(+)-(1S,4S,5S,6S)-6-exo-Hydroxy-2,2-dimethoxy-1,5-endo-dimethyl-7-oxabicyclo<2.2.1>heptane | 161317-35-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (+)-(1S,4S,5S,6S)-6-exo-Hydroxy-2,2-dimethoxy-1,5-endo-dimethyl-7-oxabicyclo<2.2.1>heptane
• 英文别名: (1S,2S,3S,4S)-6,6-dimethoxy-1,3-dimethyl-7-oxabicyclo[2.2.1]heptan-2-ol
• CAS: 161317-35-7
• 化学式: C₁₀H₁₈O₄
• 分子量: 202.251
• InChiKey: QWHNZBCMVGCILN-XGEHTFHBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  47.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (+)-(1S,4S,5S,6S)-6-exo-Hydroxy-2,2-dimethoxy-1,5-endo-dimethyl-7-oxabicyclo<2.2.1>heptane 在 Nafion NR₅₀ 、 四丁基碘化铵 、 sodium hydride 作用下， 以 四氢呋喃 、 水 、 丙酮 为溶剂， 反应 4.0h， 生成 (1SR,4SR,5SR,6SR)-6-exo-(Benzyloxy)-1,5-endo-dimethyl-7-oxabicyclo<2.2.1>heptane-2-one
  参考文献：
  名称：

  A New Stereoselective and Convergent Approach to the Synthesis of Long-Chain Polypropionate Fragments

  摘要：

  Optically pure Diels-Alder adducts of 2,4-dimethylfuran and 1-cyanovinyl (1'R)- or (1'S)-camphanate are obtained readily. These 1,5-dimethyl-7-oxabicyclo[2.2.1]hept-5-en-1-yl derivatives can be converted with high stereoselectivity into polypropionate fragments such as (-)-(2R,3R,4R,5S)-5-(benzyloxy)-3-(isopropyloxy)-2,4-dimethylhept-6-enal ((-)-16) or (-)-(2R,2'S,3'S,4'S,5'S)-2-[4-(benzyloxy)tetrahydro-3,5-dimethyl-5-methoxyfur-2-yl]propanal ((-)-20). The latter underwent stereoselective cross-aldolization with the lithium enolate of (+)-(1S,4S,5S,6S)-6-exo-(benzyloxy)-1,5-endo-dimethyl-7-oxabicyclo[2.2.1]heptan-2-one ((+)-9) giving an aldol ((-)-23); like mode of aldolization) that can be converted into a polypropionate fragment containing nine contiguous stereogenic centers.

  DOI：

  10.1021/jo00099a020
• 作为产物：
  描述：

  (1S,4R)-4,7,7-Trimethyl-3-oxo-2-oxa-bicyclo[2.2.1]heptane-1-carboxylic acid (1S,2R,4S)-2-cyano-1,5-dimethyl-7-oxa-bicyclo[2.2.1]hept-5-en-2-yl ester 在 sodium perborate 、 氢氧化钾 、 Montmorillonite 、 聚合甲醛 、 dimethyl sulfide borane 作用下， 以 正己烷 为溶剂， 反应 6.5h， 生成 (+)-(1S,4S,5S,6S)-6-exo-Hydroxy-2,2-dimethoxy-1,5-endo-dimethyl-7-oxabicyclo<2.2.1>heptane
  参考文献：
  名称：

  A New Stereoselective and Convergent Approach to the Synthesis of Long-Chain Polypropionate Fragments

  摘要：

  Optically pure Diels-Alder adducts of 2,4-dimethylfuran and 1-cyanovinyl (1'R)- or (1'S)-camphanate are obtained readily. These 1,5-dimethyl-7-oxabicyclo[2.2.1]hept-5-en-1-yl derivatives can be converted with high stereoselectivity into polypropionate fragments such as (-)-(2R,3R,4R,5S)-5-(benzyloxy)-3-(isopropyloxy)-2,4-dimethylhept-6-enal ((-)-16) or (-)-(2R,2'S,3'S,4'S,5'S)-2-[4-(benzyloxy)tetrahydro-3,5-dimethyl-5-methoxyfur-2-yl]propanal ((-)-20). The latter underwent stereoselective cross-aldolization with the lithium enolate of (+)-(1S,4S,5S,6S)-6-exo-(benzyloxy)-1,5-endo-dimethyl-7-oxabicyclo[2.2.1]heptan-2-one ((+)-9) giving an aldol ((-)-23); like mode of aldolization) that can be converted into a polypropionate fragment containing nine contiguous stereogenic centers.

  DOI：

  10.1021/jo00099a020