tert-butyl (1SR,4RS,5SR,6RS)-5-hydroxy-6-[(4-methylphenyl)sulfonyl]-7-azabicyclo[2.2.1]hept-2-ene-7-carboxylate

• 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: tert-butyl (1SR,4RS,5SR,6RS)-5-hydroxy-6-[(4-methylphenyl)sulfonyl]-7-azabicyclo[2.2.1]hept-2-ene-7-carboxylate
• 英文别名: (+/-)-(1SR,4RS,5SR,6RS)-7-tert-butoxycarbonyl-6-endo-p-toluenesulfonyl-7-azabicyclo[2.2.1]hept-2-en-5-endo-ol；tert-butyl (1R,4S,5R,6S)-5-hydroxy-6-(4-methylphenyl)sulfonyl-7-azabicyclo[2.2.1]hept-2-ene-7-carboxylate
• 化学式: C₁₈H₂₃NO₅S
• 分子量: 365.45
• InChiKey: HEAIOYWOPVVORW-JJXSEGSLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  25
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  92.3
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  tert-butyl (1SR,4RS,5SR,6RS)-5-hydroxy-6-[(4-methylphenyl)sulfonyl]-7-azabicyclo[2.2.1]hept-2-ene-7-carboxylate 在 吡啶 、 N-morpholine oxide 、 4-二甲氨基吡啶 、 四氧化锇 、 sodium methylate 、 对甲苯磺酸 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 四氯化碳 、 二氯甲烷 、 水 、 丙酮 为溶剂， 反应 20.38h， 生成 tert-butyl (3aR,4S,7R,7aS)-2,2-dimethyl-5-[(4-methylphenyl)sulfonyl]-3a,4,7,7a-tetrahydro-4,7-epimino-1,3-benzodioxole-8-carboxylate
  参考文献：
  名称：

  Synthesis of Enantiomerically Pure 1,2-Diamine Derivatives of 7-Azabicyclo[2.2.1]heptane. New Leads as Glycosidase Inhibitors and Rigid Scaffolds for the Preparation of Peptide Analogues

  摘要：

  Enantiomerically pure alcohols (-)- and (+)-7-tert-butoxycarbonyl-6-endo-p-toluenesulfonyl-7azabicyclo[2.2.1]hept-2-en-5-endo-ol ((-)-11 and (+)-11) have been obtained from the Diels-Alder adduct of N-(tert-butoxycarbonyl)pyrroel and 2-bromo-1-p-toluenesulfonylacetylene, including a resolution method. These two alcohols were converted into (+)- and (-)-5-exo-amino-7-(tertbutoxycarbonyl))-2,3-exo-isopropylidenedioxy-7-azabicyclo[2.2.1]heptane ((+)-18 and (-)-18) and (+)and (-)-5-endo-amino-7-(tert-butoxycarbonyl)-2,3-exo-isopropylidenedioxy-7-azabicyclo[2.2.1]heptane ((+)-19 and (-)-19) after adequate fanctionalization and desulfonylation steps. The corresponding conformationally constrained bicyclic 1,2-diamines (+)-4, (-)-4, (+/-)-5, (+/-)-6, (+)-7, and (-)-7 were obtained from the protected precursors 18 and 19 and evaluated as glycosidase inhibitors. Diamines (+)-4, (-)-4, (+)-6, and (-)-6 can be seen as new nonpeptide molecular scaffolds for the design of peptide analogues.

  DOI：

  10.1021/jo0301088
• 作为产物：
  描述：

  tert-butyl (1S,4R,5S,6R)-5-[(4-methylphenyl)sulfonyl]-6-({[(1S,4R)-4,7,7-trimethyl-3-oxo-2-oxabicyclo[2.2.1]hept-1-yl]carbonyl}oxy)-7-azabicyclo[2.2.1]hept-2-ene-7-carboxylate 在 sodium methylate 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 4.0h， 以90%的产率得到tert-butyl (1SR,4RS,5SR,6RS)-5-hydroxy-6-[(4-methylphenyl)sulfonyl]-7-azabicyclo[2.2.1]hept-2-ene-7-carboxylate
  参考文献：
  名称：

  Synthesis of Enantiomerically Pure 1,2-Diamine Derivatives of 7-Azabicyclo[2.2.1]heptane. New Leads as Glycosidase Inhibitors and Rigid Scaffolds for the Preparation of Peptide Analogues

