(3aR*,8aR*)-2(R*)-<(Benzoyloxy)methyl>-5-oxotetrahydrofuro<3,2-b>oxepane

• 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: (3aR*,8aR*)-2(R*)-<(Benzoyloxy)methyl>-5-oxotetrahydrofuro<3,2-b>oxepane
• 英文别名: [(2R,3aR,8aR)-5-oxo-3,3a,6,7,8,8a-hexahydro-2H-furo[3,2-b]oxepin-2-yl]methyl benzoate
• 化学式: C₁₆H₁₈O₅
• 分子量: 290.316
• InChiKey: KASFDCSIVMCIEW-MGPQQGTHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (3aR*,8aR*)-2(R*)-<(Benzoyloxy)methyl>-5-oxotetrahydrofuro<3,2-b>oxepane 在 吡啶 、 臭氧 、 lithium hexamethyldisilazane 作用下， 反应 1.33h， 生成 (3aR*,8aR*)-2(R*)-<(Benzoyloxy)methyl>-5-oxo-3a,5,8,8a-(tetrahydro)tetrahydrofuro<3,2-b>oxepin
  参考文献：
  名称：

  General approach to halogenated tetrahydrofuran natural products from red algae of the genus Laurencia. Total synthesis of (.+-.)-kumausallene and (.+-.)-1-epi-kumausallene

  摘要：

  An efficient, stereocontrolled entry to the dioxabicyclo[3.3.0]octane ring system of (+/-)-kumausallene has been developed. This synthesis builds upon our general strategy for preparing C-15 halogenated tetrahydrofuranoid marine lipids using the ring-enlarging tetrahydrofuran annulation of cyclic, allylic diols as the central step. The key intermediate, hydrobenzofuranone 8, is available with complete stereocontrol from the Lewis acid-catalyzed condensation of 1-vinylcyclopentanediol (4) and alpha-(benzoyloxy)acetaldehyde(Scheme II). Elaboration of 8 into the bicyclic ring system of 13 requires only four steps and proceeds with excellent stereocontrol in 41% overall yield. The total synthesis of (+/-)-kumausallene from 8 is accomplished in 17 steps and 2% overall yield. As a corollary, the total synthesis of (+/-)-1-epi-kumausallene confirms the stereochemical assignment for the bromoallene moiety of the natural product.

  DOI：

  10.1021/jo00061a021
• 作为产物：
  描述：

  (2R^*,3aR^*,7aR^*)-hexahydro-2-<(benzoyloxy)methyl>-4(2H)-benzofuranone 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 72.0h， 以70%的产率得到(3aR*,8aR*)-2(R*)-<(Benzoyloxy)methyl>-5-oxotetrahydrofuro<3,2-b>oxepane
  参考文献：
  名称：

  General approach to halogenated tetrahydrofuran natural products from red algae of the genus Laurencia. Total synthesis of (.+-.)-kumausallene and (.+-.)-1-epi-kumausallene

  摘要：

  An efficient, stereocontrolled entry to the dioxabicyclo[3.3.0]octane ring system of (+/-)-kumausallene has been developed. This synthesis builds upon our general strategy for preparing C-15 halogenated tetrahydrofuranoid marine lipids using the ring-enlarging tetrahydrofuran annulation of cyclic, allylic diols as the central step. The key intermediate, hydrobenzofuranone 8, is available with complete stereocontrol from the Lewis acid-catalyzed condensation of 1-vinylcyclopentanediol (4) and alpha-(benzoyloxy)acetaldehyde(Scheme II). Elaboration of 8 into the bicyclic ring system of 13 requires only four steps and proceeds with excellent stereocontrol in 41% overall yield. The total synthesis of (+/-)-kumausallene from 8 is accomplished in 17 steps and 2% overall yield. As a corollary, the total synthesis of (+/-)-1-epi-kumausallene confirms the stereochemical assignment for the bromoallene moiety of the natural product.

  DOI：

  10.1021/jo00061a021

文献信息

• General approach to halogenated tetrahydrofuran natural products from red algae of the genus Laurencia. Total synthesis of (.+-.)-kumausallene and (.+-.)-1-epi-kumausallene
  作者：Timothy A. Grese、Kira D. Hutchinson、Larry E. Overman

  DOI：10.1021/jo00061a021

  日期：1993.4

  An efficient, stereocontrolled entry to the dioxabicyclo[3.3.0]octane ring system of (+/-)-kumausallene has been developed. This synthesis builds upon our general strategy for preparing C-15 halogenated tetrahydrofuranoid marine lipids using the ring-enlarging tetrahydrofuran annulation of cyclic, allylic diols as the central step. The key intermediate, hydrobenzofuranone 8, is available with complete stereocontrol from the Lewis acid-catalyzed condensation of 1-vinylcyclopentanediol (4) and alpha-(benzoyloxy)acetaldehyde(Scheme II). Elaboration of 8 into the bicyclic ring system of 13 requires only four steps and proceeds with excellent stereocontrol in 41% overall yield. The total synthesis of (+/-)-kumausallene from 8 is accomplished in 17 steps and 2% overall yield. As a corollary, the total synthesis of (+/-)-1-epi-kumausallene confirms the stereochemical assignment for the bromoallene moiety of the natural product.