(-)-4-oxostenine | 171523-55-0

• 分子结构分类: 有机化合物 - 生物碱及其衍生物 - 百部生物碱
• 英文名称: (-)-4-oxostenine
• 英文别名: (7aR,8R,8aS,11S,11aR,11bR,11cR)-8-ethyl-11-methyldecahydroazepino[3,2,1-hi]furo[3,2-e]indole-4,10(11bH,11cH)-dione；oxostenine；(1R,9R,10R,11S,14S,15S,16R)-10-ethyl-14-methyl-12-oxa-4-azatetracyclo[7.6.1.04,16.011,15]hexadecane-5,13-dione
• CAS: 171523-55-0
• 化学式: C₁₇H₂₅NO₃
• 分子量: 291.39
• InChiKey: WQTVRIFDQIVHSW-BKQRAYJDSA-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：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (-)-4-oxostenine 在 劳森试剂 、 镍 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 3.5h， 生成 (7aR,8R,8aS,11S,11aS,11bR,11cR)-8-乙基十二氢-11-甲基-呋喃并[2,3-h]吡咯并[3,2,1-jk][1]苯并氮杂卓-10(2H)-酮
  参考文献：
  名称：

  Asymmetric Total Synthesis of the Stemona Alkaloid (-)-Stenine

  摘要：

  Stenine can be extracted from the roots of the Chinese medicinal plant Stemona tuberosa (Stemonaceae), and its structure and absolute configuration were derived by comparison to the major Stemona alkaloid tuberostemonine. We report the first enantioselective total synthesis of (-)-stenine by a strategy that takes advantage of a diastereoselective end-group-differentiating cyclization in the oxidation of L-tyrosine, The resulting cis-fused indolone is converted to the trans-fused core of stenine upon reduction of a pi-allylpalladium complex, and by stereoselective introduction of four additional stereocenters, a butyrolactone and an azepine ring are attached to this alkaloid building block.

  DOI：

  10.1021/ja00150a010
• 作为产物：
  描述：

  (2S,3aR,7aR)-3a-hydroxy-6-oxo-2,3,3a,6,7,7a-hexahydroindole-1,2-dicarboxylic acid 1-benzyl ester 2-methyl ester 在 palladium dihydroxide 吡啶 、 咪唑 、 六甲基磷酰三胺 、 4-二甲氨基吡啶 、 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 lithium hydroxide 、 sodium chlorite 、 sodium tetrahydroborate 、 sodium periodate 、 四氧化锇 、 甲酸 、 phosphate buffer 、 cerium(III) chloride 、 四丙基高钌酸铵 、 potassium hexamethyldisilazane 、 偶氮二异丁腈 、 三丁基膦 、 五氟苯基二苯基磷酸酯 、 氢氟酸 、 氢气 、 双氧水 、 碘 、 三正丁基氢锡 、 戴斯-马丁氧化剂 、 N-甲基吗啉氧化物 、 二氯磷酸苯酯 、 氢化奎尼定 1,4-(2,3-二氮杂萘)二醚 、 三乙胺 、 sodium phosphate 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 异丙醚 、 水 、 乙腈 、 xylene 为溶剂， 反应 203.75h， 生成 (-)-4-oxostenine
  参考文献：
  名称：

  Asymmetric Total Synthesis of the Stemona Alkaloid (-)-Stenine

  摘要：

  Stenine can be extracted from the roots of the Chinese medicinal plant Stemona tuberosa (Stemonaceae), and its structure and absolute configuration were derived by comparison to the major Stemona alkaloid tuberostemonine. We report the first enantioselective total synthesis of (-)-stenine by a strategy that takes advantage of a diastereoselective end-group-differentiating cyclization in the oxidation of L-tyrosine, The resulting cis-fused indolone is converted to the trans-fused core of stenine upon reduction of a pi-allylpalladium complex, and by stereoselective introduction of four additional stereocenters, a butyrolactone and an azepine ring are attached to this alkaloid building block.

  DOI：

  10.1021/ja00150a010

文献信息

• Syntheses of the <i>Stemona</i> Alkaloids (±)-Stenine, (±)-Neostenine, and (±)-13-Epineostenine Using a Stereodivergent Diels–Alder/Azido-Schmidt Reaction
  作者：Kevin J. Frankowski、Jennifer E. Golden、Yibin Zeng、Yao Lei、Jeffrey Aubé

  DOI：10.1021/ja800574m

  日期：2008.5.1

  A tandem Diels-Alder/azido-Schmidt reaction sequence provides rapid access to the core skeleton shared by several Stemona alkaloids including stenine, neostenine, tuberostemonine, and neotuberostemonine. The discovery and evolution of inter- and intramolecular variations of this process and their applications to total syntheses of (+/-)-stenine and (+/-)-neostenine are described. The stereochemical

  串联 Diels-Alder/叠氮基-Schmidt 反应序列提供了对包括 Stemona 生物碱（包括 Stemona 生物碱，包括 stemona、neostenine、tuberostemonine 和 neotuberostemonine）共有的核心骨架的快速访问。描述了该过程的分子间和分子内变异的发现和演变及其在 (+/-)-stenine 和 (+/-)-neostenine 全合成中的应用。反应的立体化学结果取决于底物类型和反应条件，从而能够从相同的二烯/亲二烯体组合中制备 (+/-)-stenine 和 (+/-)-neostenine。
• An Expeditious Total Synthesis of (±)-Stenine
  作者：Yibin Zeng、Jeffrey Aubé

  DOI：10.1021/ja055629m

  日期：2005.11.1

  (+/-)-Stenine was synthesized in eight steps from a known ketophosphonate reagent. The key step was an exo-selective Diels-Alder/intramolecular Schmidt domino reaction that afforded three of the four rings and four stereocenters in a single reaction.

  (+/-)-Stenine是从一种已知的酮磷酸酯试剂经过八步合成的。关键步骤是一个exo选择性的Diels-Alder与分子内施密特反应的多米诺反应，这一步骤在单次反应中生成了四个环中的三个，并形成了四个立体中心。
• Asymmetric Total Synthesis of the Stemona Alkaloid (-)-Stenine
  作者：Peter Wipf、Yuntae Kim、David M. Goldstein

  DOI：10.1021/ja00150a010

  日期：1995.11

  Stenine can be extracted from the roots of the Chinese medicinal plant Stemona tuberosa (Stemonaceae), and its structure and absolute configuration were derived by comparison to the major Stemona alkaloid tuberostemonine. We report the first enantioselective total synthesis of (-)-stenine by a strategy that takes advantage of a diastereoselective end-group-differentiating cyclization in the oxidation of L-tyrosine, The resulting cis-fused indolone is converted to the trans-fused core of stenine upon reduction of a pi-allylpalladium complex, and by stereoselective introduction of four additional stereocenters, a butyrolactone and an azepine ring are attached to this alkaloid building block.
• Enantioselective Total Synthesis of (−)-Stenine
  作者：Jingbo Chen、Jingchao Chen、Yan Xie、Hongbin Zhang

  DOI：10.1002/anie.201106587

  日期：2012.1.23