13-(1'-methenylethyl)-12-methoxy-podocarpane-8,11,13-triene | 10064-25-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 13-(1'-methenylethyl)-12-methoxy-podocarpane-8,11,13-triene
• 英文别名: 13-(isopropenyl)-12-methoxy-podocarpane-8,11,13-triene；12-methoxy-8,11,13,15-abietatetraene；12-methoxyabieta-8,11,13,15-tetraene；(4aS,10aS)-6-methoxy-1,1,4a-trimethyl-7-prop-1-en-2-yl-2,3,4,9,10,10a-hexahydrophenanthrene
• CAS: 10064-25-2
• 化学式: C₂₁H₃₀O
• 分子量: 298.469
• InChiKey: GWOFXKYEXUQPSP-PZJWPPBQSA-N

物化性质

• 熔点：
  92-93 °C
• 沸点：
  396.9±42.0 °C(Predicted)
• 密度：
  0.959±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.3
• 重原子数：
  22
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  13-(1'-methenylethyl)-12-methoxy-podocarpane-8,11,13-triene 在 chromium(VI) oxide 、 甲醇 、 sodium hydroxide 、 dimethyl sulfide borane 、 硫酸 、 双氧水 、 溴 、 乙酸酐 、 溶剂黄146 、 二乙胺 作用下， 以 吡啶 、 乙醚 为溶剂， 生成 [(1S,2S)-4'-((R)-2-Hydroxy-1-methyl-ethyl)-5'-methoxy-1,3,3-trimethyl-3',6'-dioxo-bicyclohexyl-1',4'-dien-2-yl]-acetic acid
  参考文献：
  名称：

  Burnell, Robert H.; Neron-Desbiens, Martine; Savard, Sylvain, Synthetic Communications, 1982, vol. 12, # 1, p. 11 - 14

  摘要：

  DOI：
• 作为产物：
  描述：

  (S)-α-Cyclogeraniol 在 palladium on activated charcoal 正丁基锂 、 三氯化铝 、 三氟化硼乙醚 、 氢气 、 sodium acetate 、 对甲苯磺酸 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 乙醇 、 正己烷 、 二氯甲烷 、 苯 为溶剂， 反应 10.5h， 生成 13-(1'-methenylethyl)-12-methoxy-podocarpane-8,11,13-triene
  参考文献：
  名称：

  Stereoselective synthesis of (−)-6,7-dehydroferruginyl methyl ether

  摘要：

  A stereoselective synthetic route to (-)-6,7-dehydroferruginyl methyl ether was developed from (S)-(-)-alpha-cyclocitral. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(00)00007-0

文献信息

• Revision of Structures of Nellionol and Dehydronellionol
  作者：Takashi Matsumoto、Sachihiko Imai、Shoji Takeda、Masanori Mitsuki

  DOI：10.1246/bcsj.56.2013

  日期：1983.7

  The structures of nellionol and dehydronellionol were revised respectively to 6α,11,12,16-tetrahydroxyabieta-8,11,13-trien-7-one (12) and 6,11,12,16-tetrahydroxyabieta-5,8,11,13-tetraen-7-one (13) by the following syntheses. A mixture of (15R)- and (15S)-12-methoxyabieta-8,11,13-trien-16-ol, prepared from 13-acetyl-12-methoxypodocarpa-8,11,13-triene, was converted into 11,12,16-triacetoxyabieta-8,11,13-trien-7-one (22) via 16-acetoxy-12-benzoyloxyabieta-8,11,13-trien-11-ol. Treatment of 22 with isopropenyl acetate, followed by oxidation with m-chloroperbenzoic acid and subsequent acetylation, afforded 6α, 11,12,16-tetraacetoxyabieta-8,11,13-trien-7-one, which was hydrolyzed with dilute hydrochloric acid to 12. The ketone 22 was also converted into 13  via 11,12,16-triacetoxyabieta-8,11,13-trien-6-one. The spectral data of 12 and 13 were in good agreement with those of natural nellionol and dehydronellionol.

