(+/-)-invictolide

• 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: (+/-)-invictolide
• 英文别名: (3S,5S,6R)-3,5-dimethyl-6-[(2S)-pentan-2-yl]oxan-2-one
• 化学式: C₁₂H₂₂O₂
• 分子量: 198.305
• InChiKey: AZBHSLUQWMFDHU-XWLWVQCSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  2-甲基戊醛 在 4-二甲氨基吡啶 、 lithium aluminium tetrahydride 、 potassium tert-butylate 、 三乙胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 24.83h， 生成 (+/-)-invictolide
  参考文献：
  名称：

  Stereoselective total synthesis of (.+-.)-invictolide. An efficient preparation of a trisubstituted .delta.-lactone from aldol precursors

  摘要：

  The stereoselective total synthesis of (+/-)-invictolide (1), a component of the queen recognition pheromone of Solenopsis invicta, is described. The TiCl4-mediated addition of silyl ketene thioacetal 8 to (+/-)-3-(benzyloxy)-2-methylpropionaldehyde afforded exclusively thioester 10, in 65% yield, which was straightforwardly converted to diol 5 (ca. 31% yield). Diol 5 was also prepared after LiAlH4 reduction of the major aldol formed in the condensation between the lithium enolate of 2,6-di-tert-butyl-4-methylphenyl propanoate and (+/-)-2-methylvaleraldehyde (ca.50% overall yield). Intramolecular alkylation (t-BuOK-THF) of 6 or 7 gave a 40:60 mixture of (+/-)-1 and its C(3) epimer. Catalytic hydrogenation of unsaturated lactone 17 afforded (+/-)-1 in 80% yield.

  DOI：

  10.1021/jo00054a014

文献信息

• Desymmetrization of <i>C</i> ₂ ‐Symmetric Bis(Boronic Esters) by Zweifel Olefinations
  作者：Yannick Linne、Axel Schönwald、Sebastian Weißbach、Markus Kalesse

  DOI：10.1002/chem.202000599

  日期：2020.6.26

  anti ‐Configured 1,3‐dimethyl deoxypropionate motifs are important sub structures in natural products. Herein, we describe a bidirectional approach for the rapid construction of natural products featuring such motifs by using C 2‐symmetrical 1,3‐bis(boronic esters). As for its application in convergent syntheses it was important to establish a selective mono‐Zweifel olefination we describe the scope

  抗构型的1,3-二甲基脱氧丙酸酯基序是天然产物中的重要子结构。在这里，我们描述了一种双向方法，用于通过使用C 2对称的1,3-双（硼酸酯）快速构建具有此类图案的天然产物。至于其在收敛合成中的应用，建立选择性单-Zweifel烯烃化非常重要，我们通过使用不同的1,3-双（硼酸酯）和亲核试剂来描述范围和局限性。该方案利用了霍普-马特森-茨威费尔化学的结合，Aggarwal等人将其巧妙地付诸实践。为了显示其适用性，进行了两种天然产物Serricornin和（+）-invictolide的总合成。
• Diastereotopic selectivity at prochiral carbon centers: functionalization of differentiated hydroxymethyl groups provides access to either stereoisomeric configuration
  作者：Stuart L. Schreiber、Zhaoyin Wang

  DOI：10.1021/ja00304a062

  日期：1985.9

  Application de la spiroacetalisation a la synthese de (±)-invictolide et a la synthese non racemique du fragment C 1 -C 9 de l'ionomycine

  应用 de la spiroacetalisation a la synthese de (±)-invictolide et a la synthese nonracemique du fragment C 1 -C 9 de l'ionomycine
• Remote chirality control in 1,2-asymmetric induction: a remarkable difference between the meso- and (±)-isomers of dimethylglutaric hemialdehyde
  作者：Yoshinori Yamamoto、Kensaku Taniguchi、Kazuhiro Maruyama

  DOI：10.1039/c39850001429

  日期：——

  The Lewis acid mediated reaction of the meso-dimethylglutaric hemialdehyde (2) with pent-3-en–2-yltributyltin (1) gave the anti-Cram erythro isomer (4) predominantly, while the reaction of the (±)-isomer (3) produced the Cram erythro derivative (5) preferentially.

  路易斯酸介导的内消旋-二甲基戊二醛（2）与戊-3-烯-2-基三丁基锡（1）的反应主要产生抗Cram赤型异构体（4），而（±）-异构体（3）优先产生Cram erythro衍生物（5）。
• Applications of the 3-methyl-.gamma.-butyrolactone strategy to the synthesis of polypropionates: the Prelog-Djerassi lactonic ester, ent-invictolide, and the C19-C27 fragment of rifamycin S
  作者：Frederick E. Ziegler、William T. Cain、Alyssa. Kneisley、Eugene P. Stirchak、Ronald T. Wester

  DOI：10.1021/ja00224a032

  日期：1988.8
• R-3-methyl-γ-butyrolactone as a template for the synthesis of (+)-invictolide
  作者：Frederick E. Ziegler、Eugene P. Stirchak、Ronald T. Wester

  DOI：10.1016/s0040-4039(00)84224-0

  日期：——