3-羟基-2-甲基戊-4-烯酸甲酯 | 1059575-18-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羟基酸及其衍生物
• 中文名称: 3-羟基-2-甲基戊-4-烯酸甲酯
• 英文名称: 3-hydroxy-2-methylpent-4-enoic acid methyl ester
• 英文别名: methyl 3-hydroxy-2-methyl-4-pentenoate；Methyl 3-hydroxy-2-methylpent-4-enoate
• CAS: 1059575-18-6
• 化学式: C₇H₁₂O₃
• 分子量: 144.17
• InChiKey: FCGFELSCDSTPKX-UHFFFAOYSA-N

物化性质

• 沸点：
  205.8±20.0 °C(Predicted)
• 密度：
  1.023±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  10
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-羟基-2-甲基戊-4-烯酸甲酯 在 chromium(VI) oxide 、 硫酸 作用下， 以 丙酮 为溶剂， 反应 2.0h， 以56%的产率得到methyl 2-methyl-3-oxo-4-pentenoate
  参考文献：
  名称：

  Synthesis of inhibitors of 2,3-oxidosqualene-lanosterol cyclase. 2. Cyclocondensation of .gamma.,.delta.-unsaturated-.beta.-keto esters with imines

  摘要：

  Synthesis and the biological evaluation of ammonium ion analogues of the first carbocyclic cationic intermediate 4 presumed to formed during the cyclization of 2,3-oxidosqualene to protosterol, 2, by 2,3-oxidisqualene-lanosterol cyclase (OSC) is presented. Preparation of the required 4-hydroxy-2,3-substituted-4-piperidine 12 (and its corresponding methiiodide salt 13) involved, as a key step, cyclocondensation of imine 17 with methyl 2-methyl-3-oxo-4-pentenoate (16) to give C-2,C-3-substituted 4-piperidone 15 as a single diastersoisomer. Subsequent elaboration to give 13 was accomplished in six steps in an overall yield of 50%. Analogue 12 inhibited 2,3-oxidosqualene-lanosterol cyclase of Candida albicans with an IC50 of 0.23 muM.

  DOI：

  10.1021/jo00052a043
• 作为产物：
  描述：

  3-(1-tert-Butyl-siletan-1-yloxy)-2-methyl-pent-4-enoic acid methyl ester 在 氢氟酸 作用下， 以 四氢呋喃 为溶剂， 生成 3-羟基-2-甲基戊-4-烯酸甲酯
  参考文献：
  名称：

  烯氧基硅杂环丁烷化学：高选择性未催化羟醛加成

  摘要：

  由酯、硫羟酸酯和酰胺衍生的 O(Silacyclobuty1) 烯酮缩醛在室温下与各种醛轻松进行醛醇加成，无需催化剂。O(silacyclobuty1) 烯酮缩醛的未催化羟醛加成反应具有以下特征：(1) 反应速率高度依赖于硅上的观察者取代基和烯酮缩醛的几何形状，(2) 0,O-烯酮E 构型的缩醛提供了具有高非对映选择性（93/7 到 99/1）的合成羟醛产物，（3）共轭醛比脂肪醛反应更快，（4）反应对溶​​剂温和。此外，发现醇醛反应被金属醇盐有效催化。标记实验表明，热醛醇反应通过直接分子内硅基团转移进行，而醇盐催化的反应可能通过原位生成的金属烯醇化物进行。过渡态的计算模型表明船型过渡结构是优选的，支持观察到的热醛醇反应的顺式选择性。研究了热催化和醇盐催化的迈克尔加成，揭示了 1,2- 和 1 之间的竞争，加成有利于前者。

  DOI：

  10.1021/ja00095a004

文献信息

• Stereocontrolled Synthesis of the Highly Functionalized Core Structure of Aurisides by Ring-Closing Metathesis
  作者：Emmanuel Bourcet、Fabienne Fache、Olivier Piva

  DOI：10.1002/ejoc.201000331

  日期：2010.7

  Two approaches based on the ring-closing metathesis reaction have been explored for the synthesis of the core structure of the marine natural products, the aurisides. The second approach, accomplished in a stereocontrolled manner, used both a Brown's allylation and an Evans' aldolisation, and finally a transannular ketalization to deliver a highly functionalized auriside analogue.

