methyl 4-methylpent-2-ynoate | 80866-47-3

• 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 4-methylpent-2-ynoate
• CAS: 80866-47-3
• 化学式: C₇H₁₀O₂
• 分子量: 126.155
• InChiKey: FAXBYZVWLRYYIY-UHFFFAOYSA-N

物化性质

• 沸点：
  70 °C(Press: 0.2 Torr)
• 密度：
  0.961±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  methyl 4-methylpent-2-ynoate 在 溶剂黄146 、 potassium iodide 作用下， 反应 2.0h， 以100%的产率得到
  参考文献：
  名称：

  Scalable and Divergent Total Synthesis of (+)-Colletoic Acid, a Selective 11β-Hydroxysteroid Dehydrogenase Type 1 Inhibitor

  摘要：

  An efficient and divergent total synthesis of (+)-colletoic acid, a selective 11-beta hydroxysteroid dehydrogenase 1 (11-beta HSD1) inhibitor, is presented along with its biological activity at the whole-cell level. A scalable, asymmetric synthetic strategy was designed featuring a diversity-oriented synthesis utilizing a diastereoselective intramolecular 5-exo-Heck reaction as the key step to provide the quaternary spirocenter intermediate 9 in multigram scale, thus establishing a platform for further structure-activity relationship studies and providing access to other acorane family members.

  DOI：

  10.1021/ol402842u
• 作为产物：
  描述：

  异丁酰醋酸甲酯 在 三乙胺 、 lithium hydroxide 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 11.3h， 生成 methyl 4-methylpent-2-ynoate
  参考文献：
  名称：

  Scalable and Divergent Total Synthesis of (+)-Colletoic Acid, a Selective 11β-Hydroxysteroid Dehydrogenase Type 1 Inhibitor

  摘要：

  An efficient and divergent total synthesis of (+)-colletoic acid, a selective 11-beta hydroxysteroid dehydrogenase 1 (11-beta HSD1) inhibitor, is presented along with its biological activity at the whole-cell level. A scalable, asymmetric synthetic strategy was designed featuring a diversity-oriented synthesis utilizing a diastereoselective intramolecular 5-exo-Heck reaction as the key step to provide the quaternary spirocenter intermediate 9 in multigram scale, thus establishing a platform for further structure-activity relationship studies and providing access to other acorane family members.

  DOI：

  10.1021/ol402842u

文献信息

• Annulations leading to diene systems. Total syntheses of the dolastane-type diterpenoids (±)-(5<i>S</i>,12<i>R</i>,14<i>S</i>)-dolasta-1(15),7,9-trien-14-ol and (±)-amijitrienol
  作者：Edward Piers、Richard W. Friesen

  DOI：10.1139/v92-157

  日期：1992.4.1

  Alkylation of the substituted cycloalkanones 14a–d and 30 with (Z)-1-bromo-4-methyl-3-trimethylstannyl-2-pentene (13) produced compounds 15a–d and 33, which were readily converted into the correspo...

  取代的环烷酮 14a-d 和 30 与 (Z)-1-bromo-4-methyl-3-trimethylstannyl-2-pentene (13) 烷基化产生化合物 15a-d 和 33，它们很容易转化为相应的化合物。 .
• Regiodivergent Ligand-Controlled Rhodium-Catalyzed [(2+2)+2] Carbocyclization Reactions with Alkyl Substituted Methyl Propiolates
  作者：P. Andrew Evans、James R. Sawyer、Phillip A. Inglesby

  DOI：10.1002/anie.201002117

  日期：——

  Choice is yours: In the title reaction the selective formation of either regioisomer can be controlled through judicious choice of the ancillary ligands (see scheme). Central to this accomplishment was the realization that residual silver salts from the salt metathesis of the neutral complex have a strong effect on the regio‐ and diastereoselectivity.

