(5S,9S,10S,E)-12,12-diethyl-9-(4-methoxybenzyloxy)-2,2,3,3-tetramethyl-5-((S)-4-methyl-2-methylene-5-((2R,6R)-6-(prop-2-ynyl)-3,6-dihydro-2H-pyran-2-yl)pentyl)-10-((E)-2-((S)-4-methyl-3,6-dihydro-2H-pyran-2-yl)vinyl)-4,11-dioxa-3,12-disilatetradec-6-ene | 1072083-02-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (5S,9S,10S,E)-12,12-diethyl-9-(4-methoxybenzyloxy)-2,2,3,3-tetramethyl-5-((S)-4-methyl-2-methylene-5-((2R,6R)-6-(prop-2-ynyl)-3,6-dihydro-2H-pyran-2-yl)pentyl)-10-((E)-2-((S)-4-methyl-3,6-dihydro-2H-pyran-2-yl)vinyl)-4,11-dioxa-3,12-disilatetradec-6-ene
• 英文别名: tert-butyl-[(2S,6S,7E,10S,11S,12E)-10-[(4-methoxyphenyl)methoxy]-2-methyl-13-[(2S)-4-methyl-3,6-dihydro-2H-pyran-2-yl]-4-methylidene-1-[(2R,6R)-6-prop-2-ynyl-3,6-dihydro-2H-pyran-2-yl]-11-triethylsilyloxytrideca-7,12-dien-6-yl]oxy-dimethylsilane
• CAS: 1072083-02-3
• 化学式: C₄₉H₇₈O₆Si₂
• 分子量: 819.326
• InChiKey: ZTUFFKXHDOXYRB-SXGIPWSTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.7
• 重原子数：
  57
• 可旋转键数：
  25
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.63
• 拓扑面积：
  55.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  二氧化碳 、 (5S,9S,10S,E)-12,12-diethyl-9-(4-methoxybenzyloxy)-2,2,3,3-tetramethyl-5-((S)-4-methyl-2-methylene-5-((2R,6R)-6-(prop-2-ynyl)-3,6-dihydro-2H-pyran-2-yl)pentyl)-10-((E)-2-((S)-4-methyl-3,6-dihydro-2H-pyran-2-yl)vinyl)-4,11-dioxa-3,12-disilatetradec-6-ene 在 正丁基锂 、 氟化氢吡啶 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 0.34h， 以85%的产率得到4-((2R,6R)-6-((2S,6S,7E,10S,11S,12E)-6-(tert-butyldimethylsilyloxy)-11-hydroxy-10-(4-methoxybenzyloxy)-2-methyl-13-((S)-4-methyl-3,6-dihydro-2H-pyran-2-yl)-4-methylenetrideca-7,12-dienyl)-5,6-dihydro-2H-pyran-2-yl)but-2-ynoic acid
  参考文献：
  名称：

  Total Synthesis of Neolaulimalide and Isolaulimalide

  摘要：

  The first total syntheses of the potential antitumoral leads neolaulimalide (2) and isolaulimalide (3) have been achieved. Key steps in our convergent, fully stereocontrolled route are a Yamaguchi macrolactonization, a Julia-Lythgoe-Kocienski olefination, a Kulinkovich reaction, and a cyclopropyl-allyl rearrangement to install the exo-methylene group. Overall, we synthesized 2 in 21 linear steps (3% yield) and 3 in 24 steps (2% yield).

  DOI：

  10.1021/ol802075v
• 作为产物：
  描述：

  (2S,6S)-2-(tert-butyldimethylsilyloxy)-6-methyl-4-methylene-7-((2R,6R)-6-(prop-2-ynyl)-3,6-dihydro-2H-pyran-2-yl)heptanal 、 5-((3S,4S,E)-3-(4-methoxybenzyloxy)-6-((S)-4-methyl-3,6-dihydro-2H-pyran-2-yl)-4-(triethylsilyloxy)hex-5-enylsulfonyl)-1-phenyl-1H-tetrazole 在 双(三甲基硅烷基)氨基钾 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 1.7h， 以76%的产率得到(5S,9S,10S,E)-12,12-diethyl-9-(4-methoxybenzyloxy)-2,2,3,3-tetramethyl-5-((S)-4-methyl-2-methylene-5-((2R,6R)-6-(prop-2-ynyl)-3,6-dihydro-2H-pyran-2-yl)pentyl)-10-((E)-2-((S)-4-methyl-3,6-dihydro-2H-pyran-2-yl)vinyl)-4,11-dioxa-3,12-disilatetradec-6-ene
  参考文献：
  名称：

  Total Synthesis of Neolaulimalide and Isolaulimalide

  摘要：

  The first total syntheses of the potential antitumoral leads neolaulimalide (2) and isolaulimalide (3) have been achieved. Key steps in our convergent, fully stereocontrolled route are a Yamaguchi macrolactonization, a Julia-Lythgoe-Kocienski olefination, a Kulinkovich reaction, and a cyclopropyl-allyl rearrangement to install the exo-methylene group. Overall, we synthesized 2 in 21 linear steps (3% yield) and 3 in 24 steps (2% yield).

  DOI：

  10.1021/ol802075v

文献信息

• The Laulimalide Family: Total Synthesis and Biological Evaluation of Neolaulimalide, Isolaulimalide, Laulimalide and a Nonnatural Analogue
  作者：Andreas Gollner、Karl-Heinz Altmann、Jürg Gertsch、Johann Mulzer

  DOI：10.1002/chem.200802605

  日期：2009.6.8

  A sensitive family: The first total synthesis of the antitumor agents neolaulimalide and isolaulimalide as well as a highly efficient route to laulimalide is described. A Kulinkovich reaction followed by a cyclopropyl–allyl rearrangement is used to install the exo‐methylene group. The cytotoxicity of neolaulimalide could be confirmed for the first time since its original isolation and it could be shown

  敏感家族：描述了抗肿瘤药新月桂酰亚胺和异乌贼胺的第一个全合成方法以及高效的合成方法。先进行Kulinkovich反应，然后再进行环丙基-烯丙基重排，以安装exo-亚甲基。自从最初分离出新月桂利特以来，它的细胞毒性首次得到证实，并且可以证明它诱导的微管蛋白聚合作用与劳来那利一样有效。
• Total Synthesis of Neolaulimalide and Isolaulimalide
  作者：Andreas Gollner、Johann Mulzer

  DOI：10.1021/ol802075v

  日期：2008.10.16

  The first total syntheses of the potential antitumoral leads neolaulimalide (2) and isolaulimalide (3) have been achieved. Key steps in our convergent, fully stereocontrolled route are a Yamaguchi macrolactonization, a Julia-Lythgoe-Kocienski olefination, a Kulinkovich reaction, and a cyclopropyl-allyl rearrangement to install the exo-methylene group. Overall, we synthesized 2 in 21 linear steps (3% yield) and 3 in 24 steps (2% yield).