Di-tert-butyl (4-(benzyloxy)-(S)-2-hydroxybutyl)malonate | 161111-09-7

• 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: Di-tert-butyl (4-(benzyloxy)-(S)-2-hydroxybutyl)malonate
• 英文别名: ditert-butyl 2-[(2S)-2-hydroxy-4-phenylmethoxybutyl]propanedioate
• CAS: 161111-09-7
• 化学式: C₂₂H₃₄O₆
• 分子量: 394.508
• InChiKey: RLTCHUIUCDNJAL-QGZVFWFLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  28
• 可旋转键数：
  13
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  82.1
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  Di-tert-butyl (4-(benzyloxy)-(S)-2-hydroxybutyl)malonate 在 palladium on activated charcoal 氢气 、 sodium hydride 、 三苯基膦 、 三氟乙酸 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 叔丁醇 为溶剂， 反应 49.5h， 生成 (1R,6R)-2-oxo-3-oxabicyclo[4.1.0]heptan-1-carboxylic acid
  参考文献：
  名称：

  Diastereo- and Enantioselective Synthesis of 2-Substituted 1-Aminocyclo­propane-1-Carboxylic Acids. Application to the Synthesis of Protected 2,3-Methano Analogs of Ornithine and Glutamic Acid

  摘要：

  本文描述了一种受保护的 2,3-甲桥氨基酸类似物的对映异构合成方法。由(S)-天冬氨酸制备的(R)-2-苄氧基乙基环氧乙烷与丙二酸叔丁酯反应，并进一步转化为一对对映体的中间环丙烷融合内酯--1-羧基-2-氧代-3-氧杂双环[4.1.0]庚烷。这些对映体中的每一种对映体都可以区分羧基功能，并在环丙烷上生成一个 2-羟乙基，从而获得任何或所有四种立体异构体。这种双碳垂体可以直接合成谷氨酸和鸟氨酸的受保护 2,3-甲烷类似物，并可用于其他有用的转化。

  DOI：

  10.1055/s-2005-870007
• 作为产物：
  描述：

  (2R)-2-(2-benzyloxyethyl)oxirane 在 4-二甲氨基吡啶 、 N,N-二甲基丙烯基脲 、 氢氧化钾 、 N,N'-二环己基碳二亚胺 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 5.25h， 生成 Di-tert-butyl (4-(benzyloxy)-(S)-2-hydroxybutyl)malonate
  参考文献：
  名称：

  Synthesis of (1R,3R,5S)-1-Amino-3-(hydroxymethyl)bicyclo[3.1.0]hexane as a Precursor for the Synthesis of Carbocyclic Nucleosides

  摘要：

  The stereocontrolled synthesis has been achieved of a 1,5-methano-1-amino-5-(hydroxymethyl)cyclopentane, a potential component for carbocyclic nucleosides. Stereocontrol was manifest by converting (R)-2-((benzyloxy)ethyl)oxirane specifically to (2S,3S)-2-amino-2,3-methanoadipate through a series of lactones. This aminocyclopropanecarboxylate was then cyclized to the corresponding cyclopentanone ester. Reduction of the ketone, elimination, and hydrogenation of the double bond led primarily to the cyclopentane with the amino and ester groups trans (9/1). Enolization followed by an ammonium chloride quench then inverted this to a mixture in which the cis isomer was dominant(4/1). Simple functional group manipulation then gave the target (1R,3R,5S)-1-amino-3-(hydroxymethyl)bicyclo[3.1.0]hexane.

  DOI：

  10.1021/jo00097a040

文献信息

• Synthesis of (1R,3R,5S)-1-Amino-3-(hydroxymethyl)bicyclo[3.1.0]hexane as a Precursor for the Synthesis of Carbocyclic Nucleosides
  作者：Hae Sung Chang、Stephen C. Bergmeier、Jeffrey A. Frick、Andreas Bathe、Henry Rapoport

  DOI：10.1021/jo00097a040

  日期：1994.9

  The stereocontrolled synthesis has been achieved of a 1,5-methano-1-amino-5-(hydroxymethyl)cyclopentane, a potential component for carbocyclic nucleosides. Stereocontrol was manifest by converting (R)-2-((benzyloxy)ethyl)oxirane specifically to (2S,3S)-2-amino-2,3-methanoadipate through a series of lactones. This aminocyclopropanecarboxylate was then cyclized to the corresponding cyclopentanone ester. Reduction of the ketone, elimination, and hydrogenation of the double bond led primarily to the cyclopentane with the amino and ester groups trans (9/1). Enolization followed by an ammonium chloride quench then inverted this to a mixture in which the cis isomer was dominant(4/1). Simple functional group manipulation then gave the target (1R,3R,5S)-1-amino-3-(hydroxymethyl)bicyclo[3.1.0]hexane.
• Diastereo- and Enantioselective Synthesis of 2-Substituted 1-Aminocyclo­propane-1-Carboxylic Acids. Application to the Synthesis of Protected 2,3-Methano Analogs of Ornithine and Glutamic Acid
  作者：Jeffrey A. Frick、John B. Klassen、Henry Rapoport

  DOI：10.1055/s-2005-870007

  日期：——

  An enantiodivergent synthesis of protected 2,3-methano amino acid analogs is described. (R)-2-benzyloxyethyloxirane, prepared from (S)-aspartic acid, was reacted with tert-butyl hydrogen malonate and further transformed into an enantiomeric pair of intermediate cyclopropane-fused-lactones, 1-carboxy-2-oxo-3-oxabicyclo[4.1.0]heptane. Each of these enantiomers allowed differentiation of the carboxy functions and generation of a 2-hydroxyethyl group on the cyclopropanes, thus affording access to any or all four stereoisomers. The two-carbon pendant allowed for the direct synthesis of protected 2,3-methano analogs of glutamic acid and ornithine and can be used for other useful transformations.

  本文描述了一种受保护的 2,3-甲桥氨基酸类似物的对映异构合成方法。由(S)-天冬氨酸制备的(R)-2-苄氧基乙基环氧乙烷与丙二酸叔丁酯反应，并进一步转化为一对对映体的中间环丙烷融合内酯--1-羧基-2-氧代-3-氧杂双环[4.1.0]庚烷。这些对映体中的每一种对映体都可以区分羧基功能，并在环丙烷上生成一个 2-羟乙基，从而获得任何或所有四种立体异构体。这种双碳垂体可以直接合成谷氨酸和鸟氨酸的受保护 2,3-甲烷类似物，并可用于其他有用的转化。