methyl (1S,2R,4R)-N-benzoyl-2-formyl-7-azabicyclo[2.2.1]heptane-1-carboxylate | 365538-26-7

• 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: methyl (1S,2R,4R)-N-benzoyl-2-formyl-7-azabicyclo[2.2.1]heptane-1-carboxylate
• 英文别名: methyl (1S,2R,4R)-7-benzoyl-2-formyl-7-azabicyclo[2.2.1]heptane-1-carboxylate
• CAS: 365538-26-7
• 化学式: C₁₆H₁₇NO₄
• 分子量: 287.315
• InChiKey: VEYSIOXAPFBWBP-ZENOOKHLSA-N

物化性质

• 熔点：
  110 °C
• 沸点：
  435.1±40.0 °C(Predicted)
• 密度：
  1.353±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  63.7
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl (1S,2R,4R)-N-benzoyl-2-formyl-7-azabicyclo[2.2.1]heptane-1-carboxylate 在 sodium tetrahydroborate 、 18-冠醚-6 、 三乙胺 、 lithium bromide 作用下， 以 甲醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 168.83h， 生成 methyl (1S,2S,4R)-N-benzoyl-2-cyanomethyl-7-azabicyclo[2.2.1]heptane-1-carboxylate
  参考文献：
  名称：

  New enantiopure 7-azanorbornane β-substituted prolines by SN2 displacements at the Cγ of the side chain

  摘要：

  Continuing our work on building new beta-substituted prolines in en antiomerically pure form as new surrogates to be incorporated into model peptides, we describe functional group conversions and carbon-carbon bond forming reactions by S(N)2 displacements at the gamma-position of the alpha-amino acid side chain of an azanorbornane derivative. This work extends efforts on the elaboration of the side arm at carbon C2 of the 7-azabicyclo[2.2.1]heptane core. (C) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2005.08.003
• 作为产物：
  描述：

  methyl (1S,2R,4R)-N-benzoyl-2-[(S)-1,2-dihydroxyethyl]-7-azabicyclo[2.2.1]heptane-1-carboxylate 在 sodium periodate 作用下， 以 四氢呋喃 、 水 为溶剂， 以90%的产率得到methyl (1S,2R,4R)-N-benzoyl-2-formyl-7-azabicyclo[2.2.1]heptane-1-carboxylate
  参考文献：
  名称：

  以（R）-甘油醛为原料的手性不饱和恶唑酮通过Diels-Alder反应合成脯氨酸

  摘要：

  该报告描述了对映体纯的2-取代的7-氮杂双环[2.2.1]庚烷-1-羧酸的不对称合成的新途径，所述新的构象受限的β-官能化的脯氨酸类似物。我们的策略是通过关键步骤制备有价值的氮杂双环中间体，该关键步骤涉及分子内环化衍生自衍生自（R）-甘油醛的手性恶唑酮的不对称Diels-Alder反应提供的加合物转化衍生的衍生物。与Danishefsky的二烯。该方法在（1 S，2 R，4 R）-7-氮杂双环[2.2.1]庚烷-1,2-二羧酸和（1 S，2 R，4 ）的合成中的应用R）-2-丙基-7-氮杂双环[2.2.1]庚烷-1-羧酸盐酸盐，也可以分别视为1-天冬氨酸和1-正亮氨酸类似物，可用于说明我们方法学的多功能性。

  DOI：

  10.1016/s0040-4020(01)00533-6

文献信息

• Synthesis of enantiopure 7-azanorbornane proline–α-amino acid chimeras by highly efficient HPLC resolution of a phenylalanine analogue
  作者：Ana M. Gil、Elena Buñuel、Pilar López、Carlos Cativiela

  DOI：10.1016/j.tetasy.2003.12.008

  日期：2004.3

  4S)-2-phenyl-7-azabicyclo [2.2.1]heptane-1-carboxylic acid hydrochlorides, which are proline–phenylalanine chimeras, have been separately obtained by resolution of a key intermediate using chiral high performance liquid chromatography. The efficiency of the chromatographic resolution provides a general methodology for the preparation of both enantiomers of a broad variety of proline–α-amino acid chimeras with a

