1β,4α-dihydroxy-3α,11β-H-eudesman-6α,12-olide | 66428-35-1

• 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-dihydroxy-3α,11β-H-eudesman-6α,12-olide
• 英文别名: 1β,4α-dihydroxy-5α,11β-H-eudesman-6α,12-olide；1β-hydroxycolartin；(3S,3aS,5aR,6R,9R,9aS,9bS)-6,9-dihydroxy-3,5a,9-trimethyl-3a,4,5,6,7,8,9a,9b-octahydro-3H-benzo[g][1]benzofuran-2-one
• CAS: 66428-35-1
• 化学式: C₁₅H₂₄O₄
• 分子量: 268.353
• InChiKey: JZWIOLGEFWVOLI-PDIQHLCYSA-N

物化性质

• 沸点：
  434.8±45.0 °C(Predicted)
• 密度：
  1.180±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  19
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  66.8
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1β,4α-dihydroxy-3α,11β-H-eudesman-6α,12-olide 在 吡啶 、 sodium tetrahydroborate 、 lithium aluminium tetrahydride 、 氯化亚砜 作用下， 以 四氢呋喃 、 吡啶 、 乙醇 为溶剂， 反应 24.5h， 生成 1β-acetoxy-12-hydroxy-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：

  4α-hydroxy-1-oxo-5α,11β-H-eudesman-6α,12-olide 在 sodium tetrahydroborate 作用下， 以 乙醇 为溶剂， 反应 0.5h， 以57.8%的产率得到1β,4α-dihydroxy-3α,11β-H-eudesman-6α,12-olide
  参考文献：
  名称：

  Biomimetic cyclization of gallicin to form guaianolides

  摘要：

  DOI：

  10.1016/0040-4020(80)80216-x

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.
• Unified Synthesis of Eudesmanolides, Combining Biomimetic Strategies with Homogeneous Catalysis and Free-Radical Chemistry
  作者：Alejandro F. Barrero、Antonio Rosales、Juan M. Cuerva、J. Enrique Oltra

  DOI：10.1021/ol034510k

  日期：2003.5.1

  [reaction: see text] A general procedure for the synthesis of both 12,6- and 12,8-eudesmanolides has been developed. The key step is the titanocene-catalyzed radical cyclization of accessible epoxygermacrolides. The novel reagent 2,4,6-trimethyl-1-trimethylsilylpyridinium chloride, both compatible with oxiranes and capable of regenerating Cp(2)TiCl(2) from Cp(2)Ti(Cl)H and Cp(2)Ti(Cl)OAc, played an

  [反应：见正文]已经开发了合成12，6-和12，8-十二烷内酯的通用方法。关键步骤是钛环茂金属催化可及的环氧锗烷的自由基环化。新型试剂2,4,6-三甲基-1-三甲基甲硅烷基吡啶鎓氯化物，与二恶英兼容，能够从Cp（2）Ti（Cl）H和Cp（2）Ti（Cl）再生Cp（2）TiCl（2） ）OAc在导致环外烯烃的催化循环中起着重要作用。
• Biomimetic cyclization of gallicin to form guaianolides
  作者：Antonio G. Gonzlez、Antonio Galindo、Horacio Mansilla

  DOI：10.1016/0040-4020(80)80216-x

  日期：1980.1
• Regioselective Enzymatic Acylations of Polyhydroxylated Eudesmanes:  Semisynthesis, Theoretical Calculations, and Biotransformation of Cyclic Sulfites
  作者：Andrés García-Granados、Enrique Melguizo、Andrés Parra、Yolanda Simeó、Beatriz Viseras、J. A. Dobado、José Molina、J. M. Arias

  DOI：10.1021/jo0008183

  日期：2000.12.1

  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.