(+)-(E)-16-epiaffinisine | 139067-48-4

• 分子结构分类: 有机化合物 - 生物碱及其衍生物 - 大灵碱生物碱
• 英文名称: (+)-(E)-16-epiaffinisine
• 英文别名: [(1S,12S,13S,14R,15E)-15-ethylidene-3-methyl-3,17-diazapentacyclo[12.3.1.02,10.04,9.012,17]octadeca-2(10),4,6,8-tetraen-13-yl]methanol
• CAS: 139067-48-4
• 化学式: C₂₀H₂₄N₂O
• 分子量: 308.423
• InChiKey: UVWQYWHKTZABSO-GVFJQQJRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  23
• 可旋转键数：
  1
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  28.4
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (+)-(E)-16-epiaffinisine 在 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以97%的产率得到dehydro-16-epiaffinisine
  参考文献：
  名称：

  Alkaloids from leaves and root bark ofErvatamia hirta

  摘要：

  During chemical investigation of the leaves and root bark of Ervatamia hirta, 33 alkaloids were isolated. Seven are new: six are the 'monomeric' alkaloids (E) 16-epi-normacusine B, (E) 16-epi-affinisine, O-acetyl-16-epi-affinisine, affinisine-N(4)-oxide, dehydro-16-epi-affinisine, norfluorocurarine-N(4)-oxide, and the seventh is the bisindole 16-decarbomethoxyvoacamine-pseudoindoxyl. The known alkaloids are: (E) 16-epi-isositsirikine, beta-yohimbine, yohimbine, 19,20-dehydro-beta-yohimbine, beta-yohimbine-pseudoindoxyl, isositsirikine, 19,20-dihydroisositsirikine, beta-yohimbine-oxindole, normacusine B, affinisine, vobasine, dregamine, tabernaemontanine, norfluorocurarine, 12-hydroxynorfluorocurarine, apparicine, 3,14-dihydroellipticine, antirhine, voacristine, ibogaine, iboxygaine, iboxygaine-hydroxyindolenine, iboluteine, 4',17,(17-beta)-dihydrotchibangensine, 16-decarbomethoxyvoacamine and 19,20-dihydro-16-decarbomethoxyvoacamine. Structural elucidation of the new alkaloids is based on spectral data and chemical correlations.

  DOI：

  10.1016/0031-9422(91)80111-d
• 作为产物：
  描述：

  (6S,10S)-(-)-5-methyl-9-oxo-12-benzyl-6,7,8,9,10,11-hexahydro-6,10-imino-5H-cyclooctaindole 在 potassium carbonate 盐酸 、 diisoamyl borane 、 potassium tert-butylate 、 四丁基溴化铵 、 氢气 、 potassium carbonate 、 三苯基膦 作用下， 以 四氢呋喃 、 乙醇 、 水 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 63.0h， 生成 (+)-(E)-16-epiaffinisine
  参考文献：
  名称：

  serpagine吲哚生物碱（E）16-epiaffinisine，（E）16-epinormacusine B和dehydro-16-epiaffinisine的立体特异性，对映体总合成。

  摘要：

  [反应：见正文]沙雷帕啶吲哚生物碱（E）16-表阿非尼辛（1），（E）16-表阿卡比辛B（2）和脱氢16-表阿非尼辛（4）的第一个立体定向全合成已经完成；该方法还导致合成了脱氢的16-表皮苹果碱B（5）。在用DDQ / THF分别以98％和95％的产率处理相应的醇时，从顶面完全控制了在4和5中所需醚的形成。

  DOI：

  10.1021/ol020209c

文献信息

• General Approach for the Synthesis of 12-Methoxy-Substituted Sarpagine Indole Alkaloids Including (−)-12-Methoxy-<i>N</i>_b-methylvoachalotine, (+)-12-Methoxy-<i>N</i>_a-methylvellosimine, (+)-12-Methoxyaffinisine, and (−)-Fuchsiaefoline
  作者：Hao Zhou、Xuebin Liao、Wenyuan Yin、Jun Ma、James M. Cook

  DOI：10.1021/jo052081t

  日期：2006.1.1

  a Schöllkopf-based chiral auxiliary in good yield. This ester was then employed in the first regiospecific, stereospecific total synthesis of (+)-12-methoxy-Na-methylvellosimine, (+)-12-methoxyaffinisine, (−)-fuchsiaefoline, and 12-methoxy-Nb-methylvoachalotine in excellent overall yield. The asymmetric Pictet−Spengler reaction and enolate-driven palladium-catalyzed cross-coupling processes served as

