oxoepistephamiersine

• 分子结构分类: 有机化合物 - 生物碱及其衍生物 - 哈苏巴南生物碱
• 英文名称: oxoepistephamiersine
• 英文别名: (1R,8S,10S,11R,12S)-3,4,11,12-tetramethoxy-17-methyl-18-oxa-17-azapentacyclo[8.4.3.18,11.01,10.02,7]octadeca-2(7),3,5-triene-13,16-dione
• 化学式: C₂₁H₂₅NO₇
• 分子量: 403.432
• InChiKey: UMLCCHVXIGOAFZ-CARQKBIPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  29
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  83.5
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  oxoepistephamiersine 在 sodium tetrahydroborate 作用下， 以 甲醇 、 水 为溶剂， 生成 二氢氧代表千金藤默星碱
  参考文献：
  名称：

  Constitution of four new hasubanan alkaloids from Stephania japonica miers.

  摘要：

  Four new hasubanan alkaloids, stephamiersine (1), epistephamiersine (2), oxostephamiersine (3) and stephasunoline (4) were isolated together with seven known and three unidentified alkaloids from Stephania japonica MIERS (Menispermaceae). Among these new alkaloids, 1 and 2 were found to be epimeric isomers with respect to the C-7 methoxyl group. Permanganate oxidation of 1 gave 3, and borohydride reduction of 1 and 2 gave the highly stereoselective products, dihydrostephamiersine (6) and dihydroepistephamiersine (5). On mild treatment of 5 with hydrochloric acid gave 4. Acetolyses of 1, 2, 5 and 6 gave the phenanthrene derivatives, 7, 8 and 9, respectively. Further, both 1 and 2 were converted to the conjugated carbonyl compound (14) which was obtained from dihydro-16-oxohasubanonine (17a) (17b). On the other hand, the stereochemistry of 1, 2, 3 and 4 was elucidated by nuclear magnetic resonance (NMR) spectroscopic studies as follows : the C-7 methoxyl group of 1 has the α-axial and that of 2 and 4 has the β-equatorial configuration, and the hydroxyl group of 4 has the β-axial one. On the basis of the above chemical correlation coupled with the spectral arguments, the constitution of the new alkaloids was represented as drawn in the formulas, 1, 2, 3 and 4.

  DOI：

  10.1248/cpb.23.1323
• 作为产物：
  描述：

  在 碳酸氢钠 、 戴斯-马丁氧化剂 作用下， 以 二氯甲烷 为溶剂， 以90 %的产率得到oxoepistephamiersine
  参考文献：
  名称：

  Metaphanine 和 Oxoepistephamiersine 的全合成

  摘要：

  通过钯催化级联环化的不同路线，由廉价的环己二酮单乙烯缩醛合成了两种复杂的哈苏巴南生物碱。区域选择性Baeyer-Villiger氧化随后MeNH 2触发的骨架重组形成了苯并环氮杂[4.4.3]丙烷，而sp 3 C−H键的后期区域和非对映选择性氧化环形成了具有挑战性的四氢呋喃环系统。

  DOI：

  10.1002/anie.202310917

文献信息

• Total Synthesis of Metaphanine and Oxoepistephamiersine
  作者：Ya‐Kui Sun、Jin‐Bao Qiao、Yu‐Meng Xin、Qin Zhou、Zhi‐Hua Ma、Hui Shao、Yu‐Ming Zhao

  DOI：10.1002/anie.202310917

  日期：2023.10.2

  inexpensive cyclohexanedione monoethylene acetal by a divergent route featuring a palladium-catalyzed cascade cyclization. Regioselective Baeyer–Villiger oxidation followed by MeNH2-triggered skeletal reorganization formed the benzannulated aza[4.4.3]propellane, and late-stage regio- and diastereoselective oxidative annulation of a sp3 C−H bond formed the challenging tetrahydrofuran ring system.

  通过钯催化级联环化的不同路线，由廉价的环己二酮单乙烯缩醛合成了两种复杂的哈苏巴南生物碱。区域选择性Baeyer-Villiger氧化随后MeNH 2触发的骨架重组形成了苯并环氮杂[4.4.3]丙烷，而sp 3 C−H键的后期区域和非对映选择性氧化环形成了具有挑战性的四氢呋喃环系统。
• Constitution of four new hasubanan alkaloids from Stephania japonica miers.
  作者：MATAO MATSUI、YASUO WATANABE、TOSHIRO IBUKA、KIYOSHI TANAKA

  DOI：10.1248/cpb.23.1323

  日期：——

  Four new hasubanan alkaloids, stephamiersine (1), epistephamiersine (2), oxostephamiersine (3) and stephasunoline (4) were isolated together with seven known and three unidentified alkaloids from Stephania japonica MIERS (Menispermaceae). Among these new alkaloids, 1 and 2 were found to be epimeric isomers with respect to the C-7 methoxyl group. Permanganate oxidation of 1 gave 3, and borohydride reduction of 1 and 2 gave the highly stereoselective products, dihydrostephamiersine (6) and dihydroepistephamiersine (5). On mild treatment of 5 with hydrochloric acid gave 4. Acetolyses of 1, 2, 5 and 6 gave the phenanthrene derivatives, 7, 8 and 9, respectively. Further, both 1 and 2 were converted to the conjugated carbonyl compound (14) which was obtained from dihydro-16-oxohasubanonine (17a) (17b). On the other hand, the stereochemistry of 1, 2, 3 and 4 was elucidated by nuclear magnetic resonance (NMR) spectroscopic studies as follows : the C-7 methoxyl group of 1 has the α-axial and that of 2 and 4 has the β-equatorial configuration, and the hydroxyl group of 4 has the β-axial one. On the basis of the above chemical correlation coupled with the spectral arguments, the constitution of the new alkaloids was represented as drawn in the formulas, 1, 2, 3 and 4.