1-acetylvinyl (1S,5R,7S)-3-ethyl-2-oxo-6,8-dioxa-3-azabicyclo<3.2.1>octane-7-exo-carboxylate | 147863-52-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧氮杂卓类
• 英文名称: 1-acetylvinyl (1S,5R,7S)-3-ethyl-2-oxo-6,8-dioxa-3-azabicyclo<3.2.1>octane-7-exo-carboxylate
• 英文别名: 1-acetylvinyl (1'R,5'S,7'R)-3'-ethyl-2'-oxo-3'-aza-6',8'-dioxabicyclo<3.2.1>octane-7'-carboxylate；3-oxobut-1-en-2-yl (1R,5S,7R)-3-ethyl-2-oxo-6,8-dioxa-3-azabicyclo[3.2.1]octane-7-carboxylate
• CAS: 147863-52-3
• 化学式: C₁₂H₁₅NO₆
• 分子量: 269.254
• InChiKey: PQLFRCXTMJRYLR-IVZWLZJFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  82.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1-acetylvinyl (1S,5R,7S)-3-ethyl-2-oxo-6,8-dioxa-3-azabicyclo<3.2.1>octane-7-exo-carboxylate 在 吡啶 、 三氟甲磺酸三甲基硅酯 、 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 反应 168.0h， 生成 (2'R)-12'-acetoxy-2'-acetyl-5'-formyl-1',2',3',4'-tetrahydronaphthacen-2'-yl (1R,5S,7R)-3-ethyl-2-oxo-6,8-dioxa-3-azabicyclo<3.2.1>octane-7-exo-carboxylate
  参考文献：
  名称：

  （R）-（-）-2-乙酰基-2,5,12-三氢-1,2,3,4-四氢-6,11-萘并苯醌的对映选择性合成

  摘要：

  BF 3 ·Et 2 O促进的1-乙酰乙烯基（1'R，5'S，7'R）-3'-乙基-2'-oxo-3'-aza-6'，8的Diels-Alder加成反应′-二氧杂双环[3.2.1]辛烷-7′-羧酸盐（1-乙酰基乙烯基RADO（Et））变成1-（二甲氧基甲基）-2,3,5,6-四亚甲基-7-氧杂环[2.2.1]庚烷区域，立体和非对映选择性，得到一加合物，将其转变为（R）-（-）-4-demethoxy-7-deoxydaunomycinone。

  DOI：

  10.1016/s0040-4039(00)77479-x
• 作为产物：
  描述：

  (1R,5S,7R)-3-Ethyl-2-oxo-6,8-dioxa-3-aza-bicyclo[3.2.1]octane-7-carbonyl chloride 、 2,3-丁二酮 在 吡啶 作用下， 以 甲苯 为溶剂， 生成 1-acetylvinyl (1S,5R,7S)-3-ethyl-2-oxo-6,8-dioxa-3-azabicyclo<3.2.1>octane-7-exo-carboxylate
  参考文献：
  名称：

  （R）-（-）-2-乙酰基-2,5,12-三氢-1,2,3,4-四氢-6,11-萘并苯醌的对映选择性合成

  摘要：

  BF 3 ·Et 2 O促进的1-乙酰乙烯基（1'R，5'S，7'R）-3'-乙基-2'-oxo-3'-aza-6'，8的Diels-Alder加成反应′-二氧杂双环[3.2.1]辛烷-7′-羧酸盐（1-乙酰基乙烯基RADO（Et））变成1-（二甲氧基甲基）-2,3,5,6-四亚甲基-7-氧杂环[2.2.1]庚烷区域，立体和非对映选择性，得到一加合物，将其转变为（R）-（-）-4-demethoxy-7-deoxydaunomycinone。

  DOI：

  10.1016/s0040-4039(00)77479-x

文献信息

• Asymmetric Synthesis and DNA Intercalation of (−)-6-[[(Aminoalkyl)oxy]methyl]-4-demethoxy-6,7- dideoxydaunomycinones¹^,
  作者：Zoltán Dienes、Pierre Vogel