  对映体纯的构象受限的脯氨酸（1 S，2 S，4 R）-和（1 R，2 R，4 S）-2-苯基-7-氮杂双环[2.2.1]庚烷-1-羧酸盐酸盐，它们是脯氨酸-苯丙氨酸嵌合体，是通过使用手性高效液相色谱拆分关键中间体而单独获得的。色谱分离的效率为制备具有7-氮杂降硼烷骨架的多种脯氨酸-α-氨基酸嵌合体的两种对映异构体提供了一种对映体纯形式的通用方法。
• Olefination of methyl (1S,2R,4R)-N-benzoyl-2-formyl-7-azabicyclo[2.2.1]heptane-1-carboxylate, a synthetic approach to new conformationally constrained prolines
  作者：Ana M. Gil、Elena Buñuel、Marı́a D. Dı́az-de-Villegas、Carlos Cativiela

  DOI：10.1016/s0957-4166(03)00200-3

  日期：2003.6

  Wittig olefinations of methyl (1S,2R,4R)-N-benzoyl-2-formyl-7-azabicyclo[2.2.1]heptane-1-carboxylate with several phosphoranes and the Horner-Wittig reaction, using methyl diethylphosphonoacetate, have been tested in order to evaluate their utility in the synthesis of beta-substituted conformationally constrained prolines. Subsequent elaboration of the resulting alkenes has provided proline-amino acid chimeras [combinations of proline with other alpha-amino acids, such as L-norvaline, L-norleucine, L-alpha-(3-phenylpropyl)glycine or L-homoglutamic acid] with the 7-azabicyclo[2.2.1]heptane skeleton in an enantiomerically pure form. (C) 2003 Elsevier Science Ltd. All rights reserved.
• New enantiopure 7-azanorbornane β-substituted prolines by SN2 displacements at the Cγ of the side chain
  作者：Ana M. Gil、Ester Orús、Verónica López-Carrillo、Elena Buñuel、Carlos Cativiela

  DOI：10.1016/j.tetasy.2005.08.003

  日期：2005.9

  Continuing our work on building new beta-substituted prolines in en antiomerically pure form as new surrogates to be incorporated into model peptides, we describe functional group conversions and carbon-carbon bond forming reactions by S(N)2 displacements at the gamma-position of the alpha-amino acid side chain of an azanorbornane derivative. This work extends efforts on the elaboration of the side arm at carbon C2 of the 7-azabicyclo[2.2.1]heptane core. (C) 2005 Elsevier Ltd. All rights reserved.
• Synthesis of constrained prolines by Diels–Alder reaction using a chiral unsaturated oxazolone derived from (R)-glyceraldehyde as starting material
  作者：Elena Buñuel、Ana M Gil、Marı́a D Dı́az-de-Villegas、Carlos Cativiela

  DOI：10.1016/s0040-4020(01)00533-6

  日期：2001.7

  This report describes a new route for the asymmetric synthesis of enantiomerically pure 2-substituted 7-azabicyclo[2.2.1]heptane-1-carboxylic acids, which are new conformationally constrained β-functionalised proline analogues. Our strategy is based on the preparation of a valuable azabicyclic intermediate by a key step that involves the intramolecular cyclisation of a derivative obtained from the

  该报告描述了对映体纯的2-取代的7-氮杂双环[2.2.1]庚烷-1-羧酸的不对称合成的新途径，所述新的构象受限的β-官能化的脯氨酸类似物。我们的策略是通过关键步骤制备有价值的氮杂双环中间体，该关键步骤涉及分子内环化衍生自衍生自（R）-甘油醛的手性恶唑酮的不对称Diels-Alder反应提供的加合物转化衍生的衍生物。与Danishefsky的二烯。该方法在（1 S，2 R，4 R）-7-氮杂双环[2.2.1]庚烷-1,2-二羧酸和（1 S，2 R，4 ）的合成中的应用R）-2-丙基-7-氮杂双环[2.2.1]庚烷-1-羧酸盐酸盐，也可以分别视为1-天冬氨酸和1-正亮氨酸类似物，可用于说明我们方法学的多功能性。