(6R,9S)-1-aza-3-amino-4-benzyl-9-<(tert-butyldimethylsiloxy)methyl>-2-oxobicyclo<4.3.0>non-3-ene | 161555-31-3

• 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: (6R,9S)-1-aza-3-amino-4-benzyl-9-<(tert-butyldimethylsiloxy)methyl>-2-oxobicyclo<4.3.0>non-3-ene
• 英文别名: (3S,8aR)-6-amino-7-benzyl-3-[[tert-butyl(dimethyl)silyl]oxymethyl]-2,3,8,8a-tetrahydro-1H-indolizin-5-one
• CAS: 161555-31-3
• 化学式: C₂₂H₃₄N₂O₂Si
• 分子量: 386.61
• InChiKey: YILLYTQHMGGYPA-MOPGFXCFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.23
• 重原子数：
  27
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  55.6
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (6R,9S)-1-aza-3-amino-4-benzyl-9-<(tert-butyldimethylsiloxy)methyl>-2-oxobicyclo<4.3.0>non-3-ene 在 N-乙基吗啉 、 4-二甲氨基吡啶 、 jones reagent 、 氰化钠 、 氨 、 1-羟基苯并三唑 、 1-(3-二甲基氨基丙基)-3-乙基碳二亚胺 作用下， 以 甲醇 、 二氯甲烷 、 丙酮 为溶剂， 反应 140.67h， 生成 (6R,9S,12S)-1-aza-3-(pyroglutamylamino)-4-benzyl-9-carbomoyl-2-oxobicyclo<4.3.0>nonene
  参考文献：
  名称：

  Conformationally Restricted Peptide Mimetics: The Incorporation of 6,5-Bicyclic Lactam Ring Skeletons into Peptides

  摘要：

  This manuscript describes a convenient procedure for the synthesis of peptide fragments containing 6,5-bicyclic lactam-based conformational constraints. The syntheses capitalize on an electrochemical oxidation to functionalize a substituted proline derivative, an N-acyliminium ion-initiated cyclization in order to form a transient seven-membered-ring lactam, and a rearrangement reaction to form the desired six-membered-ring lactam. The bicyclic lactam products were converted into peptide building blocks and the stereochemistry of the building blocks assigned using two-dimensional NMR techniques. Once synthesized, the building blocks were readily incorporated into peptide fragments with the use of standard peptide synthesis techniques. The synthetic route employed was shown to be compatible with both aryl and branched amino acid side chains.

  DOI：

  10.1021/jo00130a015
• 作为产物：
  描述：

  L-脯氨醇 在 palladium on activated charcoal 正丁基锂 、 氨 、 氢气 、 氧气 、 sodium methylate 、 四氯化钛 、 sodium hydride 、 四乙基对甲苯磺酸铵 、 1-羟基苯并三唑 、 1-(3-二甲基氨基丙基)-3-乙基碳二亚胺 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 二异丙胺 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 、 paraffin 为溶剂， 反应 1.58h， 生成 (6R,9S)-1-aza-3-amino-4-benzyl-9-<(tert-butyldimethylsiloxy)methyl>-2-oxobicyclo<4.3.0>non-3-ene
  参考文献：
  名称：

  Conformationally Restricted Peptide Mimetics: The Incorporation of 6,5-Bicyclic Lactam Ring Skeletons into Peptides

  摘要：

  This manuscript describes a convenient procedure for the synthesis of peptide fragments containing 6,5-bicyclic lactam-based conformational constraints. The syntheses capitalize on an electrochemical oxidation to functionalize a substituted proline derivative, an N-acyliminium ion-initiated cyclization in order to form a transient seven-membered-ring lactam, and a rearrangement reaction to form the desired six-membered-ring lactam. The bicyclic lactam products were converted into peptide building blocks and the stereochemistry of the building blocks assigned using two-dimensional NMR techniques. Once synthesized, the building blocks were readily incorporated into peptide fragments with the use of standard peptide synthesis techniques. The synthetic route employed was shown to be compatible with both aryl and branched amino acid side chains.

  DOI：

  10.1021/jo00130a015

文献信息

• The use of HMQC-TOCSY experiments for elucidating the structures of bicyclic lactams: Uncovering a surprise rearrangement in the synthesis of a key prophe building block
  作者：Kevin D. Moeller、Cathleen E. Hanau、Andrè d'Avignon

  DOI：10.1016/s0040-4039(00)75973-9

  日期：1994.1

  were used to unequivocally assign the ring skeletons of several bicyclic lactams. This work demonstrated the power of these techniques for establishing the complete carbon connectivity of peptide building blocks with closely overlapping protons. In addition, it has led to the discovery of a surprise rearrangement reaction and allowed for the correction of a previously misassigned Pro-Phe building block

  HMQC-TOCSY实验用于明确分配几个双环内酰胺的环骨架。这项工作证明了这些技术在建立具有紧密重叠质子的肽构件的完整碳连接性方面的力量。此外，它还导致了令人惊讶的重排反应的发现，并允许更正先前错配的Pro-Phe砌块环骨架。
• Conformationally Restricted Peptide Mimetics: The Incorporation of 6,5-Bicyclic Lactam Ring Skeletons into Peptides
  作者：Wenhao Li、Cathleen E. Hanau、Andre dAvignon、Kevin D. Moeller

  DOI：10.1021/jo00130a015

  日期：1995.12

  This manuscript describes a convenient procedure for the synthesis of peptide fragments containing 6,5-bicyclic lactam-based conformational constraints. The syntheses capitalize on an electrochemical oxidation to functionalize a substituted proline derivative, an N-acyliminium ion-initiated cyclization in order to form a transient seven-membered-ring lactam, and a rearrangement reaction to form the desired six-membered-ring lactam. The bicyclic lactam products were converted into peptide building blocks and the stereochemistry of the building blocks assigned using two-dimensional NMR techniques. Once synthesized, the building blocks were readily incorporated into peptide fragments with the use of standard peptide synthesis techniques. The synthetic route employed was shown to be compatible with both aryl and branched amino acid side chains.