(+)-(1S,2R,3S,4S,5S,6R)-5-endo-azido-7-tert-butoxycarbonyl-2,3-exo-isopropylidenedioxy-6-exo-p-toluenesulfonyl-7-azabicyclo[2.2.1]heptane | 573716-87-7

• 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: (+)-(1S,2R,3S,4S,5S,6R)-5-endo-azido-7-tert-butoxycarbonyl-2,3-exo-isopropylidenedioxy-6-exo-p-toluenesulfonyl-7-azabicyclo[2.2.1]heptane
• 英文别名: tert-butyl (1S,2R,6S,7S,8S,9S)-8-azido-4,4-dimethyl-9-(4-methylphenyl)sulfonyl-3,5-dioxa-10-azatricyclo[5.2.1.02,6]decane-10-carboxylate
• CAS: 573716-87-7
• 化学式: C₂₁H₂₈N₄O₆S
• 分子量: 464.543
• InChiKey: HPNGLTBCBZDQLQ-UXJCHEOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  32
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  105
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (+)-(1S,2R,3S,4S,5S,6R)-5-endo-azido-7-tert-butoxycarbonyl-2,3-exo-isopropylidenedioxy-6-exo-p-toluenesulfonyl-7-azabicyclo[2.2.1]heptane 在 palladium on activated charcoal sodium amalgam 、 氢气 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 2.0h， 生成 (-)-(1R,2R,3S,4S,5R)-5-endo-amino-7-tert-butoxycarbonyl-2,3-exo-isopropylidenedioxy-7-azabicyclo[2.2.1]heptane
  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 (1R,4S,5R,6S)-5-[(4-methylphenyl)sulfonyl]-6-({[(1R,4S)-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 吡啶 、 N-morpholine oxide 、 4-二甲氨基吡啶 、 四氧化锇 、 叠氮基三甲基硅烷 、 四丁基氟化铵 、 sodium methylate 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 甲醇 、 四氯化碳 、 水 、 丙酮 为溶剂， 反应 18.13h， 生成 (+)-(1S,2R,3S,4S,5S,6R)-5-endo-azido-7-tert-butoxycarbonyl-2,3-exo-isopropylidenedioxy-6-exo-p-toluenesulfonyl-7-azabicyclo[2.2.1]heptane
  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

• Regioselective rearrangement of 7-azabicyclo[2.2.1]hept-2-aminyl radicals: first synthesis of 2,8-diazabicyclo[3.2.1]oct-2-enes and their conversion into 5-(2-aminoethyl)-2,3,4-trihydroxypyrrolidines, new inhibitors of α-mannosidases
  作者：Antonio J Moreno-Vargas、Pierre Vogel

  DOI：10.1016/s0040-4039(03)01141-9

  日期：2003.6

  Enantiomerically pure 2,8-diazabicyclo[3.2.1]oct-2-ene derivatives (+)-5 and (-)-5 have been obtained from 2-azido-3-tosyl-7-azabicyclo[2.2.1]heptanes (+)-1 and (-)-2 and their enantiomers, by ring expansion under radical conditions. Compounds (+)-5 and (-)-5 were transformed into hemiaminals 9 ((3S,4R,5R)- and 10 ((3R,4S,5S)-5-(2-aminoethyl)-2,3,4-trihydroxypyrrolidine) that are good inhibitors of alpha-mannosidases. (C) 2003 Published by Elsevier Science Ltd.
• 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.