(13R,14R)-13,14-bis[[tert-butyl(dimethyl)silyl]oxy]-4-phenylmethoxy-2,11-dioxatricyclo[13.2.2.13,7]icosa-1(17),3,5,7(20),15,18-hexaen-10-one | 172919-11-8

• 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: (13R,14R)-13,14-bis[[tert-butyl(dimethyl)silyl]oxy]-4-phenylmethoxy-2,11-dioxatricyclo[13.2.2.13,7]icosa-1(17),3,5,7(20),15,18-hexaen-10-one
• CAS: 172919-11-8
• 化学式: C₃₇H₅₂O₆Si₂
• 分子量: 648.987
• InChiKey: DDRSDDSTMDEELP-VLZNPVHKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.0
• 重原子数：
  45
• 可旋转键数：
  9
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.49
• 拓扑面积：
  63.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (13R,14R)-13,14-bis[[tert-butyl(dimethyl)silyl]oxy]-4-phenylmethoxy-2,11-dioxatricyclo[13.2.2.13,7]icosa-1(17),3,5,7(20),15,18-hexaen-10-one 在 palladium on activated charcoal 4-二甲氨基吡啶 、 四丁基氟化铵 、 氢气 、 N,N'-二环己基碳二亚胺 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 二氯甲烷 、 乙酸乙酯 、 N,N-二甲基甲酰胺 为溶剂， 反应 9.67h， 生成 combretastatin D-1-(S)-(O-acetyl) mandelate
  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 吡啶 、 咪唑 、 lithium hydroxide 、 potassium dioxotetrahydroxoosmate(VI) 、 copper(I) bromide dimethylsulfide complex 、 二异丁基氢化铝 、 potassium carbonate 、 氢化奎尼定 1,4-(2,3-二氮杂萘)二醚 、 三苯基膦 、 potassium hexacyanoferrate(III) 、 偶氮二甲酸二乙酯 作用下， 以 水 、 N,N-二甲基甲酰胺 、 甲苯 、 叔丁醇 为溶剂， 反应 35.17h， 生成 (13R,14R)-13,14-bis[[tert-butyl(dimethyl)silyl]oxy]-4-phenylmethoxy-2,11-dioxatricyclo[13.2.2.13,7]icosa-1(17),3,5,7(20),15,18-hexaen-10-one
  参考文献：
  名称：

  天然（-）-combretastatin D-1的全合成。

  摘要：

  Combretastatin D-1（2）是通过12个步骤序列合成的。使用了尖锐的不对称二羟基化反应以引入适当的不对称性。二醇3的区域特异性环脱水得到96％ee的标题化合物。

  DOI：

  10.1016/0040-4039(95)01987-s

文献信息

• Total synthesis of natural (−)-combretastatin D-1.
  作者：Elias A. Couladouros、Ioanna C. Soufli

  DOI：10.1016/0040-4039(95)01987-s

  日期：1995.12

  Combretastatin D-1, (2), was synthesized via a 12 step sequence. Sharpless asymmetric dihydroxylation was used in order to introduce the appropriate asymmetry. Regiospecific cyclodehydration of the diol 3 gave the title compound in 96% ee.

  Combretastatin D-1（2）是通过12个步骤序列合成的。使用了尖锐的不对称二羟基化反应以引入适当的不对称性。二醇3的区域特异性环脱水得到96％ee的标题化合物。
• Total Synthesis of Combretastatins D
  作者：Elias A. Couladouros、Ioanna C. Soufli、Vassilios I. Moutsos、Raj K. Chadha

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

  日期：1998.1

  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.