diethyl (R)-(α-methylbenzyl)aminomalonate | 592531-06-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: diethyl (R)-(α-methylbenzyl)aminomalonate
• 英文别名: diethyl 2-(1R-phenylethyl)aminomalonate；diethyl 2-[[(1R)-1-phenylethyl]amino]propanedioate
• CAS: 592531-06-1
• 化学式: C₁₅H₂₁NO₄
• 分子量: 279.336
• InChiKey: ZLOUCDGERAQFGP-LLVKDONJSA-N

物化性质

• 沸点：
  165 °C(Press: 0.18 Torr)
• 密度：
  1.096±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  20
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  64.6
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  diethyl (R)-(α-methylbenzyl)aminomalonate 在 sodium tetrahydroborate 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 15.0h， 以22.0 g的产率得到(R)-2-[(α-methylbenzyl)amino]-1,3-propanediol
  参考文献：
  名称：

  A novel dynamic kinetic resolution accompanied by intramolecular transesterification: asymmetric synthesis of a 4-hydroxymethyl-2-oxazolidinone from serinol derivatives

  摘要：

  Reaction paths of the one-pot reaction of (R)-2-(alpha-methylbenzyl)amino-1,3-propanediol (1) and 2-chloroethyl chloroformate with DBU giving (4S,alphaR)-4-hydroxymethyl-3-(alpha-methylbenzyl)-2-oxazolidinone [(4S)-2] (94% de) were investigated. Intermediates of this reaction, 2-chloroethyl (2S)- and 2-chloroethyl (2R)-3-hydroxy-2-[(alphaR)-alpha-methylbenzyl]aminopropyl carbonates [(2S)-4 and (2R)-4], were synthesized individually. After the addition of DBU to the respective solution of the carbonate (2S)-4 and that of (2R)-4 in dichloromethane, the intramolecular transesteritication between (2S)-4 and (2R)-4 and the diastereoselective intramolecular cyclization proceeded to afford (4S)-2 in high diastereomeric excess. Therefore, two monocarbonates (2S)-4 and (2R)-4 were kinetically resolved by this cyclization during the intramolecular transesterification between (2S)-4 and (2R)-4. We found that this process involved dynamic kinetic resolution accompanied by intramolecular transesterification. (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(03)00477-0
• 作为产物：
  描述：

  R(+)-alpha-甲基苄胺 、 溴代丙二酸二乙酯 在 三乙胺 、 碳酸氢钠 作用下， 以 乙腈 、 乙醚 、 水 为溶剂， 反应 18.0h， 生成 diethyl (R)-(α-methylbenzyl)aminomalonate
  参考文献：
  名称：

  非酶促非对映选择性不对称的2-苄基丝氨酸提供光学活性的4-苄基-4-羟甲基-2-恶唑烷酮：α-（羟甲基）苯丙氨酸，N -Boc-α-甲基苯丙氨酸，西立胺和BIRT-377的不对称合成

  摘要：

  （S）-2-苄基-2-（α-甲基苄基）氨基-1,3-丙二醇（S）-4a与氯甲酸2-氯乙酯的反应，随后加入DBU得到（4R，αS）通过非对映选择性不对称脱对称过程，-4-苄基-4-羟甲基-3-（α-甲基苄基）-2-恶唑烷酮（4 R）-5a（92％de）。使用三氟甲磺酸和苯甲醚在MeNO 2中对（4 R）-5a进行脱苄基反应得到（R）-4-苄基-4-羟甲基-2-恶唑烷酮（R）-15a，将其转化为（R）-（α-羟甲基）苯丙氨酸（7）分两步进行。N - Boc -α-甲基苯丙氨酸（8），cericlamine（9）和BIRT-377（10）也使用这些不对称脱对称和脱苄基反应合成。

  DOI：

  10.1016/j.tet.2012.06.090

文献信息

• Diastereoselective construction of azetidin-2-ones by electrochemical intramolecular C–C bond forming reaction
  作者：Daishirou Minato、Satoshi Mizuta、Masami Kuriyama、Yoshihiro Matsumura、Osamu Onomura

  DOI：10.1016/j.tet.2009.09.087

  日期：2009.11

  A convenient: method for synthesis of optically active azetidin-2-ones using electrochemical oxidation has been exploited. The method consists of a diastereoselective intramolecular C-C bond forming reaction between active methylene and methyne groups through an electrochemical system in which positive iodine species acted as mediators under mild conditions. (C) 2009 Elsevier Ltd. All rights reserved.
• Asymmetric synthesis of the 4-hydroxymethyl-2-oxazolidinone from the serinol derivative and chloroformates
  作者：Shigeo Sugiyama、Shoko Watanabe、Keitaro Ishii

  DOI：10.1016/s0040-4039(99)01548-8

  日期：1999.10

  Asymmetric desymmetrization of 2-[(alpha R)-alpha-methylbenzyl]amino-1,3-propanediol (1) with 2-chloroethyl chloroformate and DBU at room temperature gave optically active (4S)-4-hydroxymethyl-N-[(alphaR)-alpha-methylbenzyl]-2-oxazolidinone [(4S)-2] (up to 94% de). This reaction involves kinetic resolution and [1,3]-alkoxyacyl migration of 2-chloroethyl (2S)- and 2-chloroethyl (2R)-3-hydroxy-2-[(alpha R)-alpha-methylbenzyl]aminopropyl carbonates [(2S)-4 and (2R)-4]. (C) 1999 Elsevier Science Ltd. All rights reserved.