(+/-)-(1RS,2SR,3SR,4RS)-3-endo-methoxy-5-oxo-7-oxabicyclo<2.2.1>hept-2-exo-yl acetate | 111197-03-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: (+/-)-(1RS,2SR,3SR,4RS)-3-endo-methoxy-5-oxo-7-oxabicyclo<2.2.1>hept-2-exo-yl acetate
• 英文别名: (1RS,2RS,3SR,4RS)-3-endo-methoxy-5-oxo-7-oxabicyclo<2.2.1>hept-2-exo-yl acetate
• CAS: 111197-03-6；115185-26-7
• 化学式: C₉H₁₂O₅
• 分子量: 200.191
• InChiKey: KLBOWWKHQRNYKN-KZVJFYERSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.33
• 重原子数：
  14.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  61.83
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为产物：
  描述：

  (1RS,4RS,5RS,6RS)-5-exo-benzeneselenyl-6-endo-methoxy-7-oxabicyclo<2.2.1>heptan-2-one 在 偶氮二异丁腈 、 三正丁基氢锡 、 sodium acetate 、 间氯过氧苯甲酸 作用下， 以 苯 为溶剂， 反应 2.08h， 生成 (+/-)-(1RS,2SR,3SR,4RS)-3-endo-methoxy-5-oxo-7-oxabicyclo<2.2.1>hept-2-exo-yl acetate
  参考文献：
  名称：

  Reductive Oxa Ring Opening of 7-Oxabicyclo[2.2.1]heptan-2-ones. Synthesis of C-.alpha.-Galactosides of Carbapentopyranoses

  摘要：

  Photoinduced electron transfer from Et(3)N to 7-oxabicyclo[2.2.1]heptan-2-ones can generate the corresponding 3-hydroxycyclohexanone derivatives. The method has been applied to the synthesis of C-alpha-D-galactopyranosides of carbapentopyranoses. Radical alpha-D-galactosidation of (+/-)-(1RS,4RS,5RS, 6RS)-6-endo-methoxy-3-methylidene-5-exo-(phenylseleno)-7-oxabicyclo[2.2.l]hept-2-one ((+)-51) followed by seleno-Pummerer rearrangement and reduction with Bu(3)SnH gave (+)- (1R,2S,3S,4R,6R)-((+)-58) and (+)-(1S,2R,3R,4S,6S)-3-endo-methoxy-5-oxo-6-endo-[(2',3',4',6'-tetra-0-acetyl-alpha-D-galactopyranosyl)methyl]-7-oxabicyclo[2.2.1]hept-2-endo-yl acetate ((+)-59), which were separated by column chromatography. Irradiation (254 nn) in the presence of Et(3)N gave (+)-(1S,2R,3R,6R)-((+)-60) and (+)-(1R,2S,3S,6S)-2-hydroxy-6-methoxy-4-oxo-3-[(2',3',4',6'-tetra-0-acetyl-alpha-D-galactopyranosyl)methyl]cyclohexyl acetate (+)-61, respectively. NaBH4 reduction and acetylation provided (+)-(1S,2S,3R,4R,5R)-((+)-62) and (+)-(1R,2R,3S,4S,5S)-5-methoxy-2-[(2',3',4',6'-tetra-0-acetyl-alpha-D-galactopyranosyl)methyl]cyclohexa-1,3,4-triyl triacetate ((+)-64).

  DOI：

  10.1021/jo00131a007

文献信息

• Facile migration of acyl groups in Wagner-Meerwein transpositions. Acid-catalyzed rearrangements of 5,6-exo-epoxy-7-oxa-2-bicyclo[2.2.1]heptanone and derivatives.
  作者：Claude Le Drian、Pierre Vogel

  DOI：10.1016/s0040-4039(01)81032-7

  日期：1987.1

  The acid promoted rearrangements of 5,6-exo-epoxy-7-oxa-2-norbornyl derivatives allowed one to compare the “true” migratory aptitudes of acyl, alkyl and α-substituted alkyl groups in Wagner-Meerwein rearrangements.

  酸促进的5,6- exo -epoxy-7-oxa-2-norbornyl衍生物的重排使得人们能够比较Wagner-Meerwein重排中的酰基，烷基和α-取代的烷基的“真”迁移能力。
• Acid-Catalyzed Rearrangements of 5,6-exo-Epoxy-7-oxabicyclo[2.2.1]hept-2-yl Derivatives. Migratory Aptitudes of Acylvs. Alkyl Groups inWagner-Meerwein Transpositions
  作者：Claude Le Drian、Pierre Vogel

  DOI：10.1002/hlca.19870700706

  日期：1987.11.4

  (6a, b) gave products derived from the epoxide-ring opening and a 1,2-shift of the unsubstituted alkyl group (σ bond C(3)–C(4)). In contrast, under similar conditions, the 5,6-exo-epoxy-7-oxabicyclo[2.2.1]heptan-2-one (6c) gave 5-oxo-2-oxabicyclo[2.2.1]heptane-3,7-diyl diacetates 20 and 21 arising from the 1,2-shift of the acyl group. Acid treatment of 5,6-exo-epoxy-2,2-dimethoxy-7-oxabicyclo[2.2.1]heptane

  在HSO的存在3 F / AC 2 ö在CH 2 CL 2，2-外-和2-内型-氰基-5,6-外-环氧-7-氧杂双环〔2.2.1〕庚-2-基乙酸酯（6a，b）给出了从环氧化物的开环和未取代的烷基（σ键C（3）–C（4））的1,2-移位衍生的产物。相比之下，在相似的条件下，5,6- exo -epoxy-7-oxabicyclo [2.2.1]庚-2--2-（6c）得到5-oxo-2-oxabicyclo [2.2.1]庚烷-3,7 -由酰基的1，2-移位产生的-二乙酸二乙酯20和21。5,6- exo的酸处理-环氧-2,2-二甲氧基-7-氧杂双环[2.2.1]庚烷（6d）和5,6-外-环氧-2,2-双（苄氧基）-7-氧杂双环[2.2.1]庚烷（图6e），得到从环氧化物的开环所产生的次要产物和σ键C的1,2-移位（3）-C（4）和主要产品（25，29从一个甲氧基的1,3-移位而引起）和分别为苄氧基。在相似的条件下，5