2-[(2R,4S,6S)-4-[tert-butyl(diphenyl)silyl]oxy-2-methoxy-6-[(2E,4S,5S,7R,8E,11R)-5,7,11-trihydroxy-4,6,6,8-tetramethylhexadeca-2,8-dien-2-yl]oxan-2-yl]acetic acid | 1000788-24-8

• 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: 2-[(2R,4S,6S)-4-[tert-butyl(diphenyl)silyl]oxy-2-methoxy-6-[(2E,4S,5S,7R,8E,11R)-5,7,11-trihydroxy-4,6,6,8-tetramethylhexadeca-2,8-dien-2-yl]oxan-2-yl]acetic acid
• CAS: 1000788-24-8
• 化学式: C₄₄H₆₈O₈Si
• 分子量: 753.105
• InChiKey: HIHMQPZNNSZHIR-PLDLPLEVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.54
• 重原子数：
  53
• 可旋转键数：
  20
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.61
• 拓扑面积：
  126
• 氢给体数：
  4
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  2-[(2R,4S,6S)-4-[tert-butyl(diphenyl)silyl]oxy-2-methoxy-6-[(2E,4S,5S,7R,8E,11R)-5,7,11-trihydroxy-4,6,6,8-tetramethylhexadeca-2,8-dien-2-yl]oxan-2-yl]acetic acid 在 2,4,6-三氯苯甲酰氯 、 三乙胺 、 4-二甲氨基吡啶 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 15.5h， 生成 (1Z,5R,7E,9R,11S,12S,13E,15S,17S)-17-[tert-butyl(diphenyl)silyl]oxy-9,11-dihydroxy-8,10,10,12,14-pentamethyl-5-pentyl-4,19-dioxabicyclo[13.3.1]nonadeca-1,7,13-trien-3-one 、 (1R,5R,7E,9R,11S,12S,13E,15S,17S)-17-[tert-butyl(diphenyl)silyl]oxy-9,11-dihydroxy-1-methoxy-8,10,10,12,14-pentamethyl-5-pentyl-4,19-dioxabicyclo[13.3.1]nonadeca-7,13-dien-3-one
  参考文献：
  名称：

  Total Synthesis of (+)-Acutiphycin

  摘要：

  [GRAPHICS]Synthetic studies toward the total synthesis of (+)-acutiphycin (1) resulted in the discovery of additive-free, highly regioselective nickel -catalyzed reductive coupling reactions of aldehydes and 1,6-enynes and the construction of an advanced intermediate in studies directed toward the synthesis of 1. Ultimately, although not employing the nickel-catalyzed reaction, a highly convergent total synthesis of (+)-acutiphycin featuring an intermolecular SMI2-mediated Reformatsky coupling reaction and macrolactonization initiated by a retro-ene reaction of an alkoxyalkyne was achieved. The resulting synthesis was 18 steps in the longest linear sequence from either methyl acetoacetate or isobutyraldehyde.

  DOI：

  10.1021/jo701821h
• 作为产物：
  描述：

  甲醇 、 (4S,6S)-4-[tert-butyl(diphenyl)silyl]oxy-6-[(2E,4S,5S,7R,8E,11R)-5,7,11-trihydroxy-4,6,6,8-tetramethylhexadeca-2,8-dien-2-yl]oxan-2-one 、 乙酸乙酯 在 lithium diisopropyl amide 、 柠檬酸 、 lithium hydroxide 作用下， 以 四氢呋喃 、 正己烷 、 甲醇 、 水 为溶剂， 反应 2.0h， 以64%的产率得到2-[(2R,4S,6S)-4-[tert-butyl(diphenyl)silyl]oxy-2-methoxy-6-[(2E,4S,5S,7R,8E,11R)-5,7,11-trihydroxy-4,6,6,8-tetramethylhexadeca-2,8-dien-2-yl]oxan-2-yl]acetic acid
  参考文献：
  名称：

  Total Synthesis of (+)-Acutiphycin

  摘要：

  [GRAPHICS]Synthetic studies toward the total synthesis of (+)-acutiphycin (1) resulted in the discovery of additive-free, highly regioselective nickel -catalyzed reductive coupling reactions of aldehydes and 1,6-enynes and the construction of an advanced intermediate in studies directed toward the synthesis of 1. Ultimately, although not employing the nickel-catalyzed reaction, a highly convergent total synthesis of (+)-acutiphycin featuring an intermolecular SMI2-mediated Reformatsky coupling reaction and macrolactonization initiated by a retro-ene reaction of an alkoxyalkyne was achieved. The resulting synthesis was 18 steps in the longest linear sequence from either methyl acetoacetate or isobutyraldehyde.

  DOI：

  10.1021/jo701821h

文献信息

• Total Synthesis of (+)-Acutiphycin
  作者：Ryan M. Moslin、Timothy F. Jamison

  DOI：10.1021/jo701821h

  日期：2007.12.1

  [GRAPHICS]Synthetic studies toward the total synthesis of (+)-acutiphycin (1) resulted in the discovery of additive-free, highly regioselective nickel -catalyzed reductive coupling reactions of aldehydes and 1,6-enynes and the construction of an advanced intermediate in studies directed toward the synthesis of 1. Ultimately, although not employing the nickel-catalyzed reaction, a highly convergent total synthesis of (+)-acutiphycin featuring an intermolecular SMI2-mediated Reformatsky coupling reaction and macrolactonization initiated by a retro-ene reaction of an alkoxyalkyne was achieved. The resulting synthesis was 18 steps in the longest linear sequence from either methyl acetoacetate or isobutyraldehyde.