  DOI：10.1021/jo960606z

  日期：1996.1.1

  The BP3 . Et(2)O-promoted Diels-Alder addition of 1-acetylvinyl RADO(Et)-ate (RADO(Et)-ate = 3-ethyl-2-oxo-6,8-dioxa-3-azabicylo[3.2.1]octane-7-exo-carboxylate) to 1-(dimethosymethyl)-2,3,5,6-tetramethylidene-7-oxabicyclo[2.2.1]heptane led to one major monoadduct that added to 1,2-didehydrobenzene and was converted into (-)-4-demethoxy-7-deoxydaunomycinone and (2R)-12-acetoxy-2-acetyl-5-(bromomethyl)-1,2,3,4-tetrahydronaphthacen-2-yl RADO(Et)-ate. The latter compound was used to construct (8R)-8-acetyl-6,8-dihydroxy-11-[[(3'-[(aminopropyl)oxy]-, -4'-[(aminobutyl)oxy], and -5'-[(aminopenty)oxy]methyl]-7,8,9,10-tetrahydronaphthacene-5,12-dione hydrochloride (-)-8, (-)-9, (-)-10, respectively, as well as (8R)-8-acetyl-6,8-dihydroxy-11-[[[2'-[(3 ''-aminopropyl)amino]ethyl]oxy]-((-)-11) and -[[[3'-[(3 ''-aminopropyl)amino]propyl]oxy]methyl]7,8,9,10--tetrahydronaphthacene-5,12-dione hydrochloride ((-)-12). (8R)-8-Acetyl-6,8-dihydroxy-11-[[(alpha-L-diaunosaminyl)oxy]methyl]-7,8,9,10-tetrahydronaphthacene-5,12-dione hydrachloride ((-)-13), a mimic of idarubicin, was also prepared. Absorbance and fluorescence titration experiments showed (-)-8, (-)-9, and (-)-10 to intercalate calf thymus DNA whereas (-)-11, (-)-12, and (-)-13 did not. The best intercalator was (-)-9 (K-b = (1.1 +/- 0.1) x 10(5) M(-1)) with the [(4'-aminobutyl)oxy]-methyl chain. Inhibition of topoisomerase II-induced DNA strand religation wats observed for (-)-8 at a concentration of 50 mu M.
• Enantioselective synthesis of (R)-(−)-2-acetyl-2,5,12-trihydro-1,2,3,4-tetrahydro-6,11-naphthacenequinone via diastereoselective diels-alder cycloaddition
  作者：Zoltán Dienes、Thomas Antonsson、Pierre Vogel

  DOI：10.1016/s0040-4039(00)77479-x

  日期：1993.2

  The BF3·Et2O-promoted Diels-Alder addition of 1-acetylvinyl (1′R,5′S,7′R)-3′-ethyl-2′-oxo-3′-aza-6′,8′-dioxabicylo[3.2.1]octane-7′-carboxylate (1-acetylvinylRADO(Et)) to 1-(dimethoxymethyl)-2,3,5,6-tetramethylidene-7-oxabicyclo[2.2.1] heptane was highly regio-, stereo and diastereoselective giving a monoadduct that was converted into (R)-(−)-4-demethoxy-7-deoxydaunomycinone.

  BF 3 ·Et 2 O促进的1-乙酰乙烯基（1'R，5'S，7'R）-3'-乙基-2'-oxo-3'-aza-6'，8的Diels-Alder加成反应′-二氧杂双环[3.2.1]辛烷-7′-羧酸盐（1-乙酰基乙烯基RADO（Et））变成1-（二甲氧基甲基）-2,3,5,6-四亚甲基-7-氧杂环[2.2.1]庚烷区域，立体和非对映选择性，得到一加合物，将其转变为（R）-（-）-4-demethoxy-7-deoxydaunomycinone。