(S)-2-(N,N-dibenzylamino)-4-<(tert-butyldimethylsilyl)oxy>butanal | 159497-68-4

• 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: (S)-2-(N,N-dibenzylamino)-4-<(tert-butyldimethylsilyl)oxy>butanal
• 英文别名: (2S)-4-[tert-butyl(dimethyl)silyl]oxy-2-(dibenzylamino)butanal
• CAS: 159497-68-4
• 化学式: C₂₄H₃₅NO₂Si
• 分子量: 397.633
• InChiKey: LTQNDERFALIRTG-QHCPKHFHSA-N

物化性质

• 沸点：
  456.2±45.0 °C(Predicted)
• 密度：
  1.006±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.67
• 重原子数：
  28
• 可旋转键数：
  11
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (S)-2-(N,N-dibenzylamino)-4-<(tert-butyldimethylsilyl)oxy>butanal 在 palladium dihydroxide 氢气 作用下， 以 甲醇 、 正己烷 、 甲苯 为溶剂， 反应 1.0h， 生成 (3S,4S)-4-Amino-6-(tert-butyl-dimethyl-silanyloxy)-hexan-3-ol
  参考文献：
  名称：

  操纵L-天冬氨酸和L-谷氨酸-对映体纯β-氨基-γ-羟基酸和γ-氨基-δ-羟基酸的非对映选择性合成

  摘要：

  Enantiopure (3S,4R)- 和 (3S,4S)-3-amino-4-hydroxyhexanoic 酸和 (4S,5R)- 和 (4S,5S)-4-amino-5-hydroxyheptanoic 酸衍生物已通过立体发散法制备分别由 L-天冬氨酸和 L-谷氨酸合成。与氨基相连的碳原子的立体化学由起始材料确定，但 C-4 或 C-5 的构型由二乙基锌或乙基溴化镁的非对映选择性烷基化控制。作为 OBO 原酸酯的羧基保护提高了最终产品的产率。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

  DOI：

  10.1002/ejoc.200300199
• 作为产物：
  描述：

  (2S)-2-[bis(phenylmethyl)amino]-1,4-butanediol 在 咪唑 、 草酰氯 、 二甲基亚砜 、 三乙胺 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 2.33h， 生成 (S)-2-(N,N-dibenzylamino)-4-<(tert-butyldimethylsilyl)oxy>butanal
  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

文献信息

• Diastereoselective Henry Reaction Catalyzed by Guanidine-Thiourea Bifunctional Organocatalyst
  作者：Kazuo Nagasawa、Yoshihiro Sohtome、Nobuko Takemura、Toshitsugu Iguchi、Yuichi Hashimoto

  DOI：10.1055/s-2005-922770

  日期：——

  A highly diastereoselective Henry reaction (diastereomer ratio of 84:16 to 99:1) of α-substituted aldehydes with nitromethane was developed using guanidine-thiourea bifunctional catalyst 1. N,N-Dibenzyl-protected α-amino aldehydes (2a, 2d-h) and α-hydroxy aldehydes protected as silyl ethers (2i-j) were suitable substrates. The matched combination of this catalytic system, i.e., S-aldehydes and (R,R)-1

  使用胍-硫脲双功能催化剂开发了 α-取代醛与硝基甲烷的高度非对映选择性亨利反应（非对映异构体比例为 84:16 至 99:1） 1. N,N-二苄基保护的 α-氨基醛 (2a, 2d- h) 和保护为甲硅烷基醚 (2i-j) 的 α-羟基醛是合适的底物。这种催化体系的匹配组合，即 S-醛和 (R,R)-1 催化剂，可以从由 1 催化的亨利反应的不对称形式的过渡态来理解。
• Stereoselective syntheses of (+)-α- and (−)-β-conhydrine from L-aspartic acid
  作者：Satyendra Kumar Pandey、Pradeep Kumar

  DOI：10.1016/j.tetlet.2005.04.013

  日期：2005.6

  An efficient synthesis of (+)-α-conhydrine 1 and (−)-β-conhydrine 2 has been achieved by diastereoselective alkylation of an amino aldehyde derivative 7 with ethylmagnesium bromide or diethylzinc.

  的有效的合成（+） - α-conhydrine 1和（ - ） - β-conhydrine 2已经通过氨基醛衍生物的非对映选择性烷基化实现7中用溴化乙基镁或二乙基锌。
• ManipulatingL-Aspartic andL-Glutamic Acids− Diastereoselective Synthesis of Enantiopureβ-Amino-γ-hydroxy Acids andγ-Amino-δ-hydroxy Acids
  作者：José M. Andrés、Eva M. Muñoz、Rafael Pedrosa、Alfonso Pérez-Encabo

  DOI：10.1002/ejoc.200300199

  日期：2003.9

  Enantiopure (3S,4R)- and (3S,4S)-3-amino-4-hydroxyhexanoic acids and (4S,5R)- and (4S,5S)-4-amino-5-hydroxyheptanoic acid derivatives have been prepared by stereodivergent synthesis from L-aspartic and L-glutamic acids, respectively. The stereochemistry at the carbon atom attached to the amino group was determined from the starting material, but the configuration at C-4 or C-5 is controlled by diastereoselective

  Enantiopure (3S,4R)- 和 (3S,4S)-3-amino-4-hydroxyhexanoic 酸和 (4S,5R)- 和 (4S,5S)-4-amino-5-hydroxyheptanoic 酸衍生物已通过立体发散法制备分别由 L-天冬氨酸和 L-谷氨酸合成。与氨基相连的碳原子的立体化学由起始材料确定，但 C-4 或 C-5 的构型由二乙基锌或乙基溴化镁的非对映选择性烷基化控制。作为 OBO 原酸酯的羧基保护提高了最终产品的产率。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
• 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.