3-acetoxy-2-methylenehexanoic acid methyl ester | 87050-27-9

• 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: 3-acetoxy-2-methylenehexanoic acid methyl ester
• 英文别名: methyl 3-acetyloxy-2-methylidenehexanoate
• CAS: 87050-27-9
• 化学式: C₁₀H₁₆O₄
• 分子量: 200.235
• InChiKey: GSNPFCFUDGEFNR-UHFFFAOYSA-N

物化性质

• 沸点：
  262.3±23.0 °C(Predicted)
• 密度：
  1.022±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  14
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 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：

  3-acetoxy-2-methylenehexanoic acid methyl ester 在 lithium aluminium tetrahydride 作用下， 以 乙醇 为溶剂， 反应 0.33h， 以2.93 g的产率得到2-甲基己-2-烯-1-醇
  参考文献：
  名称：

  Total Synthesis and Structure Determination of JBIR-108—A 2-Hydroxy-2-(1-hydroxyethyl)-2,3-dihydro-3(2H)-furanone Isolated from Streptomyces gramineus IR087Pi-4

  摘要：

  The planar and stereostructures of JBIR-108 isolated from Streptomyces gramineus IR087Pi-4 were determined partly by spectral analysis, and these structural assignments were confirmed and completed by the total synthesis of both 1-epimers. The key stereocenters in JBIR-108 were constructed via a Corey-Bakshi-Shibata (CBS) reduction (C-1), vinylogous Mukaiyama aldol reaction (C-7), and Brown crotylation (C-14 and C-15). Although it was difficult to determine the stereochemistries at the C-1 and C-7 positions in the natural product using the modified Moshers method, the synthesis of two possible C-1 diastereomers enabled the identification of the configurations at the hitherto unknown stereocenters.

  DOI：

  10.1021/jo502198y
• 作为产物：
  描述：

  己酸,3-羟基-2-亚甲基-,甲基酯 、 乙酸酐 在 4-二甲氨基吡啶 、 三乙胺 作用下， 反应 0.5h， 生成 3-acetoxy-2-methylenehexanoic acid methyl ester
  参考文献：
  名称：

  高度取代的吲哚/吡咯基二氮杂酮的模块化和立体选择方法

  摘要：

  已经开发出一种用于吲哚/吡咯融合的1，4-二氮杂潘酮支架的一锅法合成方法。此方法涉及将1 H-吲哚/吡咯-2-羧酸与森田-贝利斯-希尔曼衍生的烯丙胺依次进行酰胺偶联/分子内氮杂-迈克尔加成反应。容易获得的起始原料，良好的立体选择性和克级合成方法使该方法对于构建含有1,4-二氮杂酮部分的高度取代的稠合杂环具有重要意义。

  DOI：

  10.1021/acs.joc.1c00303

文献信息

• The Coupling of Tertiary Amines with Acrylate Derivatives via Visible-Light Photoredox Catalysis
  作者：Xiaojun Dai、Dongping Cheng、Baochuan Guan、Wenjuan Mao、Xiaoliang Xu、Xiaonian Li

  DOI：10.1021/jo501097b

  日期：2014.8.1

  Catalyzed by Ru(bpy)3(BF4)2, the photoredox coupling of tertiary amines with acrylate derivatives including Baylis–Hillman adducts under visible light irradiation was successfully established. The scope of the substrates was broad, and thus an array of γ-aminobutyric ester derivatives was obtained in moderate to good yields.

  通过Ru（bpy）3（BF 4）2催化，成功建立了叔胺与丙烯酸酯衍生物（包括Baylis-Hillman加合物）在可见光下的光氧化还原偶联。底物的范围很广，因此以中等至良好的产率获得了一系列的γ-氨基丁酸酯衍生物。
• The coupling reaction of α-silylamines with Baylis-Hillman adducts by visible light photoredox catalysis
  作者：He Zhao、Niannian Ni、Xiaonian Li、Dongping Cheng、Xiaoliang Xu

  DOI：10.1016/j.tetlet.2020.152746

  日期：2021.2

  The preparation of N-containing α,β-unsaturated carboxylate derivatives from α-silylamine and Baylis-Hillman adducts under visible light irradiation was reported. The formation of α-aminoalkyl radical is regioselective compared with the previous reports. The reaction was successfully performed without additional additives under mild conditions.