  摘要：

  Enantiomerically pure alcohols (-)- and (+)-7-tert-butoxycarbonyl-6-endo-p-toluenesulfonyl-7azabicyclo[2.2.1]hept-2-en-5-endo-ol ((-)-11 and (+)-11) have been obtained from the Diels-Alder adduct of N-(tert-butoxycarbonyl)pyrroel and 2-bromo-1-p-toluenesulfonylacetylene, including a resolution method. These two alcohols were converted into (+)- and (-)-5-exo-amino-7-(tertbutoxycarbonyl))-2,3-exo-isopropylidenedioxy-7-azabicyclo[2.2.1]heptane ((+)-18 and (-)-18) and (+)and (-)-5-endo-amino-7-(tert-butoxycarbonyl)-2,3-exo-isopropylidenedioxy-7-azabicyclo[2.2.1]heptane ((+)-19 and (-)-19) after adequate fanctionalization and desulfonylation steps. The corresponding conformationally constrained bicyclic 1,2-diamines (+)-4, (-)-4, (+/-)-5, (+/-)-6, (+)-7, and (-)-7 were obtained from the protected precursors 18 and 19 and evaluated as glycosidase inhibitors. Diamines (+)-4, (-)-4, (+)-6, and (-)-6 can be seen as new nonpeptide molecular scaffolds for the design of peptide analogues.

  DOI：

  10.1021/jo0301088

文献信息

• Exploiting the Ring Strain in Bicyclo[2.2.1]heptane Systems for the Stereoselective Preparation of Highly Functionalized Cyclopentene, Dihydrofuran, Pyrroline, and Pyrrolidine Scaffolds
  作者：Elena Moreno-Clavijo、Antonio J. Moreno-Vargas、Raphaëlle Kieffer、Thérèse Sigstam、Ana T. Carmona、Inmaculada Robina

  DOI：10.1021/ol2027009

  日期：2011.12.2

  bridgehead substituted bicyclo[2.2.1]hept-2-enes giving rise to orthogonally functionalized cyclopentene, 2,5-dihydrofuran, and 3-pyrroline scaffolds. Retro-Dieckman reactions were easily carried out on 3-tosyl-(7-carba/7-oxa/7-aza)bicyclo[2.2.1]hept-5-en-2-ones. Retro-aldol reactions of N-Boc-3-tosyl-7-azabicyclo[2.2.1]hept-5-en-2-ol and functionalized N-Boc-3-tosyl-7-azabicyclo[2.2.1]heptan-2-ols yield

  双环体系的高应变驱动桥头取代的双环[2.2.1]庚-2-烯上的逆向缩合反应，从而产生正交官能化的环戊烯，2,5-二氢呋喃和3-吡咯啉骨架。Retro-Dieckman反应很容易在3-tosyl-（7-carba / 7-oxa / 7-aza）双环[2.2.1] hept-5-en-2-ones上进行。的复古羟醛缩合反应Ñ -Boc-3-甲苯磺酰基-7-氮杂双环[2.2.1]庚-5-烯-2-醇和官能Ñ -Boc-3甲苯磺酰基-7-氮杂双环[2.2.1]庚烷2-ols立体选择性地产生官能化的吡咯烷支架。相同的反应不适用于相应的降冰片烯和7-氧杂降冰片烯衍生物。
• Synthesis of Enantiomerically Pure 1,2-Diamine Derivatives of 7-Azabicyclo[2.2.1]heptane. New Leads as Glycosidase Inhibitors and Rigid Scaffolds for the Preparation of Peptide Analogues
  作者：Antonio J. Moreno-Vargas、Catherine Schütz、Rosario Scopelliti、Pierre Vogel

  DOI：10.1021/jo0301088

  日期：2003.7.1

  Enantiomerically pure alcohols (-)- and (+)-7-tert-butoxycarbonyl-6-endo-p-toluenesulfonyl-7azabicyclo[2.2.1]hept-2-en-5-endo-ol ((-)-11 and (+)-11) have been obtained from the Diels-Alder adduct of N-(tert-butoxycarbonyl)pyrroel and 2-bromo-1-p-toluenesulfonylacetylene, including a resolution method. These two alcohols were converted into (+)- and (-)-5-exo-amino-7-(tertbutoxycarbonyl))-2,3-exo-isopropylidenedioxy-7-azabicyclo[2.2.1]heptane ((+)-18 and (-)-18) and (+)and (-)-5-endo-amino-7-(tert-butoxycarbonyl)-2,3-exo-isopropylidenedioxy-7-azabicyclo[2.2.1]heptane ((+)-19 and (-)-19) after adequate fanctionalization and desulfonylation steps. The corresponding conformationally constrained bicyclic 1,2-diamines (+)-4, (-)-4, (+/-)-5, (+/-)-6, (+)-7, and (-)-7 were obtained from the protected precursors 18 and 19 and evaluated as glycosidase inhibitors. Diamines (+)-4, (-)-4, (+)-6, and (-)-6 can be seen as new nonpeptide molecular scaffolds for the design of peptide analogues.