1β,12-diacetoxy-5α,11β-H-eudesman-4α,6α-diyl-S(R)-cyclic sulfite | 315662-31-8

• 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,12-diacetoxy-5α,11β-H-eudesman-4α,6α-diyl-S(R)-cyclic sulfite
• 英文别名: [(2S)-2-[(1R,3R,5S,6S,9R,10R,13S)-10-acetyloxy-1,9-dimethyl-3-oxo-2,4-dioxa-3λ4-thiatricyclo[7.3.1.05,13]tridecan-6-yl]propyl] acetate
• CAS: 315662-31-8
• 化学式: C₁₉H₃₀O₇S
• 分子量: 402.509
• InChiKey: JKEHHZNBLFMLLD-JELDIUQKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  27.0
• 可旋转键数：
  4.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  88.13
• 氢给体数：
  0.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  1β,12-diacetoxy-5α,11β-H-eudesman-4α,6α-diyl-S(R)-cyclic sulfite 在 ruthenium trichloride 、 sodium periodate 作用下， 以 四氯化碳 、 水 、 乙腈 为溶剂， 反应 12.0h， 以100%的产率得到1β,12-diacetoxy-5α,11β-H-eudesman-4α,6α-diyl-S-cyclic sulfate
  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：

  vulgarin 在 platinum(IV) oxide Candida antarctica lipase 、 lithium aluminium tetrahydride 、 氯化亚砜 、 氢气 作用下， 以 四氢呋喃 、 吡啶 为溶剂， 反应 1.5h， 生成 1β,12-diacetoxy-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