(2R,3S,4aR,8S,9aS)-3-Hydroxy-2,8-dimethyl-2-propyl-octahydro-1,5-dioxa-benzocyclohepten-6-one | 221372-90-3

• 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: (2R,3S,4aR,8S,9aS)-3-Hydroxy-2,8-dimethyl-2-propyl-octahydro-1,5-dioxa-benzocyclohepten-6-one
• CAS: 221372-90-3
• 化学式: C₁₄H₂₄O₄
• 分子量: 256.342
• InChiKey: KEJLGYWFCKWVOM-XJBAAKRRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.04
• 重原子数：
  18.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  55.76
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (2R,3S,4aR,8S,9aS)-3-Hydroxy-2,8-dimethyl-2-propyl-octahydro-1,5-dioxa-benzocyclohepten-6-one 在 四(三苯基膦)钯 、 三丁基乙烯基锡 、 sodium hexamethyldisilazane 、 N,N-二异丙基乙胺 、 lithium chloride 作用下， 以 四氢呋喃 、 乙二醇二甲醚 、 二氯甲烷 为溶剂， 反应 26.25h， 生成 (2R,3S,4aR,8S,9aS)-3-(2-Methoxy-ethoxymethoxy)-2,8-dimethyl-2-propyl-6-vinyl-3,4,4a,8,9,9a-hexahydro-2H-1,5-dioxa-benzocycloheptene
  参考文献：
  名称：

  Total Synthesis of Brevetoxin A: Part 1: First Generation Strategy and Construction of BCD Ring System

  摘要：

  Discussed herein is our first generation strategy for the total synthesis of brevetoxin A. This approach relies upon dissection of the molecule at the nine-membered ring site (ring E), A Wittig coupling of requisite polycyclic fragments 3 and 4 followed by hydroxy dithioketal cyclization was expected to furnish the polycyclic framework of brevetoxin A (1). Intermediate 8 was anticipated to be a valid synthetic precursor to phosphonium salt 3, and its synthesis was accomplished by a bis(lactonization)/thionolactone formation/functionalization sequence. In order to test our synthetic strategy, the synthesis of an advanced model system (36) was attempted. Aldehyde 38 and phosphonium salt 37 were successfully synthesized and coupled through a:Wittig reaction. Unfortunately, the planned hydroxy dithioketal cyclization to form the crucial nonacene (ring E) did not proceed as anticipated and this synthetic approach was discontinued.

  DOI：

  10.1002/(sici)1521-3765(19990201)5:2<599::aid-chem599>3.0.co;2-n
• 作为产物：
  描述：

  3-deoxy-1,2;5,6-di-O-isopropylidene-α-D-glucofuranoside 在 palladium dihydroxide 、 palladium on activated charcoal 咪唑 、 titanium(IV) isopropylate 、 4-二甲氨基吡啶 、 lithium hydroxide 、 草酰氯 、 2SPh2 、 D(+)-10-樟脑磺酸 、 水 、 氢气 、 碘 、 四丁基碘化铵 、 sodium hydride 、 碳酸氢钠 、 氟化氢吡啶 、 二甲基亚砜 、 高碘酸 、 三乙胺 、 zinc(II) chloride 、 zinc dibromide 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 二氯甲烷 、 水 、 乙酸乙酯 、 丙酮 、 甲苯 、 paraffin 、 苯 为溶剂， 反应 62.75h， 生成 (2R,3S,4aR,8S,9aS)-3-Hydroxy-2,8-dimethyl-2-propyl-octahydro-1,5-dioxa-benzocyclohepten-6-one
  参考文献：
  名称：

  Total Synthesis of Brevetoxin A: Part 1: First Generation Strategy and Construction of BCD Ring System

  摘要：

  Discussed herein is our first generation strategy for the total synthesis of brevetoxin A. This approach relies upon dissection of the molecule at the nine-membered ring site (ring E), A Wittig coupling of requisite polycyclic fragments 3 and 4 followed by hydroxy dithioketal cyclization was expected to furnish the polycyclic framework of brevetoxin A (1). Intermediate 8 was anticipated to be a valid synthetic precursor to phosphonium salt 3, and its synthesis was accomplished by a bis(lactonization)/thionolactone formation/functionalization sequence. In order to test our synthetic strategy, the synthesis of an advanced model system (36) was attempted. Aldehyde 38 and phosphonium salt 37 were successfully synthesized and coupled through a:Wittig reaction. Unfortunately, the planned hydroxy dithioketal cyclization to form the crucial nonacene (ring E) did not proceed as anticipated and this synthetic approach was discontinued.

  DOI：

  10.1002/(sici)1521-3765(19990201)5:2<599::aid-chem599>3.0.co;2-n