(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 | 161441-92-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (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
• 英文别名: [(1S,2R,4S)-2-cyano-1,5-dimethyl-7-oxabicyclo[2.2.1]hept-5-en-2-yl] (1S,4R)-4,7,7-trimethyl-3-oxo-2-oxabicyclo[2.2.1]heptane-1-carboxylate
• CAS: 161441-92-5
• 化学式: C₁₉H₂₃NO₅
• 分子量: 345.395
• InChiKey: VERLZFQWGBDKBG-MQSDJCRFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  25
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.74
• 拓扑面积：
  85.6
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  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 吡啶 、 palladium diacetate 、 bis(triphenylphosphine) palladium (Il) acetate 、 copper(I) bromide dimethylsulfide complex 、 二苯基硅烷 、 diethylzinc 、 氧气 、 三氯化铁 、 三苯基膦 、 zinc(II) chloride 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 乙醚 、 氯仿 、 二甲基亚砜 、 1,2-二氯乙烷 为溶剂， 反应 77.25h， 生成 (1S,4R,5S,6S,7S)-6,7-(isopropylidenedioxy)-1,4,6-trimethyl-8-oxabicyclo[3.2.1]octan-2-one
  参考文献：
  名称：

  的总不对称合成开环的9,12- anhydroerythronolide糖苷配基-acids

  摘要：

  2,4-二甲基呋喃的Diels-Alder加成物与1-氰基乙烯基（1 'S）-樟脑酸酯转化为（2 R，3 R，4 S，5 S，6 R，7 R）-3,6-环氧-4,5-异丙基二烯二氧基-2,4,6-三甲基-7-[（叔丁基）-二薄荷基甲硅烷氧基]壬-1-基苯基亚砜（6），其缩合与（3 R，4 S，5 [R，6小号）-7-苄氧基-3,5-异亚丙基二4,6-二甲基庚-2-酮（7引导到部分保护）开环-酸的9,12- anhydroerythronolide糖苷配基（的5）。

  DOI：

  10.1016/s0040-4039(98)00691-1
• 作为产物：
  描述：

  2,4-二甲基呋喃 、 1-(Cyanovinyl) (1'S)-camphanate 在 zinc(II) iodide 作用下， 反应 24.0h， 以61%的产率得到(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
  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

• Total asymmetric synthesis of seco-acids of 9,12-anhydroerythronolide aglycons
  作者：Simon W. Ainge、Pierre Vogel

  DOI：10.1016/s0040-4039(98)00691-1

  日期：1998.6

  sulfoxides (6), the condensation of which with (3R,4S,5R,6S)-7-benzyloxy-3,5-isopropylidenedioxy-4,6-dimethylheptan-2-one (7) led to the partially-protected seco-acid of the 9,12-anhydroerythronolide aglycon (5).

  2,4-二甲基呋喃的Diels-Alder加成物与1-氰基乙烯基（1 'S）-樟脑酸酯转化为（2 R，3 R，4 S，5 S，6 R，7 R）-3,6-环氧-4,5-异丙基二烯二氧基-2,4,6-三甲基-7-[（叔丁基）-二薄荷基甲硅烷氧基]壬-1-基苯基亚砜（6），其缩合与（3 R，4 S，5 [R，6小号）-7-苄氧基-3,5-异亚丙基二4,6-二甲基庚-2-酮（7引导到部分保护）开环-酸的9,12- anhydroerythronolide糖苷配基（的5）。
• 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.