(1S,4S)-6,6-Dimethoxy-1,3-dimethyl-7-oxa-bicyclo[2.2.1]hept-2-ene | 161317-34-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1S,4S)-6,6-Dimethoxy-1,3-dimethyl-7-oxa-bicyclo[2.2.1]hept-2-ene
• CAS: 161317-34-6
• 化学式: C₁₀H₁₆O₃
• 分子量: 184.235
• InChiKey: HMHGNLCVRSWMBE-IUCAKERBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.48
• 重原子数：
  13.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  27.69
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  (1S,4S)-6,6-Dimethoxy-1,3-dimethyl-7-oxa-bicyclo[2.2.1]hept-2-ene 在 sodium perborate 、 Nafion NR₅₀ 、 dimethyl sulfide borane 、 四丁基碘化铵 、 sodium hydride 作用下， 以 四氢呋喃 、 水 、 丙酮 为溶剂， 反应 6.0h， 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 氢氧化钾 、 Montmorillonite 、 聚合甲醛 作用下， 以 正己烷 为溶剂， 反应 4.5h， 生成 (1S,4S)-6,6-Dimethoxy-1,3-dimethyl-7-oxa-bicyclo[2.2.1]hept-2-ene
  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

文献信息

• Stereoselective Synthesis of 2,4,6-Trimethylcyclohex-4-ene-1,3-diol Derivatives and of polypropionate fragments with four contiguous stereogenic centers
  作者：Maciej Bialecki、Pierre Vogel

  DOI：10.1002/hlca.19950780206

  日期：1995.3.22

  ether (36). Addition of LiAlH4 to the latter led to the 3-O-benzyl derivatives 28 and 37 of (1RS,2SR,3SR,6SR)- and (1RS,2SR,3RS,6SR)-5-(4-chlorophenylsulfonyl)-2,4,6-trimethylcyclohex-4-ene-1,3-diol, respectively. Methylenation of 6-exo-(4-chlorophenylthio)-1-methyl-5-methylidene-7-oxabicyclo[2.2.1]heptan-2-one (16), obtained by reaction of (±)-3 with 4-Cl-C6H4SCl and saponification gave, 6-exo-(4-ch

  将2，4-二甲基呋喃和乙酸1-氰基乙烯基酯的狄尔斯-阿尔德加成物（±）-3立体选择性地转化为苄基6-（4-氯苯基磺酰基）-1,3- exo，5-三甲基-7-氧杂双环[2.2]。 1]庚-5-烯-2-外基（26）和-2-内基醚（36）。LiAlH 4在后者中的加入导致了（1 RS，2 SR，3 SR，6 SR）-和（1 RS，2 SR，3 RS，6 SR的3- O-苄基衍生物28和37）-5-（4-氯苯基磺酰基）-2,4,6-三甲基环己-4-烯-1,3-二醇。通过（±）-3与4-Cl反应获得的6- exo-（4-氯苯硫基）-1-甲基-5-亚甲基-7-氧杂环[2.2.1]庚烷-2-酮（16）的亚甲基化-C 6 H 4 SCl并皂化得到6 - exo-（4-氯苯硫基）-1-甲基-3,5-二甲基-7-氧杂双环[2.2.1]庚-2--2-（43），还原其与K-Selectride一起得到6-外-（4