(-)-8-des-ethyl,(8S)-phenylseleno-13-epituberostemonine | 828921-50-2

• 分子结构分类: 有机化合物 - 生物碱及其衍生物
• 英文名称: (-)-8-des-ethyl,(8S)-phenylseleno-13-epituberostemonine
• 英文别名: (1R,3S,9S,10R,11R,15S,16S)-14-methyl-3-[(2S,4S)-4-methyl-5-oxooxolan-2-yl]-10-phenylselanyl-12-oxa-4-azatetracyclo[7.6.1.04,16.011,15]hexadecan-13-one
• CAS: 828921-50-2
• 化学式: C₂₆H₃₃NO₄Se
• 分子量: 502.512
• InChiKey: PBLIMYDVHHOYLC-LOJBUAMRSA-N

物化性质

• 沸点：
  659.9±55.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.81
• 重原子数：
  32
• 可旋转键数：
  3
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  55.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (-)-8-des-ethyl,(8S)-phenylseleno-13-epituberostemonine 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 偶氮二异丁腈 、 三氟甲苯 、 N-tritylprop-2-en-1-amine 、 对甲苯磺酸 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 76.5h， 生成 (1R,3S,9R,10R,11S,14S,15S,16R)-10-ethenyl-14-methyl-3-[(2S,4S)-4-methyl-5-oxooxolan-2-yl]-12-oxa-4-azatetracyclo[7.6.1.04,16.011,15]hexadecan-13-one
  参考文献：
  名称：

  Asymmetric Total Syntheses of Tuberostemonine, Didehydrotuberostemonine, and 13-Epituberostemonine

  摘要：

  Detailed experimental approaches toward the pentacyclic Stemona alkaloids tuberostemonine and didehydrotuberostemonine and the close analogue 13-epituberostemonine are described. The syntheses originate with a hydroindolinone derivative that can be obtained on a large scale in a single step from carbobenzoxy-protected L-tyrosine. Highlights of the conversion of this hydroindolinone to the target structures are the three-fold use of ruthenium catalysts, first in azepine ring-closing metathesis and then in alkene isomerization and cross-metathesis propenyl-vinyl exchange, as well as the stereoselective attachment of a y-butyrolactone ring to a tetracycle core structure by use of a lithiated asymmetric bicyclo[3.2.1]octane (ABO) ortho ester. Structural analysis by density functional theory (DFT) methods revealed that the ease of oxidation of the natural product is likely due to the conformational preferences of the pyrrolidine and the fused cyclohexane rings.

  DOI：

  10.1021/ja044280k
• 作为产物：
  描述：

  在 对甲苯磺酸 作用下， 以 甲醇 、 水 、 乙腈 、 xylene 为溶剂， 反应 57.0h， 生成 (-)-8-des-ethyl,(8S)-phenylseleno-13-epituberostemonine
  参考文献：
  名称：

  Asymmetric Total Syntheses of Tuberostemonine, Didehydrotuberostemonine, and 13-Epituberostemonine

  摘要：

  Detailed experimental approaches toward the pentacyclic Stemona alkaloids tuberostemonine and didehydrotuberostemonine and the close analogue 13-epituberostemonine are described. The syntheses originate with a hydroindolinone derivative that can be obtained on a large scale in a single step from carbobenzoxy-protected L-tyrosine. Highlights of the conversion of this hydroindolinone to the target structures are the three-fold use of ruthenium catalysts, first in azepine ring-closing metathesis and then in alkene isomerization and cross-metathesis propenyl-vinyl exchange, as well as the stereoselective attachment of a y-butyrolactone ring to a tetracycle core structure by use of a lithiated asymmetric bicyclo[3.2.1]octane (ABO) ortho ester. Structural analysis by density functional theory (DFT) methods revealed that the ease of oxidation of the natural product is likely due to the conformational preferences of the pyrrolidine and the fused cyclohexane rings.

  DOI：

  10.1021/ja044280k