myricerone ketal | 173554-46-6

• 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: myricerone ketal
• 英文别名: (4'aS,6'aR,6'aR,6'bR,8'aR,12'aR,14'bS)-6'a-(hydroxymethyl)-2',2',6'b,9',9',12'a-hexamethylspiro[1,3-dioxolane-2,10'-3,4,5,6,6a,7,8,8a,11,12,13,14b-dodecahydro-1H-picene]-4'a-carboxylic acid
• CAS: 173554-46-6
• 化学式: C₃₂H₅₀O₅
• 分子量: 514.746
• InChiKey: LWJUHCIVELDKRU-OHVMGTHFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  37
• 可旋转键数：
  2
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  76
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  myricerone ketal 在 盐酸 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 N,N'-羰基二咪唑 、 三氟乙酸 、 lithium chloride 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 13.75h， 生成 (4-碘-苯甲基)-膦酸二乙基酯
  参考文献：
  名称：

  Practical Partial Synthesis of Myriceric Acid A, an Endothelin Receptor Antagonist, from Oleanolic Acid

  摘要：

  Myriceric acid A (1) is an oleanane triterpene that is a potent and specific endothelin A receptor antagonist. A practical procedure for large-scale synthesis of myriceric acid A (1) has been developed starting from oleanolic acid 4. The conversion of oleanolic acid 4 to the key intermediate myricerone 3 was achieved in an efficient manner employing a photochemical reaction (the Barton reaction) of nitrite 7. Our synthetic procedure alleviated several difficulties of the original Barton's procedure with regard to yields and large-scale operation. Myricerone 3 afforded Horner-Wadsworth-Emmons (HWE) type phosphonate 2 which has proved to be a versatile precursor of 1. The preparation of phosphonate 2 on a scale of several hundred grams is described. The synthesis was completed by condensation of 2 with 3,4-bis[(diphenylmethyl)oxy]benzaldehyde (21), giving alpha,beta-unsaturated ester 22, which was deprotected to afford 1. The whole synthetic sequence is efficient (14 steps, 31% yield) and requires no chromatographic purification except to obtain the final product 1.

  DOI：

  10.1021/jo9615864
• 作为产物：
  描述：

  [(1'S,4'R,5'R,8'R,13'R,14'R,16'S,17'S,18'R)-4'-formyl-5',9',9',13',20',20'-hexamethyl-23'-oxospiro[1,3-dioxolane-2,10'-24-oxahexacyclo[15.5.2.01,18.04,17.05,14.08,13]tetracosane]-16'-yl] acetate 在 氨 、 lithium 作用下， 以 四氢呋喃 为溶剂， 反应 1.75h， 以90%的产率得到myricerone ketal
  参考文献：
  名称：

  Practical Partial Synthesis of Myriceric Acid A, an Endothelin Receptor Antagonist, from Oleanolic Acid

  摘要：

  Myriceric acid A (1) is an oleanane triterpene that is a potent and specific endothelin A receptor antagonist. A practical procedure for large-scale synthesis of myriceric acid A (1) has been developed starting from oleanolic acid 4. The conversion of oleanolic acid 4 to the key intermediate myricerone 3 was achieved in an efficient manner employing a photochemical reaction (the Barton reaction) of nitrite 7. Our synthetic procedure alleviated several difficulties of the original Barton's procedure with regard to yields and large-scale operation. Myricerone 3 afforded Horner-Wadsworth-Emmons (HWE) type phosphonate 2 which has proved to be a versatile precursor of 1. The preparation of phosphonate 2 on a scale of several hundred grams is described. The synthesis was completed by condensation of 2 with 3,4-bis[(diphenylmethyl)oxy]benzaldehyde (21), giving alpha,beta-unsaturated ester 22, which was deprotected to afford 1. The whole synthetic sequence is efficient (14 steps, 31% yield) and requires no chromatographic purification except to obtain the final product 1.

  DOI：

  10.1021/jo9615864

文献信息

• Practical Large-Scale Synthesis of Endothelin Receptor Antagonist S-0139
  作者：Toshiro Konoike、Katsuo Oda、Masaaki Uenaka、Kazuhiro Takahashi

  DOI：10.1021/op990036f

  日期：1999.9.1