1β,4α,6α,12-tetrahydroxy-5α,11β-H-eudesmane | 143729-72-0

• 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: 1β,4α,6α,12-tetrahydroxy-5α,11β-H-eudesmane
• 英文别名: (1R,4R,4aS,5S,6S,8aR)-6-[(2S)-1-hydroxypropan-2-yl]-4,8a-dimethyl-1,2,3,4a,5,6,7,8-octahydronaphthalene-1,4,5-triol
• CAS: 143729-72-0
• 化学式: C₁₅H₂₈O₄
• 分子量: 272.385
• InChiKey: OMMCLLDLFRUWBS-JPSNCLMPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  80.9
• 氢给体数：
  4
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1β,4α,6α,12-tetrahydroxy-5α,11β-H-eudesmane 在 Candida antarctica lipase 、 sodium tetrahydroborate 、 氯化亚砜 作用下， 以 吡啶 、 乙醇 为溶剂， 反应 25.5h， 生成 1β,12-dihydroxy-5α,11β-H-eudesman-4α,6α-diyl-S(R)-cyclic sulfite
  参考文献：
  名称：

  Regioselective Enzymatic Acylations of Polyhydroxylated Eudesmanes:  Semisynthesis, Theoretical Calculations, and Biotransformation of Cyclic Sulfites

  摘要：

  Different lipase enzymes have been tested in order to perform regioselective acetylations on the eudesmane tetrol from vulgarin. High yields (95%) of 1,12-diacetoxy derivative (4) were achieved in Ih with Candida antarctica Lipase (CAL). However, only the la-acetyl derivative (6) was obtained in similar yield with Mucor miehei (MML) or Candida cylindracea (CCL) lipases. The enzymatic protection at C-l and C-12 has been used to form eudesmane cyclic-sulfites between C-6 and C-4 atoms. The RIS-sulfur configuration has been assigned by means of the experimental and theoretical C-13 and H-1 NMR chemical shifts. The theoretical shifts were calculated using the GIAO method, with a MM+ geometry optimization followed by a single-point calculation at the B3LYP/6-31G* level (B3LYP/6-31G*//MM+). Moreover, B3LYP/6-31G* geometry optimizations were carried out to test the B3LYP/6-31G*//MM+ results, for the deacetylated sulfites (12 and 15). In addition to the delta (C) and delta (H) shifts, the (3)J(HH) coupling constants were also calculated and compared with the experimental values when available. Finally, different reactivities have been checked in both sulfites by biotransformation with Rhizopus nigricans. While the R-sulfite gave 2 alpha- and 11 beta -hydroxylated metabolites, the S-sulfite yielded only regioselective deacetylations. Furthermore, both sulfites showed different reactivities in redox processes.

  DOI：

  10.1021/jo0008183
• 作为产物：
  描述：

  1β,12-diacetoxy-4α,5α-dihydroxy-5α,11β-H-eudesmane 在 jones' reagent 、 Rhizopus nigricans 作用下， 以 乙醇 、 丙酮 为溶剂， 反应 336.0h， 生成 1β,4α,6α,12-tetrahydroxy-5α,11β-H-eudesmane
  参考文献：
  名称：

  几种倍半萜的黑根霉化学半合成和生物转化：获得新的1α-和2α-羟基硒代烷衍生物

  摘要：

  从从加拿大蒿属植物中分离出来的天然产物寻常素开始，半合成了几种乙酰化，丙酮化和氧化的多羟基杜鹃花和杜鹃花。这些衍生物中的一些已被真菌黑根霉菌生物转化，因此分离了具有新的羟基化，还原和/或脱乙酰基的代谢物。1β，6α-二乙酰氧基-12-羟基-5α，11β- H -eudesm-4（15）-烯的孵育以高收率（60％）得到2-羟基硒烷衍生物。1-氧代和6-氧代果糖的微生物学转化以高比例产生了其他有用的羟基硒代烷衍生物，这是由于β-面上的真菌在这些位置上的羰基立体选择性还原的结果。此外，R。nigricans 有时会产生区域选择性的脱乙酰基和/或水解的异亚丙基化合物。

  DOI：

  10.1016/s0040-4020(00)00599-8

文献信息

• Partial synthesis of 6β-sesquiterpenolides from 6α-sesquiterpenolides
  作者：José L. Bretón、Juan J. Cejudo、Andrés García-Granados、Andrés Parra、Francisco Rivas

  DOI：10.1016/s0040-4039(00)74823-4

  日期：1992.6

  Chemical means were used to achieve the epimerization at C-6 of 6α-eudesmanolides, with several functionalizations, to 7β-eudesmanolides. The process consists of the LiAlH4 reduction of a 6α-lactone, selective acetylation of the hydroxymethylene group at C-12, oxidation and reduction at C-6 to epimerize this carbon, deacetylation at C-12 and final formation of a 6β-lactone with RuH2(Ph3P)4. The whole

  使用化学方法实现了具有一些功能化的6α-大麦醇内酯在C-6的差向异构化为7β-大麦醇内酰胺。该方法包括LiAlH 4还原6α-内酯，在C-12处羟甲基的选择性乙酰化，在C-6处氧化和还原以使该碳异构化，在C-12处脱乙酰基和最终形成6β-内酯。含RuH 2（Ph 3 P）4。整个过程产生近40％的6β-内酯，限制步骤是用钌试剂（58和53％）进行氧化。
• Partial synthesis of 6β-eudesmanolides and 6β-guaianolides from 6α-eudesmanolides: Synthesis of analogues of artepaulin, colartin and tannunolide D
  作者：José L. Bretón、Juan J. Cejudo、Andrés García-Granados、Andrés Parra、Francisco Rivas

  DOI：10.1016/s0040-4020(01)87003-4

  日期：1994.2

  The epimerization process consists of the LiA1H4 reduction of a 6α-lactone, selective protection of the hydroxymethylene group at C-12, oxidation and reduction at C-6 to epimerize this carbon, deprotection at C-12 and finally, lactonization with tetrapropylammonium perruthenate (TPAP) and 4-methylmorpholine N-oxide (NMO) in yields over 80%. The rearrangement of 1β-hydroxy-6β-colartin allow us to obtain

  通过化学方法实现多官能化的6α-马来酸酐在C-6的差向异构化，以获得6β-马来酸酐，并且在重排后获得6β-愈创木酚内酯。差向异构化过程包括LiA1H 4还原6α-内酯，对C-12处的羟甲基进行选择性保护，在C-6处进行氧化和还原以使该碳异构化，在C-12处进行脱保护，最后用四丙基过钌酸内酯进行内酯化（TPAP）和4-甲基吗啉N-氧化物（NMO），收率超过80％。1β-羟基-6β-colartin的重排使我们可以获得2,3-二氢-6β-鞣酸内酯D.