  选择由您自己决定：在标题反应中，可以通过明智地选择辅助配体来控制任一区域异构体的选择性形成（请参阅方案）。这项成就的核心是认识到，中性络合物的盐复分解中残留的银盐对区域选择性和非对映选择性具有很大的影响。
• New Regio- and Stereoselective Cascades via Unstabilized Azomethine Ylide Cycloadditions for the Synthesis of Highly Substituted Tropane and Indolizidine Frameworks
  作者：Shuming Chen、Vlad Bacauanu、Tobias Knecht、Brandon Q. Mercado、Robert G. Bergman、Jonathan A. Ellman

  DOI：10.1021/jacs.6b08355

  日期：2016.9.28

  Multisubstituted tropanes and indolizidines have been prepared with high regio- and stereoselectivity by the [3+2] cycloaddition of unstabilized azomethine ylides generated from readily prepared trimethylsilyl-substituted 1,2-dihydropyridines via protonation or alkylation followed by desilylation. Starting from 1,2-dihydropyridines bearing a ring trimethylsilyl substituent at the 6-position, an intermolecular

  多取代的托烷和吲哚里西啶是通过 [3+2] 环加成反应制备的，这些不稳定的偶氮甲碱叶立德是由容易制备的三甲基甲硅烷基取代的 1,2-二氢吡啶通过质子化或烷基化然后去甲硅烷基化产生的。从在 6 位带有环三甲基甲硅烷基取代基的 1,2-二氢吡啶开始，分子间烷基化/脱甲硅烷基化提供了内环不稳定的叶立德，这些叶立德成功地与一系列对称和不对称的炔烃和烯烃亲偶极体发生环加成，得到含有季碳的密集取代的托烷产率高，区域选择性和立体选择性高。此外，分子内烷基化/脱甲硅烷基化/环加成序列可方便快速地进入桥连三环托烷骨架，允许在单个实验操作中在温和条件下设置五个连续的碳立体中心。从氮上带有三甲基甲硅烷基甲基的 1,2-二氢吡啶开始，质子化和脱甲硅烷基化生成环外不稳定叶立德，这些叶立德与不对称炔烃发生环加成，得到具有良好区域和立体选择性的吲哚里西啶。N-三甲基甲硅烷基甲基-1,2-二氢吡啶也可以被烷基化并随后脱甲
• Unified Approach to Furan Natural Products via Phosphine‐Palladium Catalysis
  作者：Violet Yijang Chen、Ohyun Kwon

  DOI：10.1002/anie.202015232

  日期：2021.4.12

  the construction of tetraalkyl furans remains non‐trivial. The prevalence of alkyl groups in bioactive furan natural products, combined with the desirable bioactivities of tetraalkyl furans, calls for a general synthetic protocol for polyalkyl furans. This paper describes a Michael–Heck approach, using sequential phosphine‐palladium catalysis, for the preparation of various polyalkyl furans from readily

  多烷基呋喃在自然界中广泛存在，通常发挥重要的生物学作用。尽管合成四取代呋喃的方法有很多，但四烷基呋喃的构建仍然很重要。生物活性呋喃天然产物中烷基的普遍存在，加上四烷基呋喃所需的生物活性，需要一种多烷基呋喃的通用合成方案。本文描述了一种 Michael-Heck 方法，使用顺序膦-钯催化，从容易获得的前体制备各种聚烷基呋喃。该方法的多功能性通过属于不同类别的九种不同的多烷基化呋喃天然产物（即呋喃萜玫瑰呋喃、倍半糖呋喃和米卡尼呋喃）的全合成来说明；海洋天然产物plakorsin A、B、D和plakorsin D甲酯；以及呋喃脂肪酸3D5和氢木霉素。
• Rhodium-Catalyzed Three-Component Cross-Addition of Silylacetylenes, Alkynyl Esters, and Electron-Deficient Alkenes or Isocyanates
  作者：Yuki Hoshino、Yu Shibata、Ken Tanaka

  DOI：10.1002/anie.201204646

  日期：2012.9.10

  ‘Rh'oad crossing: A cationic RhI/(cod)2 complex catalyzes the chemo‐, regio‐, and stereoselective title reaction with electron‐deficient alkenes leading to substituted 1,3‐dienes. The analogous three‐component cross‐addition involving isocyanates instead of alkenes has also been developed.

  'Rh'oad交叉：阳离子Rh I /（cod）2络合物催化与电子不足的烯烃的化学，区域和立体选择性标题反应，从而生成取代的1,3-二烯。还开发了类似的三组分交叉加成法，其中涉及异氰酸酯而不是烯烃。