(1R,3E,5S,8E,12E,15S)-5,17-dihydroxy-4,8,12,15-tetramethylbicyclo[13.3.0]octadeca-3,8,12,17-tetraen-16-one | 935263-65-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1R,3E,5S,8E,12E,15S)-5,17-dihydroxy-4,8,12,15-tetramethylbicyclo[13.3.0]octadeca-3,8,12,17-tetraen-16-one
• CAS: 935263-65-3
• 化学式: C₂₂H₃₂O₃
• 分子量: 344.494
• InChiKey: QCHUOVOZTXIBEJ-TVGXMWOXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  25
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  57.5
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (1R,3E,5S,8E,12E,15S)-5,17-dihydroxy-4,8,12,15-tetramethylbicyclo[13.3.0]octadeca-3,8,12,17-tetraen-16-one 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex (S,S)-DACH-phenyl Trost ligand 、 lithium hydroxide 、 sodium tetrahydroborate 、 sodium periodate 、 AD-mix-α 、 二甲基硫 、 甲基磺酰胺 、 四丁基碘化铵 、 caesium carbonate 、 magnesium bromide 作用下， 以 四氢呋喃 、 吡啶 、 甲醇 、 乙二醇二甲醚 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 叔丁醇 为溶剂， 反应 58.17h， 生成 terpestacin
  参考文献：
  名称：

  A Diosphenol-Based Strategy for the Total Synthesis of (−)-Terpestacin

  摘要：

  A novel diosphenol-based strategy has been developed for the enantioselective synthesis of (-)-terpestacin by multiple usage of the alpha-diketone functionality, first in the "Pd AAA-Claisen rearrangement" protocol, and second by the employment of its oxidized form, the ene-1,2-dione, as an excellent Michael acceptor. This synthesis demonstrates that the sequence of O-allylation-Claisen rearrangement provides a chemo- and regioselective enolate allylation, which can be performed asymmetrically with respect to the enolate or allyl fragment or both. In addition, many interesting chemoselectivity issues, including a highly selective RCM and a dihydroxylation, have been addressed. Overall, this synthesis was accomplished in 20 longest linear steps (24 total steps) from the inexpensive and commercially available 3-methyl-1,2-cyclopentanedione.

  DOI：

  10.1021/ja070571s
• 作为产物：
  描述：

  3,7-dimethyl-1-(phenylsulfonyl)-8-hydroxy-2(E),6(E)-octadiene 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 titanium(IV) isopropylate 、 palladium diacetate 吡啶 、 叔丁基过氧化氢 、 六甲基磷酰三胺 、 sodium tetrahydroborate 、 二甲基硫 、 L-(+)-酒石酸二乙酯 、 1,3-双(二苯基膦)丙烷 、 碘 、 三苯基膦 、 magnesium bromide 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 乙醚 、 癸烷 、 二氯甲烷 、 二甲基亚砜 、 乙腈 、 苯 为溶剂， 反应 46.75h， 生成 (1R,3E,5S,8E,12E,15S)-5,17-dihydroxy-4,8,12,15-tetramethylbicyclo[13.3.0]octadeca-3,8,12,17-tetraen-16-one
  参考文献：
  名称：

  A Diosphenol-Based Strategy for the Total Synthesis of (−)-Terpestacin

  摘要：

  A novel diosphenol-based strategy has been developed for the enantioselective synthesis of (-)-terpestacin by multiple usage of the alpha-diketone functionality, first in the "Pd AAA-Claisen rearrangement" protocol, and second by the employment of its oxidized form, the ene-1,2-dione, as an excellent Michael acceptor. This synthesis demonstrates that the sequence of O-allylation-Claisen rearrangement provides a chemo- and regioselective enolate allylation, which can be performed asymmetrically with respect to the enolate or allyl fragment or both. In addition, many interesting chemoselectivity issues, including a highly selective RCM and a dihydroxylation, have been addressed. Overall, this synthesis was accomplished in 20 longest linear steps (24 total steps) from the inexpensive and commercially available 3-methyl-1,2-cyclopentanedione.

  DOI：

  10.1021/ja070571s

文献信息

• Cyclic 1,2-Diketones as Core Building Blocks: A Strategy for the Total Synthesis of (−)-Terpestacin
  作者：Barry M. Trost、Guangbin Dong、Jennifer A. Vance

  DOI：10.1002/chem.200903356

  日期：——

  our work towards the total synthesis of (−)‐terpestacin (1), a sesterterpene originally isolated from fungal strain Arthrinium sp. FA1744. Its promising anti‐HIV and anti‐cancer activity, as well as its novel structure, make terpestacin an attractive synthetic target. A strategy based on the unique reactivity of cyclic 1,2‐diketones (diosphenols) was developed and total synthesis of 1 was achieved in

  我们报告了我们在全合成 (-)-terpestacin ( 1 ) 方面的工作，这是一种最初从真菌菌株Arthrinium sp. 中分离的二萜。FA1744。其有希望的抗 HIV 和抗癌活性以及其新颖的结构使 terpestacin 成为有吸引力的合成靶标。开发了一种基于环状 1,2-二酮（二酚）独特反应性的策略，并全合成了1从市售的 2-羟基-3-甲基-2-环戊烯-1-酮以最长的线性序列分 20 个步骤实现。我们合成的关键特征是“Pd AAA-Claisen”协议（AAA = 不对称烯丙基烷基化）的双重使用，首先在早期阶段生成 C1 四元中心，然后在后期阶段安装侧链。此外，合成了一个相当不寻常的 ene-1,2-dione 部分，并将其用作优秀的迈克尔受体来连接 C15 取代基。已经检查并仔细评估了几种可能的全合成路线。在我们的探索过程中，许多有趣的化学选择性问题已经得到解决，例如高选
• A Diosphenol-Based Strategy for the Total Synthesis of (−)-Terpestacin
  作者：Barry M. Trost、Guangbin Dong、Jennifer A. Vance

  DOI：10.1021/ja070571s

  日期：2007.4.1

  A novel diosphenol-based strategy has been developed for the enantioselective synthesis of (-)-terpestacin by multiple usage of the alpha-diketone functionality, first in the "Pd AAA-Claisen rearrangement" protocol, and second by the employment of its oxidized form, the ene-1,2-dione, as an excellent Michael acceptor. This synthesis demonstrates that the sequence of O-allylation-Claisen rearrangement provides a chemo- and regioselective enolate allylation, which can be performed asymmetrically with respect to the enolate or allyl fragment or both. In addition, many interesting chemoselectivity issues, including a highly selective RCM and a dihydroxylation, have been addressed. Overall, this synthesis was accomplished in 20 longest linear steps (24 total steps) from the inexpensive and commercially available 3-methyl-1,2-cyclopentanedione.