methyl 3-acetoxy-5-propyl-2-methylenepent-4-ynoate | 1378941-99-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: methyl 3-acetoxy-5-propyl-2-methylenepent-4-ynoate
• 英文别名: methyl 3-acetoxy-2-methyleneoct-4-ynoate；Methyl 3-acetyloxy-2-methylideneoct-4-ynoate；methyl 3-acetyloxy-2-methylideneoct-4-ynoate
• CAS: 1378941-99-1
• 化学式: C₁₂H₁₆O₄
• 分子量: 224.257
• InChiKey: GIKBBDYPEKOQNA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  methyl 3-acetoxy-5-propyl-2-methylenepent-4-ynoate 在 sodium azide 、 三苯基膦 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 22.0h， 以79%的产率得到methyl 5-butyl-1H-pyrrole-3-carboxylate
  参考文献：
  名称：

  膦介导的叠氮化物与炔醛的MBH-乙酸盐与取代的吡咯的级联反应：易于获得N稠合的吡咯并杂环†

  摘要：

  描述了叠氮化物与炔属醛的森田-贝利斯-希尔曼乙酸盐的级联反应的一锅法合成取代的吡咯，该反应在室温下由三苯基膦有效地介导。叠氮化钠已成功用于提供N-未取代的吡咯，而烷基叠氮化物通过一系列烯丙基取代/叠氮化物还原/环异构化反应提供了相应的N-烷基化吡咯。所获得的产品为吲哚并吲哚，吡咯并异喹啉和8-氧代-5、6、7、8-四氢吲哚并嗪提供了新的入口。

  DOI：

  10.1039/c2ob25272d
• 作为产物：
  描述：

  己-2-炔-1-醛 在 三乙烯二胺 、 4-二甲氨基吡啶 作用下， 以 二氯甲烷 、 二甲基亚砜 为溶剂， 反应 3.0h， 生成 methyl 3-acetoxy-5-propyl-2-methylenepent-4-ynoate
  参考文献：
  名称：

  Cu(I)-Catalyzed Aminative Aza-Annulation of Enynyl Azide using N-Fluorobenzenesulfonimide: Synthesis of 5-Aminonicotinates

  摘要：

  An unprecedented copper-catalyzed aminative aza-annulation of enynyl azide using commercially available N-fluorobenzenesulfonhnide (NFSI) as an amination reagent is described. The reaction proceeds via regioselective inter-/intramolecular diamination, incorporating one nitrogen from the NFSI and the other from the azide, to provide amino substituted nicotinate derivatives in a single step with moderate to high yield. This method represents an efficient way to access diverse aminonicotinates through direct C-N bond-coupling processes.

  DOI：

  10.1021/acs.orglett.8b01228

文献信息

• Copper-promoted cascade reaction of active methylenes with MBH-acetates of acetylenic aldehydes to functionalized cyclopentenes
  作者：Chada Raji Reddy、Paridala Kumaraswamy

  DOI：10.1039/c3ra46229c

  日期：——

  One-pot synthesis of substituted cyclopentenes was accomplished through a copper-mediated [4 + 1]-annulation of active methylene compounds with Morita–Baylis–Hillman (MBH) acetates of acetylenic aldehydes. The reaction sequence involves the cascade allylic substitution/5-exo-dig-carbocyclization, which was effective in providing methylene, alkylidene as well as arylidene cyclopentenes.

  通过铜催化的活性次甲基化合物与炔丙醛Morita-Baylis-Hillman（MBH）乙酸酯之间的[4+1]环化反应，成功实现了取代环戊烯的一锅法合成。该反应序列涉及级联亲电性烯丙基取代/5-外向-挖环碳环化反应，对合成次甲基、亚烷基及亚苯基环戊烯均非常有效。
• Novel [4 + 2]-Benzannulation To Access Substituted Benzenes and Polycyclic Aromatic and Benzene-Fused Heteroaromatic Compounds
  作者：Chada Raji Reddy、Uredi Dilipkumar、Motatipally Damoder Reddy

  DOI：10.1021/ol501683v

  日期：2014.7.18

  been developed for the synthesis of aromatic and heteroaromatic compounds through tandem allylic substitution/hydroarylative cycloisomerization process. This method provides a facile and general route to substituted benzenes, naphthalenes, other polycyclic aromatics, and various benzene-fused heteroaromatic compounds such as benzofuran, benzothiophene, indole, and carbazoles.

