tert-butyl (2E,4E,6R)-6-{(2R,4E,6E,10S,11S,12E,14S,18E)-10-[(4-methoxybenzyl)oxy]-4-methyl-20-oxo-11,14-bis[(tri(propan-2-yl)silyl)oxy]oxacycloicosa-4,6,12,18-tetraen-2-yl}-4-methylhepta-2,4-dienoate | 1191072-37-3

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 大环内酯类和类似物
• 英文名称: tert-butyl (2E,4E,6R)-6-{(2R,4E,6E,10S,11S,12E,14S,18E)-10-[(4-methoxybenzyl)oxy]-4-methyl-20-oxo-11,14-bis[(tri(propan-2-yl)silyl)oxy]oxacycloicosa-4,6,12,18-tetraen-2-yl}-4-methylhepta-2,4-dienoate
• 英文别名: tert-butyl (2E,4E,6R)-6-[(2R,4E,6E,10S,11S,12E,14S,18E)-10-[(4-methoxyphenyl)methoxy]-4-methyl-20-oxo-11,14-bis[tri(propan-2-yl)silyloxy]-1-oxacycloicosa-4,6,12,18-tetraen-2-yl]-4-methylhepta-2,4-dienoate
• CAS: 1191072-37-3
• 化学式: C₅₈H₉₆O₈Si₂
• 分子量: 977.566
• InChiKey: ARCKAQSNCRCEOR-KKSIIXOVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  16.06
• 重原子数：
  68
• 可旋转键数：
  20
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.66
• 拓扑面积：
  89.5
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  tert-butyl (2E,4E,6R)-6-{(2R,4E,6E,10S,11S,12E,14S,18E)-10-[(4-methoxybenzyl)oxy]-4-methyl-20-oxo-11,14-bis[(tri(propan-2-yl)silyl)oxy]oxacycloicosa-4,6,12,18-tetraen-2-yl}-4-methylhepta-2,4-dienoate 在 三氟甲磺酸三甲基硅酯 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 以94%的产率得到(2E,4E,6R)-6-{(2R,4E,6E,10S,11S,12E,14S,18E)-10-[(4-methoxybenzyl)oxy]-4-methyl-20-oxo-11,14-bis[(tri(propan-2-yl)silyl)oxy]oxacycloicosa-4,6,12,18-tetraen-2-yl}-4-methylhepta-2,4-dienoic acid
  参考文献：
  名称：

  Catalytic Asymmetric Synthesis of Palmerolide A via Organoboron Methodology

  摘要：

  A catalytic enantioselective synthesis of the antimelanoma marine natural product (-)-palmerolide A was accomplished using a longest sequence of 21 steps and without resorting to stoichiometric chiral auxiliaries or the chiral pool. The right half was constructed with a new variant of the Claisen-Ireland rearrangement exploiting an alkenylboronate as a masked hydroxyl. The left half featured the first application of a diol.SnCl4-catalyzed enantioselective crotylboration in the context of a complex target. This distinct strategy could the way to the design of simplified analogues of palmerolide.

  DOI：

  10.1021/ja906429c
• 作为产物：
  描述：

  (2E,7S,8E,10S,11S,14E,16E,19R,20R,21E,23E)-25-tert-butoxy-19-hydroxy-11-[(4-methoxybenzyl)oxy]-17,20,22-trimethyl-25-oxo-7,10-bis[(tri(propan-2-yl)silyl)oxy]pentacosa-2,8,14,16,21,23-hexaenoic 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 2.0h， 以90%的产率得到tert-butyl (2E,4E,6R)-6-{(2R,4E,6E,10S,11S,12E,14S,18E)-10-[(4-methoxybenzyl)oxy]-4-methyl-20-oxo-11,14-bis[(tri(propan-2-yl)silyl)oxy]oxacycloicosa-4,6,12,18-tetraen-2-yl}-4-methylhepta-2,4-dienoate
  参考文献：
  名称：

  Catalytic Asymmetric Synthesis of Palmerolide A via Organoboron Methodology

  摘要：

  A catalytic enantioselective synthesis of the antimelanoma marine natural product (-)-palmerolide A was accomplished using a longest sequence of 21 steps and without resorting to stoichiometric chiral auxiliaries or the chiral pool. The right half was constructed with a new variant of the Claisen-Ireland rearrangement exploiting an alkenylboronate as a masked hydroxyl. The left half featured the first application of a diol.SnCl4-catalyzed enantioselective crotylboration in the context of a complex target. This distinct strategy could the way to the design of simplified analogues of palmerolide.

  DOI：

  10.1021/ja906429c

文献信息

• Catalytic Asymmetric Synthesis of Palmerolide A via Organoboron Methodology
  作者：Marlin Penner、Vivek Rauniyar、Ludwig T. Kaspar、Dennis G. Hall

  DOI：10.1021/ja906429c

  日期：2009.10.14

  A catalytic enantioselective synthesis of the antimelanoma marine natural product (-)-palmerolide A was accomplished using a longest sequence of 21 steps and without resorting to stoichiometric chiral auxiliaries or the chiral pool. The right half was constructed with a new variant of the Claisen-Ireland rearrangement exploiting an alkenylboronate as a masked hydroxyl. The left half featured the first application of a diol.SnCl4-catalyzed enantioselective crotylboration in the context of a complex target. This distinct strategy could the way to the design of simplified analogues of palmerolide.