  已经探索了两种基于闭环复分解反应的方法来合成海洋天然产物金苷的核心结构。第二种方法以立体控制的方式完成，使用布朗烯丙基化和埃文斯醛醇化，最后使用跨环缩酮化来提供高度功能化的金苷类似物。
• Tandem-Directed Regioselective Hydroformylation/β-Elimination: A Practical Method for the Synthesis of Enals
  作者：Bernhard Breit、Achim Bruch、Antje Gebert

  DOI：10.1055/s-2008-1067140

  日期：2008.7

  A practical synthesis of α,β-unsaturated aldehydes by a tandem-directed hydroformylation/β -elimination process of allylic o-DPPB esters is reported. The o-DPPB group served as an effective controller for regioselectivity of the hydroformylation towards the desired aldolate isomer, and was subsequently eliminated in situ by mild standard bases. The reaction is rather general for the preparation of

  报道了通过烯丙基 o-DPPB 酯的串联定向加氢甲酰化/β-消除工艺实际合成 α,β-不饱和醛。o-DPPB 基团作为加氢甲酰化对所需醛醇异构体的区域选择性的有效控制剂，随后被温和的标准碱原位消除。该反应对于制备 1,1-二取代和三取代烯醛是相当普遍的，并且与许多官能团相容。o-DPPBA 可以通过色谱法或以二乙基铵盐的形式沉淀来回收。
• Optically active compounds having plural chiral centers and the production thereof
  申请人：Chisso Corporation

  公开号：EP0428392A2

  公开（公告）日：1991-05-22

  Optically active compounds, having a plurality of chiral centres, have the general formulae: or in which R', R2 and R4 are the same or are different and each is an alkyl, alkenyl or alkynyl group having up to 40 carbon atoms, the carbon chain of which may contain one or more of halogen, cyano, oxygen, nitrogen, silicon, sulfur and substituted or unsubstituted benzene, cyclohexane, pyridine, pyrimidine, pyridazine, pyrazine, dioxane or bicyclooctane ring 5; R3 is an alkyl, alkenyl or alkynyl groups having 3 to 40 carbon atoms ; X is hydrogen or an alkanoyl group having 2 to 40 carbon atoms; and the carbon atom with the sign, *, is an asymmetic carbon.

  具有多个手性中心的光学活性化合物的通式为 或 其中 R'、R2 和 R4 相同或不同，且各自为具有多达 40 个碳原子的烷基、烯基或炔基，其碳链可包含一个或多个卤素、氰基、氧、氮、硅、硫和取代或未取代的苯、环己烷、吡啶、嘧啶、哒嗪、吡嗪、二氧杂环或双环辛烷环 5； R3 是具有 3 至 40 个碳原子的烷基、烯基或炔基； X 是氢或具有 2 至 40 个碳原子的烷酰基； 符号 * 的碳原子为异构碳。
• Synthesis of the macrolactone structure of the aurisides
  作者：Emmanuel Bourcet、Fabienne Fache、Olivier Piva

  DOI：10.1016/j.tet.2009.12.008

  日期：2010.2

  The core Structure of the aurisides has been reached by the coupling of three subunits including as key step a cross/metathesis/hydrogenation/ketalisation sequence. the addition of a vinyl lithium derivative onto an aldehyde and finally a lactonization Under Yamaguchi's conditions (C) 2009 Elsevier Ltd All rights reserved
• Processes for the preparation of optically active compounds having plural chiral centers
  申请人：Chisso Corporation

  公开号：EP0428392B1

  公开（公告）日：1998-05-27