(E)-3,7-dimethylocta-2,6-dienyl 4-(2,2-dimethyl-4-oxo-4H-1,3-dioxin-6-yl)-3-oxobutanoate | 1351221-37-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (E)-3,7-dimethylocta-2,6-dienyl 4-(2,2-dimethyl-4-oxo-4H-1,3-dioxin-6-yl)-3-oxobutanoate
• 英文别名: (E)-3,7-dimethylocta-2,6-dien-1-yl 4-(2,2-dimethyl-4-oxo-4H-1,3-dioxin-6-yl)-3-oxobutanoate；[(2E)-3,7-dimethylocta-2,6-dienyl] 4-(2,2-dimethyl-6-oxo-1,3-dioxin-4-yl)-3-oxobutanoate
• CAS: 1351221-37-8
• 化学式: C₂₀H₂₈O₆
• 分子量: 364.439
• InChiKey: QBLTUJGVUAIIPP-OQLLNIDSSA-N

物化性质

• 沸点：
  508.3±50.0 °C(predicted)
• 密度：
  1.078±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  26
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  78.9
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (E)-3,7-dimethylocta-2,6-dienyl 4-(2,2-dimethyl-4-oxo-4H-1,3-dioxin-6-yl)-3-oxobutanoate 在 吡啶 、 四(三苯基膦)钯 、 magnesium chloride 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 16.75h， 生成 [(7E)-5-(2,2-dimethyl-6-oxo-1,3-dioxin-4-yl)-8,12-dimethyl-2,4-dioxotrideca-7,11-dienyl] acetate
  参考文献：
  名称：

  Total Syntheses of Angelicoin A, Hericenone J, and Hericenol A via Migratory Prenyl- and Geranylation–Aromatization Sequences

  摘要：

  A five-step synthesis of the natural product angelicoin A using a late stage highly regioselective palladium(0)-catalyzed decarboxylative prenyl migration and aromatization sequence as the key step is reported. The method was extended with geranyl migration in eight-step total syntheses of hericenone J and hericenol A from geraniol.

  DOI：

  10.1021/jo202354j
• 作为产物：
  描述：

  香叶醇 在 正丁基锂 、 2-甲基-2-丁烯 、 草酰氯 、 N,N-二甲基甲酰胺 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 甲苯 为溶剂， 反应 15.0h， 生成 (E)-3,7-dimethylocta-2,6-dienyl 4-(2,2-dimethyl-4-oxo-4H-1,3-dioxin-6-yl)-3-oxobutanoate
  参考文献：
  名称：

  Total Syntheses of Angelicoin A, Hericenone J, and Hericenol A via Migratory Prenyl- and Geranylation–Aromatization Sequences

  摘要：

  A five-step synthesis of the natural product angelicoin A using a late stage highly regioselective palladium(0)-catalyzed decarboxylative prenyl migration and aromatization sequence as the key step is reported. The method was extended with geranyl migration in eight-step total syntheses of hericenone J and hericenol A from geraniol.

  DOI：

  10.1021/jo202354j

文献信息

• Meroterpenoid total synthesis: Conversion of geraniol and farnesol into amorphastilbol, grifolin and grifolic acid by dioxinone- β -keto-acylation, palladium catalyzed decarboxylative allylic rearrangement and aromatization
  作者：Tsz-Kan Ma、Andrew J.P. White、Anthony G.M. Barrett

  DOI：10.1016/j.tetlet.2017.05.096

  日期：2017.7

  Biomimetic total syntheses of resorcinols amorphastilbol, grifolin and grifolic acid have been completed in four steps starting from geraniol and farnesol without the use of phenolic protection. The key steps involve C-acylation of dioxinone-β-keto esters, followed by palladium catalyzed decarboxylative allylic rearrangement and biomimetic aromatization.

  间苯二酚amorphastilbol，grifolin和grifolic acid的仿生总合成已从香叶醇和法尼醇开始的四个步骤中完成，无需使用酚类保护剂。关键步骤包括二恶英酮-β-酮酯的C-酰化，然后钯催化的脱羧烯丙基重排和仿生芳构化。
• Sequential Ketene Generation from Dioxane-4,6-dione-keto-dioxinones for the Synthesis of Terpenoid Resorcylates
  作者：Daniel C. Elliott、Tsz-Kan Ma、Aymane Selmani、Rosa Cookson、Philip J. Parsons、Anthony G. M. Barrett

  DOI：10.1021/acs.orglett.6b00533

  日期：2016.4.15

  Trapping of the ketene generated from the thermolysis of 2-methyl-2-phenyl-1,3-dioxane-4,6-dione-keto-dioxinone at 50 °C with primary, secondary, or tertiary alcohols gave the corresponding dioxinone β-keto-esters in good yield under neutral conditions. These intermediates were converted by palladium(0)-catalyzed decarboxylative allyl migration and aromatization into the corresponding β-resorcylates

