(1R,3Z,7S,9E,11S,17R)-11-hydroxy-7-[(E,1S)-1-hydroxy-3-[(2S)-4-methyl-3,6-dihydro-2H-pyran-2-yl]prop-2-enyl]-13-methylidene-6,21-dioxabicyclo[15.3.1]henicosa-3,9,19-trien-5-one | 688743-66-0

• 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: (1R,3Z,7S,9E,11S,17R)-11-hydroxy-7-[(E,1S)-1-hydroxy-3-[(2S)-4-methyl-3,6-dihydro-2H-pyran-2-yl]prop-2-enyl]-13-methylidene-6,21-dioxabicyclo[15.3.1]henicosa-3,9,19-trien-5-one
• CAS: 688743-66-0
• 化学式: C₂₉H₄₀O₆
• 分子量: 484.633
• InChiKey: BTIQOISAFIJFAV-AIYSHJQZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  35
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  85.2
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (1R,3Z,7S,9E,11S,17R)-11-hydroxy-7-[(E,1S)-1-hydroxy-3-[(2S)-4-methyl-3,6-dihydro-2H-pyran-2-yl]prop-2-enyl]-13-methylidene-6,21-dioxabicyclo[15.3.1]henicosa-3,9,19-trien-5-one 在 4 A molecular sieve titanium(IV) isopropylate 、 叔丁基过氧化氢 、 L-(+)-酒石酸二异丙酯 作用下， 以 二氯甲烷 为溶剂， 生成 11-desmethyl-laulimalide
  参考文献：
  名称：

  Synthesis of Novel 11-Desmethyl Analogues of Laulimalide by Nozaki−Kishi Coupling

  摘要：

  As a first entry into structurally simplified analogues of the anticancer agent laulimalide, 11-desmethyl compounds 2 and 3 were selected by molecular modeling. The unfavorable diastereoselectivity in the key synthetic step, a Nozaki-Kishi coupling between macrocyclic aldehyde 4 and vinyl iodide 5, was overcome either by use of catalytic amounts of DIANANE-type ligands or L-Selectride reduction of the derived enone. This methodology should allow modular introduction of other, unnatural, side chains.

  DOI：

  10.1021/ol049791q
• 作为产物：
  描述：

  5-氧代戊酸甲酯 在 Lindlar's catalyst 、 四(三苯基膦)钯 喹啉 、 正丁基锂 、 1-己烯 、 cerium(III) chloride 、 二甲基溴化硼 、 甲基叔丁基醚 、 四甲基乙二胺 、 (S,S)-Cr-Salen*BF₄ 、 4 A molecular sieve 、 Yamamoto's (acyloxy)borane 、 2,4,6-三氯苯甲酰氯 、 氢气 、 三正丁基氢锡 、 potassium carbonate 、 氟化氢吡啶 、 三乙胺 、 N,N-二异丙基乙胺 、 丙腈 、 lithium chloride 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 、 乙酸乙酯 、 1,2-二氯乙烷 为溶剂， -78.0~20.0 ℃ 、101.33 kPa 条件下， 反应 253.19h， 生成 (1R,3Z,7S,9E,11S,17R)-11-hydroxy-7-[(E,1S)-1-hydroxy-3-[(2S)-4-methyl-3,6-dihydro-2H-pyran-2-yl]prop-2-enyl]-13-methylidene-6,21-dioxabicyclo[15.3.1]henicosa-3,9,19-trien-5-one
  参考文献：
  名称：

  Total Synthesis and Biological Evaluation of 11-Desmethyllaulimalide, a Highly Potent Simplified Laulimalide Analogue

  摘要：

  A step-economical synthesis of 11-desmethyllaulimalide (2) is reported. This simplified analogue is available through an improved second-generation synthetic approach to the laulimalides, in a shorter step count and from much less expensive starting material than the parent compound. This new lead retains the anticancer function of laulimalide.

  DOI：

  10.1021/ol060233g

文献信息

• Synthesis of Novel 11-Desmethyl Analogues of Laulimalide by Nozaki−Kishi Coupling
  作者：Ian Paterson、Hermann Bergmann、Dirk Menche、Albrecht Berkessel

  DOI：10.1021/ol049791q

  日期：2004.4.1

  As a first entry into structurally simplified analogues of the anticancer agent laulimalide, 11-desmethyl compounds 2 and 3 were selected by molecular modeling. The unfavorable diastereoselectivity in the key synthetic step, a Nozaki-Kishi coupling between macrocyclic aldehyde 4 and vinyl iodide 5, was overcome either by use of catalytic amounts of DIANANE-type ligands or L-Selectride reduction of the derived enone. This methodology should allow modular introduction of other, unnatural, side chains.
• Total Synthesis and Biological Evaluation of 11-Desmethyllaulimalide, a Highly Potent Simplified Laulimalide Analogue
  作者：Paul A. Wender、Michael K. Hilinski、Nicolas Soldermann、Susan L. Mooberry

  DOI：10.1021/ol060233g

  日期：2006.3.1

  A step-economical synthesis of 11-desmethyllaulimalide (2) is reported. This simplified analogue is available through an improved second-generation synthetic approach to the laulimalides, in a shorter step count and from much less expensive starting material than the parent compound. This new lead retains the anticancer function of laulimalide.