  已开发出一种常见的[4 + 2]苯乙醛的Morita–Baylis–Hillman乙酸酯与硼酸苯甲酸酯化方法，用于通过串联烯丙基取代/加氢芳基环异构化过程合成芳族和杂芳族化合物。此方法为取代的苯，萘，其他多环芳烃和各种苯稠合的杂芳族化合物（如苯并呋喃，苯并噻吩，吲哚和咔唑）提供了简便而通用的途径。
• Sequential Allylic Substitution/Pauson–Khand Reaction: A Strategy to Bicyclic Fused Cyclopentenones from MBH-Acetates of Acetylenic Aldehydes
  作者：Chada Raji Reddy、Paridala Kumaraswamy、Kiran K. Singarapu

  DOI：10.1021/jo500962d

  日期：2014.9.5

  approach for the construction of novel bicyclic fused cyclopentenones starting from Morita–Baylis–Hillman (MBH) acetates of acetylenic aldehydes with flexible scaffold diversity has been achieved using a two-step reaction sequence involving allylic substitution and the Pauson–Khand reaction. This strategy provided a facile access to various bicyclic cyclopentenones fused with either a carbocyclic or a

  使用包含烯丙基取代和Pauson-Khand反应的两步反应序列，已成功构建了一种新的双环稠合环戊烯酮（从具有柔性骨架多样性的炔属乙醛的Morita-Baylis-Hillman（MBH）乙酸酯开始）的构建方法。该策略提供了以良好收率容易地获得与碳环或杂环系统稠合的各种双环环戊烯酮的途径。
• Aza-Annulation of Enynyl Azides: A New Approach to Substituted Pyridines
  作者：Chada Raji Reddy、Sujatarani A. Panda、Motatipally Damoder Reddy

  DOI：10.1021/ol503752k

  日期：2015.2.20

  Synthesis of substituted pyridines through a novel aza-annulation of 2-en-4-ynyl azides, derived from MBH-acetates of acetylenic aldehydes, is described. A variety of enynyl azides having aryl, heteroaryl, and alkyl groups on the alkyne functionality successfully participated in the Ag-mediated annulation reaction to provide the corresponding 3,6-disubstituted pyridines. I2-Mediated cyclization was

  描述了通过衍生自炔醛的MBH-乙酸酯的新的2-en-4-炔基叠氮化物的氮杂-环烷基合成取代的吡啶。在炔官能团上具有芳基，杂芳基和烷基的各种烯丙基叠氮化物成功地参与了Ag介导的环化反应，以提供相应的3，6-二取代的吡啶。发现I 2-介导的环化受到炔官能团上的取代基的控制，所述取代基由炔炔官能团上具有富电子取代基的烯丙基叠氮化物提供了5-碘-3，6-二取代的吡啶。
• A Thioannulation Approach to Substituted Thiophenes from Morita–Baylis–Hillman Acetates of Acetylenic Aldehydes
  作者：Chada Raji Reddy、Reddi Rani Valleti、Motatipally Damoder Reddy

  DOI：10.1021/jo400567h

  日期：2013.7.5

  A new protocol has been developed for the synthesis of substituted thiophenes under mild and metal-free reaction conditions via the base-promoted thioannulation of Morita–Baylis–Hillman acetates of acetylenic aldehydes with potassium thioacetate involving a tandem allylic substitution/deacetylative 5-exo-dig-thiocycloisomerization. The obtained products provide an entry to 4H-thieno[3,2-c]chromene

  已开发出一种新的方案，用于在温和且无金属的反应条件下，通过Morita-Baylis-Hillman乙炔醛乙酸盐与硫代乙酸钾的碱促进硫代环化反应，合成串联噻吩取代/去乙酰化5-exo-挖-硫代环异构化。所获得的产物提供了4 H-噻吩并[3，2- c ]亚甲基和噻吩并[3，2- c ]二氢喹啉的入口。