1,4-diacetoxy-2-methylenebutane | 90612-80-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 1,4-diacetoxy-2-methylenebutane
• 英文别名: 2-Methylene-butan-1,4-diyl diacetate；3-(acetyloxymethyl)but-3-enyl acetate
• CAS: 90612-80-9
• 化学式: C₉H₁₄O₄
• 分子量: 186.208
• InChiKey: UUHSWUKMQPDSHF-UHFFFAOYSA-N

物化性质

• 保留指数：
  1255

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  13
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1,4-diacetoxy-2-methylenebutane 在 甲醇 、 Pseudomonas sp. lipase 、 水 、 potassium carbonate 、 sodium hydroxide 作用下， 以 水 为溶剂， 反应 1.08h， 生成 (R)-2-甲基-1,4-丁二醇
  参考文献：
  名称：

  Chemo-biological preparation of the chiral building block (R)-4-acetoxy-2-methyl-1-butanol using Pseudomonas putida

  摘要：

  In order to develop new methyl substituted chiral building blocks which are useful for the synthesis of methyl branched natural products, the enantioselective bioreduction of an exo-methylene to a methyl group was investigated. 4-Acetoxy-2-methylene-1-butanol 3 was prepared from itaconic acid over four steps and converted to the chiral alcohol (R)-4-acetoxy-2-methyl-1-butanol 4, by growing cells of Pseudomonas putida. The bioconversion achieved a high enantioselectivity (92% ee) and a high chemical yield (65%) within a relatively short reaction time (18-20 h). Crown Copyright (C) 2011 Published by Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2011.09.019
• 作为产物：
  描述：

  衣康酸二甲酯 在 吡啶 、 lithium aluminium tetrahydride 、 三氯化铝 作用下， 以 乙醚 、 苯 为溶剂， 反应 18.5h， 生成 1,4-diacetoxy-2-methylenebutane
  参考文献：
  名称：

  Total Synthesis and Stereochemistry of Alternaric Acid

  摘要：

  Determination of the stereochemistry and the total synthesis of alternaric acid 1 has been achieved. The stereostructure of 1 has been elucidated by stereoselective synthesis of four diastereoisomers of the C(9)-C(14) fragment 6, which had been obtained as a degradation product during structural studies. Key reactions of the total synthesis of 1 include the Julia olefination of tertiary aldehyde 6 and phenylsulfone 7 and novel one-pot construction of 3-acyl-4-hydroxy-5,6-dihydro-2-pyrone via Fries-type rearrangement of the O-enol acyl group of beta-keto-delta-valerolactone toward the a-position of the delta-lactone. The absolute configuration of alternaric acid has been shown to be that illustrated in structure 1. The modified Fries-type rearrangement method has also been extended to the synthesis of some other compounds containing a tricarbonylmethane structure.

  DOI：

  10.1021/jo00096a016

文献信息

• Function‐Oriented and Modular (+/−)‐ <i>cis</i> ‐Pseudoguaianolide Synthesis: Discovery of New Nrf2 Activators and NF‐κB Inhibitors
  作者：Fabien Emmetiere、Ranjala Ratnayake、Henry A. M. Schares、Katherine F. M. Jones、Emily Bevan–Smith、Hendrik Luesch、Daniel A. Harki、Alexander J. Grenning

  DOI：10.1002/chem.202100038

  日期：2021.3.22

  Described herein is a function‐oriented synthesis route and biological evaluation of pseudoguaianolide analogues. The 10‐step synthetic route developed retains the topological complexity of the natural product, installs functional handles for late‐stage diversification, and forges the key bioactive Michael acceptors early in the synthesis. The analogues were found to be low‐micromolar Nrf2 activators

  本文描述的是一种以功能为导向的合成路线和拟番石榴酸内酯类似物的生物学评价。开发的10步合成路线保留了天然产物的拓扑复杂性，为后期的多样化安装了功能性手柄，并在合成初期锻造了关键的生物活性迈克尔受体。发现这些类似物是低微摩尔浓度的Nrf2激活剂和微摩尔浓度的NF-κB抑制剂，并且取决于迈克尔受体部分的局部环境。
• METHOD FOR PRODUCING BIS-ACYLOXYLATED EXOMETHYLENE COMPOUND
  申请人：KURARAY CO., LTD.

  公开号：US20200283367A1

  公开（公告）日：2020-09-10

  A method of producing a bis-acyloxylated exomethylene compound represented by general formula (III), including reacting a monoacyloxylated exomethylene compound represented by general formula (I), a carboxylic acid represented by general formula (II), and oxygen in a liquid phase in the presence of a catalyst and optionally a solvent:

  一种生产通式（III）所代表的双酰氧基外亚甲基化合物的方法，包括在催化剂和可选溶剂的存在下，在液相中反应通式（I）所代表的单酰氧基外亚甲基化合物、通式（II）所代表的羧酸和氧气。
• Method for producing bis-acyloxylated exomethylene compound
  申请人：KURARAY CO., LTD.

  公开号：US10843998B2

  公开（公告）日：2020-11-24

  A method of producing a bis-acyloxylated exomethylene compound represented by general formula (III), including reacting a monoacyloxylated exomethylene compound represented by general formula (I), a carboxylic acid represented by general formula (II), and oxygen in a liquid phase in the presence of a catalyst and optionally a solvent:

  一种生产通式(III)代表的双乙酰氧基化外亚甲基化合物的方法，包括在催化剂和任选溶剂存在下，使通式(I)代表的单乙酰氧基化外亚甲基化合物、通式(II)代表的羧酸和氧气在液相中反应：
• Ochiai, Masahito; Fujita, Eiichi; Arimoto, Masao, Chemical and pharmaceutical bulletin, 1985, vol. 33, # 1, p. 41 - 47
  作者：Ochiai, Masahito、Fujita, Eiichi、Arimoto, Masao、Yamaguchi, Hideo

  DOI：——

  日期：——
• Ochiai, Masahito; Fujita, Eiichi; Arimoto, Masao, Chemical and pharmaceutical bulletin, 1984, vol. 32, # 12, p. 5027 - 5030
  作者：Ochiai, Masahito、Fujita, Eiichi、Arimoto, Masao、Yamaguchi, Hideo

  DOI：——

  日期：——