(syni)-(2RS,3RS)-dimethyl N,N'-di-tert-butyloxycarbonyl-3-aminoaspartate

• 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: (syni)-(2RS,3RS)-dimethyl N,N'-di-tert-butyloxycarbonyl-3-aminoaspartate
• 英文别名: (2S*,3R*)-methyl 3-amino-N,N'-bis(tert-butoxycarbonyl)aspartate；meso-Dimethyl N,N'-di-tert-butoxycarbonyl-3-aminoaspartate；dimethyl (2S,3R)-2,3-bis[(2-methylpropan-2-yl)oxycarbonylamino]butanedioate
• 化学式: C₁₆H₂₈N₂O₈
• 分子量: 376.407
• InChiKey: XMHPFGREFFVISP-AOOOYVTPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  26
• 可旋转键数：
  11
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  129
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为产物：
  描述：

  dimethyl (S)-N-(9-phenyl-9H-fluoren-9-yl)aspartate 在 palladium-barium carbonate 2,4,6-三异丙基苯磺酰叠氮化物 、 氢气 、 双(三甲基硅烷基)氨基钾 作用下， 以 四氢呋喃 、 甲醇 为溶剂， -78.0~-55.0 ℃ 、101.33 kPa 条件下， 反应 7.1h， 生成 (syni)-(2RS,3RS)-dimethyl N,N'-di-tert-butyloxycarbonyl-3-aminoaspartate
  参考文献：
  名称：

  On the Stereoselectivity of the Reaction of N-(9-Phenylfluoren-9-yl)aspartate Enolates with Electrophiles. Synthesis of Enantiomerically Pure 3-Hydroxy-, 3-Amino-, and 3-Hydroxy-3-methylaspartates

  摘要：

  We have developed efficient and stereoselective preparations of enantiomerically pure (3R)- and (3S)-N-Pf-3-hydroxy- and N-Pf-3-aminoaspartates by reaction of N-Pf-aspartate enolates with electrophilic hydroxylating or aminating reagents. The stereoselectivity of the hydroxylation and amination reactions was shown to be dependent on the structure of the enolate (which is strongly affected by the presence of strong metal complexing agents) and whether the electrophile is able to complex the enolate counterion in the transition state of the reaction. We have also developed a regioselective preparation of enantiomerically pure N-Pf-3-hydroxy-3-methylaspartates, albeit with only modest stereoselectivity.

  DOI：

  10.1021/jo00104a019

文献信息

• Asymmetric Oxidative Dimerization of the Enolates of <i>N</i>-[Bis(methylthio)methylene]- and <i>N</i>-(Diphenylmethylene)glycine Esters
  作者：Carlos Alvarez-Ibarra、Aurelio G. Csákÿ、Belén Colmenero、M. Luz Quiroga

  DOI：10.1021/jo962116c

  日期：1997.4.1

  The oxidative dimerization of glycinates 1 with iodine takes place under kinetic control. The stereochemistry of the resulting 3-aminoaspartate 3 depends on the method used (base/solvent) to generate the corresponding enolate 2. Under suitable conditions, high yields and diastereomeric excesses in favor of the threo derivatives 3-I, which have C(2) symmetry, were obtained. In the presence of 8-phenylmenthol

  甘氨酸盐1与碘的氧化二聚反应是在动力学控制下进行的。生成的3-氨基天冬氨酸3的立体化学取决于所用的方法（碱/溶剂），以生成相应的烯醇盐2。在合适的条件下，高收率和非对映体过量有利于苏式衍生物3-I，其具有C（2 ）对称。在存在8-苯基薄荷醇作为手性助剂（2S，3S）-3-氨基天冬氨酸5-I的情况下。
• A Short Diastereoselective Synthesis of Orthogonally Protected Diaminosuccinic Acid Derivatives
  作者：Kirsten Zeitler、Wolfgang Steglich

  DOI：10.1021/jo049371e

  日期：2004.9.1

  Homogeneous, Rh-catalyzed hydrogenation of heteromeric olefinic glycine dimers presents an efficient route to diastereomerically pure, orthogonally protected diaminosuccinic acid derivatives depending on the double bond geometry of the starting material. The products were obtained as racemates.
• On the Stereoselectivity of the Reaction of N-(9-Phenylfluoren-9-yl)aspartate Enolates with Electrophiles. Synthesis of Enantiomerically Pure 3-Hydroxy-, 3-Amino-, and 3-Hydroxy-3-methylaspartates
  作者：Eduardo Fernandez-Megia、Manuel M. Paz、F. Javier Sardina

  DOI：10.1021/jo00104a019

  日期：1994.12

  We have developed efficient and stereoselective preparations of enantiomerically pure (3R)- and (3S)-N-Pf-3-hydroxy- and N-Pf-3-aminoaspartates by reaction of N-Pf-aspartate enolates with electrophilic hydroxylating or aminating reagents. The stereoselectivity of the hydroxylation and amination reactions was shown to be dependent on the structure of the enolate (which is strongly affected by the presence of strong metal complexing agents) and whether the electrophile is able to complex the enolate counterion in the transition state of the reaction. We have also developed a regioselective preparation of enantiomerically pure N-Pf-3-hydroxy-3-methylaspartates, albeit with only modest stereoselectivity.