  的对映体特异性合成7-甲氧基d -色氨酸乙酯通过用一个基于Schöllkopf-手性辅助良好产率的杂环化拉洛克过程的组合完成。然后将该酯在第一区域专一采用，（+）立体有择的全合成- 12甲氧基Ñ一个-methylvellosimine，（+） - 12-methoxyaffinisine，（ - ） - fuchsiaefoline和12甲氧基Ñ b -methylvoachalotine具有极好的总产量。非对称的Pictet-Spengler反应和烯醇盐驱动的钯催化的交叉偶联过程是关键步骤。通过（+）-12-甲氧基-N之间的Tollens反应建立12-甲氧基-N b-甲基voachalotine的C（16）的季中心一个-methylvellosimine和甲醛以形成二醇17。在二醇两个前手性伯醇17是由羟基的氧化环化（DDQ）在轴向位置分化17与在苄基现在的位置是[C（6）]，以形成环状醚[C（6）-O
• Enantiospecific Synthesis of (+)-<i>N</i>_a-Methylpericyclivine and (−)-<i>N</i>_a-Methylakuammidine as Well as the Ring-A Oxygenated Natural Products, (+)-10-Methoxy <i>N</i>_a-Methylpericyclivine and 10-Hydroxy <i>N</i>_a-Methylpericyclivine
  作者：P. V. V. Srirama Sarma、James M. Cook

  DOI：10.1021/ol0526266

  日期：2006.3.1

  [reaction: see text] The first enantiospecific, regiospecific total synthesis of the enantiomers of N(a)-methylpericyclivine and N(a)-methylakuammidine as well as the ring-A oxygenated natural products (+)-10-methoxy N(a)-methylpericyclivine and 10-hydroxy N(a)-methylpericyclivine was achieved. The lactones (see 19, 22, and 25) are key to the formation of the beta-axial methyl ester moiety.

  [反应：见正文] N（a）-甲基周环冰草和N（a）-甲基akuammidine的对映异构体以及环A氧化的天然产物（+）-10-甲氧基N（a）的第一个对映体特异性，区域特异性全合成）-甲基冰晶石和10-羟基N（a）-甲基冰晶石。内酯（参见19、22和25）是形成β-轴甲基酯部分的关键。
• Alkaloids from leaves and root bark ofErvatamia hirta
  作者：Pascale Clivio、Bernard Richard、Jean-Robert Deverre、Thierry Sevenet、Monique Zeches、Louisette Le Men-Oliver

  DOI：10.1016/0031-9422(91)80111-d

  日期：1991.1

  During chemical investigation of the leaves and root bark of Ervatamia hirta, 33 alkaloids were isolated. Seven are new: six are the 'monomeric' alkaloids (E) 16-epi-normacusine B, (E) 16-epi-affinisine, O-acetyl-16-epi-affinisine, affinisine-N(4)-oxide, dehydro-16-epi-affinisine, norfluorocurarine-N(4)-oxide, and the seventh is the bisindole 16-decarbomethoxyvoacamine-pseudoindoxyl. The known alkaloids are: (E) 16-epi-isositsirikine, beta-yohimbine, yohimbine, 19,20-dehydro-beta-yohimbine, beta-yohimbine-pseudoindoxyl, isositsirikine, 19,20-dihydroisositsirikine, beta-yohimbine-oxindole, normacusine B, affinisine, vobasine, dregamine, tabernaemontanine, norfluorocurarine, 12-hydroxynorfluorocurarine, apparicine, 3,14-dihydroellipticine, antirhine, voacristine, ibogaine, iboxygaine, iboxygaine-hydroxyindolenine, iboluteine, 4',17,(17-beta)-dihydrotchibangensine, 16-decarbomethoxyvoacamine and 19,20-dihydro-16-decarbomethoxyvoacamine. Structural elucidation of the new alkaloids is based on spectral data and chemical correlations.
• Stereospecific, Enantiospecific Total Synthesis of the Sarpagine Indole Alkaloids (<i>E</i>)16-Epiaffinisine, (<i>E</i>)16-Epinormacusine B, and Dehydro-16-epiaffinisine
  作者：Jianming Yu、Xuebin Liao、James M. Cook

  DOI：10.1021/ol020209c

  日期：2002.12.1

  [reaction: see text] The first stereospecific total synthesis of the sarpagine indole alkaloids (E)16-epiaffinisine (1), (E)16-epinormacusine B (2), and dehydro-16-epiaffinisine (4) has been completed; this method has also resulted in the synthesis of dehydro-16-epinormacusine B (5). The formation of the required ether in both 4 and 5 was realized with complete control from the top face on treatment

  [反应：见正文]沙雷帕啶吲哚生物碱（E）16-表阿非尼辛（1），（E）16-表阿卡比辛B（2）和脱氢16-表阿非尼辛（4）的第一个立体定向全合成已经完成；该方法还导致合成了脱氢的16-表皮苹果碱B（5）。在用DDQ / THF分别以98％和95％的产率处理相应的醇时，从顶面完全控制了在4和5中所需醚的形成。