> methanesulfonate
• 英文别名: [(2R)-4-[tert-butyl(dimethyl)silyl]oxy-1-(dibenzylamino)butan-2-yl] methanesulfonate
• CAS: 152298-97-0
• 化学式: C₂₅H₃₉NO₄SSi
• 分子量: 477.74
• InChiKey: WCVJAGAOVOUWKE-XMMPIXPASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.45
• 重原子数：
  32
• 可旋转键数：
  13
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  64.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (R)-2-<1-(N,N-dibenzylamino)-4-<(tert-butyldimethylsilyl)oxy>butyl> methanesulfonate 在 一水合肼 、 甲基磺酰氯 、 三乙胺 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 反应 65.08h， 生成 (R)-1-(N,N-dibenzylamino)-4-<(tert-butyldimethylsilyl)oxy>-2-butylamine
  参考文献：
  名称：

  Enantiomerically Pure Amino Alcohols and Diamino Alcohols from L-Aspartic Acid. Application to the Synthesis of Epi- and Diepislaframine

  摘要：

  Starting from natural aspartic acid (6) a practical method for the synthesis of enantiomerically pure 3-amino alcohols 8 including 3,4-diamino derivatives is described. After perbenzylation of 6 and reduction of both carboxylates, position 4 of the resultant (dibenzylamino)butanediol (11) could be regioselectively blocked to afford the silyloxy-protected intermediate 12a. Functionalization of position 1 was accomplished by nucleophilic displacement reactions including a 2-fold migration of the dibenzylamino substituent or by reductive amination of the amino aldehyde 15. Both routes proceeded under complete preservation of the optical purity. For envisioned SAR studies, we, furthermore, report on the application of this method to a chirospecific synthesis of epi- and diepislaframine (9a and 9b) as diastereomers of the highly bioactive indolizidine alkaloid slaframine (9c). Our first approach including reductive coupling of the chiral amino aldehyde 15 with 5-hydroxypyrrolidine failed when formation of a quaternary ammonium salt occurred, preventing the anticipated anionic cyclization. Therefore, we turned out attention to methodology developed by Wasserman. In fact, introduction of a 3-hydroxypyrrole-2-carboxylate fragment gave a cyclization precursor (30b) which could be successfully transformed into epi- and diepislaframine.

  DOI：

  10.1021/jo00101a042
• 作为产物：
  描述：

  (2S)-4-{[tert-butyl(dimethyl)silyl]oxy}-2-(dibenzylamino)butan-1-ol 、 甲基磺酸酐 在 三乙胺 作用下， 生成 (R)-2-<1-(N,N-dibenzylamino)-4-<(tert-butyldimethylsilyl)oxy>butyl> methanesulfonate
  参考文献：
  名称：

  实用的EPC合成1,2-和1,3-氨基醇

  摘要：

  据报道，通过从L-天冬氨酸获得的关键中间体2和8a，b有效合成了对映体纯的1，2-和1，3-氨基醇（4，10）。以4d为例，表明该产品可以用作不寻常的氨基醛和非蛋白氨基酸的前体。

  DOI：

  10.1016/s0040-4039(00)79340-3

文献信息

• Practical EPC synthesis of 1,2- and 1,3-amino alcohols
  作者：Peter Gmeiner、Annerose Kärtner、Dagmar Junge

  DOI：10.1016/s0040-4039(00)79340-3

  日期：1993.7

  An efficient synthesis of enantiomerically pure 1,2- and 1,3-amino alcohols (4,10) through the key intermediates 2 and 8a,b, obtained from L-aspartic acid, is reported. Using 4d as an example it is shown that the products can serve as precursors for unusual amino aldehydes and nonproteinogenic amino acids.

  据报道，通过从L-天冬氨酸获得的关键中间体2和8a，b有效合成了对映体纯的1，2-和1，3-氨基醇（4，10）。以4d为例，表明该产品可以用作不寻常的氨基醛和非蛋白氨基酸的前体。
• Enantiomerically Pure Amino Alcohols and Diamino Alcohols from L-Aspartic Acid. Application to the Synthesis of Epi- and Diepislaframine
  作者：Peter Gmeiner、Dagmar Junge、Annerose Kaertner

  DOI：10.1021/jo00101a042

  日期：1994.11

  Starting from natural aspartic acid (6) a practical method for the synthesis of enantiomerically pure 3-amino alcohols 8 including 3,4-diamino derivatives is described. After perbenzylation of 6 and reduction of both carboxylates, position 4 of the resultant (dibenzylamino)butanediol (11) could be regioselectively blocked to afford the silyloxy-protected intermediate 12a. Functionalization of position 1 was accomplished by nucleophilic displacement reactions including a 2-fold migration of the dibenzylamino substituent or by reductive amination of the amino aldehyde 15. Both routes proceeded under complete preservation of the optical purity. For envisioned SAR studies, we, furthermore, report on the application of this method to a chirospecific synthesis of epi- and diepislaframine (9a and 9b) as diastereomers of the highly bioactive indolizidine alkaloid slaframine (9c). Our first approach including reductive coupling of the chiral amino aldehyde 15 with 5-hydroxypyrrolidine failed when formation of a quaternary ammonium salt occurred, preventing the anticipated anionic cyclization. Therefore, we turned out attention to methodology developed by Wasserman. In fact, introduction of a 3-hydroxypyrrole-2-carboxylate fragment gave a cyclization precursor (30b) which could be successfully transformed into epi- and diepislaframine.