(1SR,4SR,5SR,6SR)-6-exo-(Benzyloxy)-1,5-endo-dimethyl-7-oxabicyclo<2.2.1>heptane-2-one

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (1SR,4SR,5SR,6SR)-6-exo-(Benzyloxy)-1,5-endo-dimethyl-7-oxabicyclo<2.2.1>heptane-2-one
• 英文别名: (1S,4S,5R,6S)-1,5-dimethyl-6-phenylmethoxy-7-oxabicyclo[2.2.1]heptan-2-one
• 化学式: C₁₅H₁₈O₃
• 分子量: 246.306
• InChiKey: TXETZOVYZPOXAC-UEEZHKSASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (1SR,4SR,5SR,6SR)-6-exo-(Benzyloxy)-1,5-endo-dimethyl-7-oxabicyclo<2.2.1>heptane-2-one 在 正丁基锂 、 碳酸氢钠 、 间氯过氧苯甲酸 、 六甲基二硅氮烷 作用下， 以 二氯甲烷 为溶剂， 反应 2.5h， 生成 (+)-(1S,4R,5S,6S,7S)-7-exo-(Benzyloxy)-1,4-exo,6-endo-trimethyl-2,8-dioxabicyclo<3.2.1>octan-3-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：

  2,4-二甲基呋喃 在 sodium perborate 、 氢氧化钾 、 Montmorillonite 、 聚合甲醛 、 Nafion NR₅₀ 、 dimethyl sulfide borane 、 四丁基碘化铵 、 sodium hydride 、 zinc(II) iodide 作用下， 以 四氢呋喃 、 正己烷 、 水 、 丙酮 为溶剂， 反应 34.5h， 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

文献信息

• 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
• Tandem Oxyallylations and Retro-ene Eliminations. One Pot Stereoselective Synthesis of Polypropionate Fragments with Three Contiguous Stereogenic Centers and One (E)-Alkene Unit.
  作者：Jean-Michel Roulet、Geneviève Puhr、Pierre Vogel

  DOI：10.1016/s0040-4039(97)01398-1

  日期：1997.9

  Mixtures of (EE)-2-methyl-1-silyloxypenta-1,3-dienes, enoxysilanes, SO2 and (t-Bu)Me2SiOTf (catalyst) generate (Z)-5-alkyl-1,3-dimethyl-6-oxo-4-silyloxyalk-2-enesulfinic acids that undergo stereoselective retro-ene eliminations of SO2 with the formation of corresponding (E)-3-hydroxy-2-alkyl-4-methylalk-5-en-1-ones with 2,3-syn and 3,4-anti diastereoselectivity. (C) 1997 Elsevier Science Ltd.