  在50°C下用伯，仲或叔醇热解2-甲基-2-苯基-1,3-二恶烷-4,6-二酮-酮二恶烷酮所产生的乙烯酮，得到相应的二恶英酮β-酮酯在中性条件下收率高。这些中间体通过钯（0）催化的脱羧烯丙基迁移和芳构化转化为相应的β-间苯二酸酯。这些转化应用于天然产物（±）-大麻二甲铬酸和（±）-十二碳二烯酸的合成。
• Biomimetic Total Syntheses of Amorfrutins A, B, ( <i>S</i> )‐D and ( <i>R</i> )‐D and Formal Synthesis of Amorfrutin C
  作者：Thomas Mies、Calum Patel、Philip J. Parsons、Anthony G. M. Barrett

  DOI：10.1002/ejoc.202100301

  日期：2021.5.7

  The formal and total biomimetic syntheses of amorfrutin A, B, C and both enantiomers of amorfrutin D are reported through a unified method from a common precursor prepared using a polyketide aromatization reaction.

  通过使用聚酮化合物芳构化反应制备的普通前体的统一方法，报告了阿莫frutin A，B，C和阿莫夫汀D的两种对映异构体的正式和总体仿生合成。
• [EN] PROCESS FOR THE PRODUCTION OF CANNABINOIDS AND CANNABINOID ACIDS<br/>[FR] PROCÉDÉ DE PRODUCTION DE CANNABINOÏDES ET D'ACIDES CANNABINOÏDES
  申请人：BERKOWITZ BARRY A

  公开号：WO2021071908A1

  公开（公告）日：2021-04-15

  The present invention relates to a process for the preparation of diverse known and novel cannabinoids 5, which include cannabigerol (CBG, 1), cannabigerolic acid (CBGA, 2), cannabigerovarin (CBGV, 3), cannabigerovarinic acid (CBGVA, 4) and other naturally occurring monocyclic cannabinoids and other analogues from simple inexpensive starting materials using a cascade sequence of allylic rearrangement and aromatization. Novel cannabinoids of series 5 are also claimed as part of the invention. These synthesized cannabinoids, unlike the minor cannabinoids isolated from Cannabis saliva or synthesized from the condensation reactions such as the reactions of substituted resorcinols with monoterpenes, are much easier to obtain at high purity levels. In particular, these cannabinoids, including but not limited to cannabigerol (CBG, 1), cannabigerolic acid (CBGA, 2), cannabigerovarin (CBGV, 3) and cannabigerovarinic acid (CBGVA, 4) are obtained without contamination with impurities with variation in RA and RB (e.g. contamination of CBG with CBGV).

  本发明涉及一种制备多种已知和新型大麻素的过程，包括大麻酚醇（CBG, 1）、大麻酚醇酸（CBGA, 2）、大麻酚酮（CBGV, 3）、大麻酚酮酸（CBGVA, 4）等以及其他天然存在的单环大麻素和其他类似物，利用一系列烯丙基重排和芳构化的级联序列从简单廉价的起始原料中制备。系列5的新型大麻素也作为本发明的一部分声明。与从大麻唾液中分离或通过与单萜烃的缩合反应等反应合成的微量大麻素不同，这些合成的大麻素更容易以高纯度水平获得。特别是这些大麻素，包括但不限于大麻酚醇（CBG, 1）、大麻酚醇酸（CBGA, 2）、大麻酚酮（CBGV, 3）和大麻酚酮酸（CBGVA, 4），可以在不受杂质污染的情况下获得，RA和RB的变化（例如CBG与CBGV的污染）。
• Meroterpenoid Synthesis via Sequential Polyketide Aromatization and Cationic Polyene Cyclization: Total Syntheses of (+)-Hongoquercin A and B and Related Meroterpenoids
  作者：Tsz-Kan Ma、Daniel C. Elliott、Stephanie Reid、Andrew J. P. White、Philip J. Parsons、Anthony G. M. Barrett

  DOI：10.1021/acs.joc.8b02095

  日期：2018.11.2

  were synthesized from commercially available trans, trans-farnesol in six and eleven steps, respectively, using dual biomimetic strategies with polyketide aromatization and subsequent polyene functionalization from a common farnesyl-resorcylate intermediate. Key steps involve Pd(0)-catalyzed decarboxylative allylic rearrangement of a dioxinone β,δ-diketo ester to a β,δ-diketo dioxinone, which was readily

  （+）-Hongoquercin A和B分别通过双重仿生策略，聚酮化合物芳构化和随后的多烯官能化从普通的法呢基-间苯二酸酯中间体分别由市售反式，反式-法尼索尔合成，分六步和十一步进行合成。关键步骤涉及Pd（0）催化的二恶英酮β，δ-二酮二酮的Pd（0）催化脱羧烯丙基重排，使其易于芳香化为相应的间苯二酸酯，随后通过对映选择性质子化或区域选择性末端烯烃进行多烯环化对映体富集的环氧化物的氧化和阳离子环化，以提供四环天然产物核心。hongoquercin的类似物是通过ha诱导的多烯环化合成的，