seco-plakortolide E | 1353566-42-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: seco-plakortolide E
• 英文别名: (4R,5R)-4-hydroxy-5-((R)-2-hydroxy-2-methyl-12-phenyldodecyl)-5-methyldihydrofuran-2(3H)-one；(4R,5R)-4-hydroxy-5-[(2R)-2-hydroxy-2-methyl-12-phenyldodecyl]-5-methyloxolan-2-one
• CAS: 1353566-42-3
• 化学式: C₂₄H₃₈O₄
• 分子量: 390.563
• InChiKey: GFBQUZIAOMGAPQ-GMKZXUHWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.8
• 重原子数：
  28
• 可旋转键数：
  13
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  66.8
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  seco-plakortolide E 、 (S)-(+)-alpha-甲氧基苯乙酸 在 4-二甲氨基吡啶 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 以68%的产率得到(S)-(2R,3R)-2-[(R)-2-hydroxy-2-methyl-12-phenyldodecyl]-2-methyl-5-oxotetrahydrofuran-3-yl 2-methoxy-2-phenylacetate
  参考文献：
  名称：

  Plakortolide Stereochemistry Revisited: The Checkered History of Plakortolides E and I

  摘要：

  The relative configuration of the plakortolide metabolite (4) isolated from a Madagascan Plakortis sp. and named (+)-plakortolide I is revised following reassignment of the C-13 signals for C-7 and C-16, thereby establishing that the metabolite isolated was likely (+)-plakortolide E (3). 'We propose that the name "plakortolide I" should be retained for the plakortolide metabolite 5 first isolated by the Faulkner group; its enantiomer 4 can then be named ent-plakortolide I in line with the description of Barnych and Vatele. The spectroscopic data for MPA esters prepared from synthetic samples of seco derivatives of plakortolide E (3) and ent-plakortolide I (4) were compared with those of MPA esters of seco derivatives from naturally isolated plakortolides L (1) and K (2) and of seco-plakortolide E (6a). Likewise, the spectroscopic data for MTPA esters derived from 3 and 4 were compared with data for the MTPA esters derived from S. These various comparisons established that the sign of the specific rotation associated with the natural isolates is an unreliable indicator of absolute configuration and verify that the absolute configurations of plakortolides L (1), K (2), E (3), and I (5) are (3S, 4S, 6S), (3R, 4R, 6S), (3R, 4R, 6R), and (3S, 4S, 6R), respectively.

  DOI：

  10.1021/np3005634
• 作为产物：
  描述：

  9-phenyl-1-bromononane 在 titanium(IV) isopropylate 、 4-二甲氨基吡啶 、 草酰氯 、 双(2,2,6,6,-四甲基-3,5-庚二酮酸)钴 、 四丁基氟化铵 、 叔丁基锂 、 氧气 、 silica gel 、 四氯化钛 、 magnesium 、 溶剂黄146 、 二甲基亚砜 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三乙胺 、 锌 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 1,2-二氯乙烷 、 Petroleum ether 、 正戊烷 为溶剂， 反应 56.17h， 生成 seco-plakortolide E
  参考文献：
  名称：

  的全合成塞科（ - - ）-Plakortolide E和耳鼻喉科自然的绝对构形修订Plakortolide我：-Plakortolide我

  摘要：

  （ - ） -的第一全合成ENT -plakortolide I和开环-plakortolide E的从（完成小号）-2- methylglycidol。相关的关键反应包括非对映选择性的Mukaiyama羟醛反应，区域选择性的氢过氧化甲硅烷基化，以及通过分子内迈克尔将氢过氧化物基团加到丁烯酸内酯来精制1,2-二恶烷环。该合成允许对普拉托利特I的绝对构型进行修改，并对普拉托利特E进行结构上的修改。

  DOI：

  10.1021/ol203185f

文献信息

• Total Synthesis of <i>seco</i>-Plakortolide E and (−)-<i>ent</i>-Plakortolide I: Absolute Configurational Revision of Natural Plakortolide I
  作者：Bogdan Barnych、Jean-Michel Vatèle

  DOI：10.1021/ol203185f

  日期：2012.1.20

  A first total synthesis of (−)-ent-plakortolide I and seco-plakortolide E was accomplished from (S)-2-methylglycidol. The relevant key reactions involve a diastereoselective Mukaiyama aldol reaction, a regioselective hydroperoxysilylation, and elaboration of the 1,2-dioxane ring by intramolecular Michael addition of a hydroperoxide group to a butenolide. This synthesis allowed the revision of the absolute

  （ - ） -的第一全合成ENT -plakortolide I和开环-plakortolide E的从（完成小号）-2- methylglycidol。相关的关键反应包括非对映选择性的Mukaiyama羟醛反应，区域选择性的氢过氧化甲硅烷基化，以及通过分子内迈克尔将氢过氧化物基团加到丁烯酸内酯来精制1,2-二恶烷环。该合成允许对普拉托利特I的绝对构型进行修改，并对普拉托利特E进行结构上的修改。
• Plakortolide Stereochemistry Revisited: The Checkered History of Plakortolides E and I
  作者：Ken W. L. Yong、Bogdan Barnych、James J. De Voss、Jean-Michel Vatèle、Mary J. Garson

  DOI：10.1021/np3005634

  日期：2012.10.26

  The relative configuration of the plakortolide metabolite (4) isolated from a Madagascan Plakortis sp. and named (+)-plakortolide I is revised following reassignment of the C-13 signals for C-7 and C-16, thereby establishing that the metabolite isolated was likely (+)-plakortolide E (3). 'We propose that the name "plakortolide I" should be retained for the plakortolide metabolite 5 first isolated by the Faulkner group; its enantiomer 4 can then be named ent-plakortolide I in line with the description of Barnych and Vatele. The spectroscopic data for MPA esters prepared from synthetic samples of seco derivatives of plakortolide E (3) and ent-plakortolide I (4) were compared with those of MPA esters of seco derivatives from naturally isolated plakortolides L (1) and K (2) and of seco-plakortolide E (6a). Likewise, the spectroscopic data for MTPA esters derived from 3 and 4 were compared with data for the MTPA esters derived from S. These various comparisons established that the sign of the specific rotation associated with the natural isolates is an unreliable indicator of absolute configuration and verify that the absolute configurations of plakortolides L (1), K (2), E (3), and I (5) are (3S, 4S, 6S), (3R, 4R, 6S), (3R, 4R, 6R), and (3S, 4S, 6R), respectively.