  报道了在可见光照射下由α-甲硅烷基胺和Baylis-Hillman加合物制备含N的α，β-不饱和羧酸酯衍生物。与先前的报道相比，α-氨基烷基的形成具有区域选择性。在温和条件下，无需添加其他添加剂即可成功进行反应。
• NaNO2–Ceric ammonium nitrate mediated conversion of acrylic esters and Baylis–Hillman derived acrylic esters into corresponding β-nitro acrylic esters
  作者：K Jayakanthan、K.P Madhusudanan、Yashwant D Vankar

  DOI：10.1016/j.tet.2003.11.013

  日期：2004.1

  A variety of acrylic esters, including those derived from Baylis–Hillman reactions, react with NaNO2–ceric ammonium nitrate to form the corresponding β-nitro alcohols 2 and 5 whose dehydration, via their mesylates, leads to β-nitro acrylic esters, in good to excellent yields. Further, β-nitro acrylic esters containing a mesylate group 6, obtained from the Baylis–Hillman products, react with NaN3 to

  各种丙烯酸酯，包括那些由Baylis-Hillman反应衍生的丙烯酸酯，与NaNO 2-铈硝酸铵反应生成相应的β-硝基醇2和5，它们通过甲磺酸酯的脱水作用，生成β-硝基丙烯酸酯。好到极好的产量。此外，从Baylis-Hillman产品获得的含有甲磺酸酯基团6的β-硝基丙烯酸酯与NaN 3反应，以极好的收率形成2-氰基-3-取代的丙烯酸酯10。
• Chemo-, regio- and stereoselective addition of triorganoindium reagents to acetates of Baylis–Hillman adducts: a new strategy for the synthesis of (E)- and (Z)-trisubstituted alkenes
  作者：Brindaban C. Ranu、Kalicharan Chattopadhyay、Ranjan Jana

  DOI：10.1016/j.tetlet.2007.03.154

  日期：2007.5

  The addition of several trialkyl or triarylindium reagents to the acetates of Baylis–Hillman adducts proceeds readily under the catalysis of copper and palladium derivatives. The reactions of trialkylindiums are catalyzed efficiently by CuI whereas additions of triarylindiums produce better results with Pd(PPh3)4. The reactions with 3-acetoxy-2-methylenealkanoates provide (E)-alkenes, whereas similar

  在铜和钯衍生物的催化下，向Baylis-Hillman加合物的乙酸酯中添加几种三烷基或三芳基鎓试剂很容易。CuI可以有效地催化三烷基铟的反应，而Pd（PPh 3）4可以增加三芳基铟的生成效果。与3-乙酰氧基-2-亚甲基链烷酸酯的反应提供了（E）-烯烃，而与3-乙酰氧基-2-亚甲基链烷烯腈的类似反应导致了（Z）-烯烃。所有反应都具有高度的区域选择性和立体选择性，并且产率高。
• Nucleophilic addition of triethyl phosphite to acetates of the baylis-hillman adducts: Stereoselective synthesis of (E)- and (Z)-allylphosphonates
  作者：Deevi Basavaiah、Subramanian Pandiaraju

  DOI：10.1016/0040-4020(95)01055-6

  日期：1996.2

  Nucleophilic addition of triethyl phosphite to 3-acetoxy-2-methylenealkanenitriles and methyl 3-acetoxy-2-methylenealkanoates provides (2E)-2-(diethoxyphosphorylmethyl)alk-2- enenitriles and methyl (2Z)-2-(diethoxy-phosphorylmethyl)alk-2-enoates respectively with good stereoselectivity.

  将亚磷酸三乙酯亲核加成到3-乙酰氧基-2-亚甲基链烷腈和3-乙酰氧基-2-亚甲基链烷酸甲酯中，得到（2E）-2-（二乙氧基磷酰基甲基）alk-2-烯腈和甲基（2Z）-2-（二乙氧基磷酰基甲基）烷基-2-烯酸酯分别具有良好的立体选择性。