  通过以下合成方法，将内六烯醇和脱水内六烯醇的结构分别修正为 6α,11,12,16-四羟基阿松香-8,11,13-三烯-7-酮 (12) 和 6,11,12,16-四羟基阿松香-5,8,11,13-四烯-7-酮 (13)。由 13-acetyl-12-methoxypodocarpa-8,11,13-triene 制备的 (15R)- 和 (15S)-12-methoxyabieta-8,11,13-trien-16-ol 混合物通过 16-acetoxy-12-benzoyloxyabieta-8,11,13-trien-11-ol 转化为 11,12,16-三乙酰氧基阿松香-8,11,13-三烯-7-酮 (22)。用乙酸异丙烯酯处理 22，然后用间氯过苯甲酸氧化，再进行乙酰化，得到 6α，11,12,16-四乙酰氧基阿松香-8,11,13-三烯-7-酮，用稀盐酸水解得到 12。酮 22 也通过 11,12,16-三乙酰氧基阿松香-8,11,13-三烯-6-酮转化为 13。12 和 13 的光谱数据与天然橙皮烯醇和脱水橙皮烯醇的光谱数据十分吻合。
• The Syntheses and Absolute Configurations of Nellionol and 5-Dehydronellionol
  作者：Takashi Matsumoto、Sachihiko Imai、Takashi Yoshinari

  DOI：10.1246/bcsj.58.1165

  日期：1985.4

  To determine the absolute configurations of C-15 in natural nellionol and 5-dehydronellionol, (15R)-8,11,13-abietatriene-12,16-diol was converted into (15R)-6α,11,12,16-tetrahydroxy-8,11,13-abietatrien-7-one (3a) and (15R)-6,11,12,16-tetrahydroxy-5,8,11,13-abietatetraen-7-one (4a), which were identical with natural products. For direct comparisons with 3a and 4a, (15S)-6α,11,12,16-tetrahydroxy-8,11

  为了确定天然 nellionol 和 5-dehydronellionol 中 C-15 的绝对构型，将 (15R)-8,11,13-abietatriene-12,16-diol 转化为 (15R)-6α,11,12,16-tetrahydroxy -8,11,13-abietatrien-7-one (3a) 和 (15R)-6,11,12,16-tetrahydroxy-5,8,11,13-abietatetraen-7-one (4a)，它们是相同的与天然产品。对于与 3a 和 4a 的直接比较，(15S)-6α,11,12,16-tetrahydroxy-8,11,13-abietatrien-7-one (3b) 和 (15S)-6,11,12,16-tetrahydroxy -5,8,11,13-abietatetraen-7-one (4b) 也由 (15S)-8,11,13-abietatriene-12
• Biosynthesis of the abietane type diterpene ferruginol in cell cultures of Salvia miltiorrhiza: synthesis of (15S)- and (15R)-[16-2H1]12-O-methylferruginol by enzymatic resolution of 12-O-methyl-16-hydroxyferruginol and stereochemistry of 1,2-methyl migration in the formation of the isopropyl group
  作者：Yutaka Tomita、Michiyo Annaka、Yasumasa Ikeshiro

  DOI：10.1039/c39890000108

  日期：——

  The signals for the pro(R) and pro(S) methyl groups of the isopropyl group, in the 13C1H} n.m.r. spectrum of 12-O-methylferruginol, have been assigned by the synthesis of the title compounds and the stereochemistry of 1,2-methyl migration for biosynthesis of the abietane skeleton of ferruginol has been established.

  为信号亲（[R ）和亲（小号）的异丙基的甲基，在13 C 1 1个H} -12-的NMR谱ø -methylferruginol，已经由标题化合物和立体化学的合成分配1,2-甲基迁移用于生物合成ferruginol的abietane骨架的方法已经建立。
• Stereoselective synthesis of (−)-6,7-dehydroferruginyl methyl ether
  作者：Yonghong Gan、Anpai Li、Xinfu Pan、Albert S.C Chan、Teng-Kuei Yang

  DOI：10.1016/s0957-4166(00)00007-0

  日期：2000.2

  A stereoselective synthetic route to (-)-6,7-dehydroferruginyl methyl ether was developed from (S)-(-)-alpha-cyclocitral. (C) 2000 Elsevier Science Ltd. All rights reserved.
• TOMITA, YUTAKA;ANNAKA, MICHIYO;IKESHIRO, YASUMASA, J. CHEM. SOC. CHEM. COMMUN.,(1989) N, C. 108-110
  作者：TOMITA, YUTAKA、ANNAKA, MICHIYO、IKESHIRO, YASUMASA

  DOI：——

  日期：——