4-methoxy-13-iodo-2,11-dioxatricyclo[13.2.2.1^3,7]eicosa-1(18),3,5,7(20),1(19),16-hexaen-10-one | 157035-22-8

• 分子结构分类: 有机化合物 - 木脂素、新木脂素和相关化合物 - 木脂素内酯
• 英文名称: 4-methoxy-13-iodo-2,11-dioxatricyclo[13.2.2.1^3,7]eicosa-1(18),3,5,7(20),1(19),16-hexaen-10-one
• 英文别名: 13-Iodo-4-methoxy-2,11-dioxatricyclo[13.2.2.13,7]icosa-1(17),3,5,7(20),15,18-hexaen-10-one
• CAS: 157035-22-8
• 化学式: C₁₉H₁₉IO₄
• 分子量: 438.262
• InChiKey: QXYZGPIHWFQASX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  24
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4-methoxy-13-iodo-2,11-dioxatricyclo[13.2.2.1^3,7]eicosa-1(18),3,5,7(20),1(19),16-hexaen-10-one 在 potassium fluoride 、 三碘化硼 、 N,N-二甲基苯胺 作用下， 以 二甲基亚砜 、 苯 为溶剂， 反应 4.0h， 生成 combretastatin D-2
  参考文献：
  名称：

  Total Synthesis of Combretastatins D

  摘要：

  The 15-membered caffrane ring of the natural product group of combretastatins D is synthesized in high yield with suitably functionalized saturated seco acids. The key step is a Mitsunobu-type macrolactonization. A common synthon is used for the construction of both combretastatins. The synthesis of combretastatin D-2 is completed by the use of Sammuelson's dehydroxylation protocol, The asymmetric epoxide of combretastatin D-1 is constructed in two separate operations: one asymmetric center is fixed at an early stage of the synthetic route by Sharpless AD of a trans-styrene derivative, inducing the intramolecular formation of the asymmetric epoxide at the final stages. The synthesis of the title compounds is accomplished in high overall yields (37% for D-1 and 41% for D-2, 9 steps in both cases). X-ray crystallographic analysis of the (S)-(+) acetylmandelic ester of (-)-combretastatin D-1 verified its revised structure.

  DOI：

  10.1002/(sici)1521-3765(199801)4:1<33::aid-chem33>3.0.co;2-8
• 作为产物：
  描述：

  3-(4-溴苯基)丙-2-烯-1-醇 在 咪唑 、 lithium hydroxide 、 copper(I) bromide dimethylsulfide complex 、 四丁基氟化铵 、 碘 、 四丁基碘化铵 、 sodium hydride 、 二异丁基氢化铝 、 potassium carbonate 、 间氯过氧苯甲酸 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 吡啶 、 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 、 苯 为溶剂， 反应 34.67h， 生成 4-methoxy-13-iodo-2,11-dioxatricyclo[13.2.2.1^3,7]eicosa-1(18),3,5,7(20),1(19),16-hexaen-10-one
  参考文献：
  名称：

  Total Synthesis of Combretastatins D

  摘要：

  The 15-membered caffrane ring of the natural product group of combretastatins D is synthesized in high yield with suitably functionalized saturated seco acids. The key step is a Mitsunobu-type macrolactonization. A common synthon is used for the construction of both combretastatins. The synthesis of combretastatin D-2 is completed by the use of Sammuelson's dehydroxylation protocol, The asymmetric epoxide of combretastatin D-1 is constructed in two separate operations: one asymmetric center is fixed at an early stage of the synthetic route by Sharpless AD of a trans-styrene derivative, inducing the intramolecular formation of the asymmetric epoxide at the final stages. The synthesis of the title compounds is accomplished in high overall yields (37% for D-1 and 41% for D-2, 9 steps in both cases). X-ray crystallographic analysis of the (S)-(+) acetylmandelic ester of (-)-combretastatin D-1 verified its revised structure.

  DOI：

  10.1002/(sici)1521-3765(199801)4:1<33::aid-chem33>3.0.co;2-8

文献信息

• Synthesis of combretastatin D-2. An efficient route to caffrane macrolactones
  作者：Elias A. Couladouros、Ioanna C. Soufli

  DOI：10.1016/s0040-4039(00)73369-7

  日期：1994.6

  Combretastatin D-2, (1), was synthesized via a 10 step sequence. Macrolactonization was performed on saturated substrate 12 in high yield and the double bond was established via dehalogenation of intermediate 15.