1,5-dimethyl-7-oxabicyclo<2.2.1>hept-5-en-2-one

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,5-dimethyl-7-oxabicyclo<2.2.1>hept-5-en-2-one
• 英文别名: (1SR,4SR)-1,5-Dimethyl-7-oxabicyclo<2.2.1>hept-5-en-2-one；1,5-dimethyl-7-oxabornenone；(1S,4S)-1,5-dimethyl-7-oxabicyclo[2.2.1]hept-5-en-2-one
• 化学式: C₈H₁₀O₂
• 分子量: 138.166
• InChiKey: FGXHAOVWQHWGCB-XPUUQOCRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,5-dimethyl-7-oxabicyclo<2.2.1>hept-5-en-2-one 在 sodium perborate 、 Montmorillonite 、 dimethyl sulfide borane 、 四丁基碘化铵 、 sodium hydride 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 4.0h， 生成 (+)-(1S,4S,5S,6S)-6-exo-(Benzyloxy)-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
• 作为产物：
  描述：

  2,4-二甲基呋喃 在 聚合甲醛 、 sodium methylate 、 zinc(II) iodide 作用下， 反应 26.5h， 生成 1,5-dimethyl-7-oxabicyclo<2.2.1>hept-5-en-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

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
• Synthesis of Polypropionate Fragments Containing Tertiary-Alcohol Moieties. Cross-aldolisations with lithium enolates of 7-oxabicyclo[2.2.1]heptan-2-one derivatives
  作者：Philippe Kernen、Pierre Vogel

  DOI：10.1002/hlca.19950780205

  日期：1995.3.22

  into (−)-(3R,4R,5R,6S)-3,4:5,7-bis(isopropylidenedioxy)-4,6-dimethylheptan-2-one ((−)-22), and into (+)-(2R,3R,4R,5S,6S)-3,4:5,6-bis(isopropylidenedioxy)-2,4-dimethylheptanal ((+)-34). Condensation of ((+)-34 with the lithium enolate of (−)-(1R,4R,5S,6R)-6-exo-[(tert-butyl)dimethylsilyloxy]-1,5-endo-dimethyl-7-oxabicyclo[2.2.1] heptan-2-one ((−)-38; derived from (+)-1) gave a 3:2 mixture of aldols (+)-39

  的狄尔斯-阿德耳2,4-二甲基呋喃的加成物1-氰基乙烯基（1' - [R）-camphanate（（+） - （1 - [R，2小号，4 - [R）-2-外型-氰基-1,5-二甲基7-氧杂二环[2.2.1]庚-5-烯-2-内型-基（1' - [R）-camphanate（（+） - 1））转化为（+） - 2,7-二脱氧-2,4- -di- C-甲基-L-甘油-（（+）- 6）和-D-甘油-L- altro-庚酮-1,4-内酯（（+）- 7），变成（-）-（3 [R，4 - [R，5 - [R，6小号）-3,4：5,7-双（异丙基二烯二氧基）-4,6-二甲基庚-2--2-（（-）- 22），并成（+）-（2 R，3 R，4 R，5 S，6 S）-3,4：5,6-双（异丙基二烯二氧基）-2,4-二甲基庚醛（（+）- 34）。（（+）- 34与（-）-（1 R，4 R，5 S，6 R）-6- exo
• Base-Induced Bridge Cleavage of 1,5-Dimethyl-7-oxabicyclo[2.2.1]hept-5-ene Derivatives:  A Short Synthesis of an Advanced Intermediate for the A and C Ring Subunits of Taxol
  作者：Odón Arjona、MLuisa León、Joaquín Plumet

  DOI：10.1021/jo9809534

  日期：1999.1.1
• Base-induced bridge cleavage of 1,5-dimethyl-7-oxabicyclo-[2.2.1]hept-5-ene systems
  作者：Odón Arjona、Susana Conde、Joaquín Plumet、Alma Viso

  DOI：10.1016/0040-4039(95)01167-g

  日期：1995.8

  Treatment of 1,5-dimethyl-7-oxabicyclo[2.2.1]hept-5-enes 2 c-e with LDA produces good yields of hydroxy dienes 3 c-e through a novel and efficient bridge cleavage process; these dienes may undergo selective epoxidation to yield highly functionalized vinyl oxiranes such as 4.
• A New Stereoselective and Convergent Approach to the Synthesis of Long-Chain Polypropionate Fragments
  作者：Anne-Francoise Sevin、Pierre Vogel

  DOI：10.1021/jo00099a020

  日期：1994.10

  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.