2-(ethylenedioxy)-7-methylene-1α,4aβ,8aβ-trimethyl-1,2,3,4,4a,6,7,8,8a,9-decahydrophenanthrene-8α-ethanol | 131250-76-5

• 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: 2-(ethylenedioxy)-7-methylene-1α,4aβ,8aβ-trimethyl-1,2,3,4,4a,6,7,8,8a,9-decahydrophenanthrene-8α-ethanol
• 英文别名: 2-[(1R,4bR,8R,10aR)-4b,8,10a-trimethyl-2-methylidenespiro[1,3,5,6,8,10-hexahydrophenanthrene-7,2'-1,3-dioxolane]-1-yl]ethanol
• CAS: 131250-76-5
• 化学式: C₂₂H₃₂O₃
• 分子量: 344.494
• InChiKey: BIAXVDPNTRHWTK-DEPWHIHDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  25
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-(ethylenedioxy)-7-methylene-1α,4aβ,8aβ-trimethyl-1,2,3,4,4a,6,7,8,8a,9-decahydrophenanthrene-8α-ethanol 在 platinum(IV) oxide 吡啶 、 氢氧化钾 、 chromium trioxide-pyridine complex 、 氢气 作用下， 以 甲醇 、 乙醇 、 二氯甲烷 、 水 为溶剂， 25.0 ℃ 、101.33 kPa 条件下， 反应 7.5h， 生成 2-(ethylenedioxy)-8α-(2-hydroxyethyl)-1α,4aβ,7α,8aβ-tetramethyl-1,2,3,4,4a,6,7,8,8a,9-decahydrophenanthren-6-one
  参考文献：
  名称：

  Total synthesis of (.+-.)-amarolide, a quassinoid bitter principle

  摘要：

  The first total synthesis of amarolide (1), a bitter tasting quassinoid having a picrasane skeleton with 10 chiral centers, is described in racemic form. The synthesis of (+/-)-1 was accomplished stereoselectively in 35 steps and 0.5% overall yield from a known tricyclic compound 7. An orthoester Claisen rearrangement and a lead tetraacetate oxidation were utilized as key reactions to prepare hydroxy ketone 14 with a complete picrasane skeleton. This hydroxy ketone was transformed into 1 in 18 steps that included 1,3-carbonyl transposition, introduction of hydroxyl groups at C-2 and C-11 positions, and oxidation of an ether to afford a delta-lactone.

  DOI：

  10.1021/jo00003a039
• 作为产物：
  描述：

  ethyl 2-(ethylenedioxy)-1α,4aβ,8aβ-trimethyl-7-methylene-1,2,3,4,4a,6,7,8,8a,9-decahydrophenanthrene-8α-acetate 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 反应 1.5h， 以72%的产率得到2-(ethylenedioxy)-7-methylene-1α,4aβ,8aβ-trimethyl-1,2,3,4,4a,6,7,8,8a,9-decahydrophenanthrene-8α-ethanol
  参考文献：
  名称：

  Total synthesis of (.+-.)-amarolide, a quassinoid bitter principle

  摘要：

  The first total synthesis of amarolide (1), a bitter tasting quassinoid having a picrasane skeleton with 10 chiral centers, is described in racemic form. The synthesis of (+/-)-1 was accomplished stereoselectively in 35 steps and 0.5% overall yield from a known tricyclic compound 7. An orthoester Claisen rearrangement and a lead tetraacetate oxidation were utilized as key reactions to prepare hydroxy ketone 14 with a complete picrasane skeleton. This hydroxy ketone was transformed into 1 in 18 steps that included 1,3-carbonyl transposition, introduction of hydroxyl groups at C-2 and C-11 positions, and oxidation of an ether to afford a delta-lactone.

  DOI：

  10.1021/jo00003a039

文献信息

• HIROTA, HIROSHI;YOKOYAMA, AKIHISA;MIYAJI, KATSUAKI;NAKAMURA, TOSHIO;IGARA+, J. ORG. CHEM., 56,(1991) N, C. 1119-1127
  作者：HIROTA, HIROSHI、YOKOYAMA, AKIHISA、MIYAJI, KATSUAKI、NAKAMURA, TOSHIO、IGARA+

  DOI：——

  日期：——