ethyl lithioisobutyrate | 138767-03-0

• 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: ethyl lithioisobutyrate
• 英文别名: ethyl 2-methylpropanoate anion lithium；ethyl isobutyrate, lithium enolate；ethyl isobutyrate lithium salt；lithium 1-ethoxy-2-methylprop-1-en-1-olate；lithium ethyl isobutyrate；Lithium;ethyl 2-methylpropanoate
• CAS: 138767-03-0
• 化学式: C₆H₁₁O₂*Li
• 分子量: 122.093
• InChiKey: SSYGIEMPCXSAKN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.83
• 重原子数：
  9
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  ethyl lithioisobutyrate 在 碘 作用下， 生成 diethyl 2,2,3,3-tetramethylsuccinate
  参考文献：
  名称：

  SN2 displacements and reductive coupling of ketones with olefins in N,N-diethylacetamide and N-ethylpyrrolidone

  摘要：

  DOI：

  10.1021/jo01328a008
• 作为产物：
  描述：

  异丁酸乙酯 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 生成 ethyl lithioisobutyrate
  参考文献：
  名称：

  Uncatalyzed aldol reaction using a dimethylsilyl enolate and α-dimethylsilyl ester in N,N-dimethylformamide

  摘要：

  Dimethylsilyl enolates and alpha-dimethylsilyl esters reacted with aldehydes in N,N-dimethyl-formamide without an activator to give aldol adducts in moderate to good yields. Under the same conditions, the corresponding trimethylsilyl derivatives exhibited lower reactivities toward the aldol reaction. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(98)00275-5

文献信息

• Enantioselective Total Synthesis of (−)-Taxol
  作者：Hiroyuki Kusama、Ryoma Hara、Shigeru Kawahara、Toshiyuki Nishimori、Hajime Kashima、Nobuhito Nakamura、Koichiro Morihira、Isao Kuwajima

  DOI：10.1021/ja9939439

  日期：2000.4.1

  Enantioselective total synthesis of taxol has been accomplished. Coupling reaction of the optically pure A-ring hydroxy aldehyde with the aromatic C-ring fragment followed by Lewis acid mediated eight-membered B-ring cyclization gave the desired ABC endo-tricarbocycle. The C-ring moiety of this product was reduced under Birch conditions to the cyclohexadiene derivative, which was oxygenated by singlet

  完成了紫杉醇的对映选择性全合成。光学纯 A 环羟基醛与芳族 C 环片段的偶联反应，然后是路易斯酸介导的八元 B 环环化，得到所需的 ABC 内三碳环。该产物的 C 环部分在 Birch 条件下被还原为环己二烯衍生物，该衍生物被来自凸 β 面的单线态氧氧化，立体选择性地得到 C4β、C7β-二醇。为了引入C19-甲基，环丙基酮通过C-环烯丙醇的环丙烷化或氰基与C-环烯酮的共轭加成来制备。环丙烷环的还原裂解，然后将所得烯醇异构化为相应的酮，得到含有 C19-甲基的关键合成中间体。
• Practical hydroxymethylation of aldehydes and ketones via pinacol cross-coupling reactions with paraformaldehyde
  作者：Jeonghan Park、Steven F. Pedersen

  DOI：10.1016/s0040-4020(01)88875-x

  日期：——

  method for the direct hydroxymethylation of aldehydes and ketones via pinacol cross-coupling with paraformaldehyde is described. The reaction is promoted by vanadium(II) ions which are conveniently generated from the reduction of VCl3(THF)3 with zinc dust. Excellent yields of terminal diols are obtained and stereoselective coupling is observed with some chiral aldehydes and ketones.

  描述了通过频哪醇与多聚甲醛交叉偶联直接醛和酮进行羟甲基化的一般实用方法。钒（II）离子可促进反应，钒离子可通过用锌粉还原VCl 3（THF）3方便地产生。获得了优异的末端二醇收率，并且观察到与一些手性醛和酮的立体选择性偶联。
• Synthesis of Tetramic Acid Derivatives via a Tandem Umpolung Alkylation/Reduction/Cyclization Reaction of γ-Hydrazono β-Ketoester
  作者：Isao Mizota、Miki Maeda、Kiho Imoto、Makoto Shimizu

  DOI：10.1021/acs.orglett.0c00824

  日期：2020.4.17

  An efficient method for the one-pot synthesis of tetramic acid derivatives was developed utilizing tandem umpolung N-alkylation/reduction/cyclization of γ-hydrazono β-ketoester. By using this reaction as a key step, the total synthesis of the 3-spiro 7-hydroxamic acid tetralin which possesses an HDAC inhibitory activity was also achieved.

  开发了一种高效的一锅法合成四酸衍生物的方法，该方法利用了串联反应中的γ-肼基β-酮酸酯的N-烷基化/还原/环化反应。通过将该反应用作关键步骤，还实现了具有HDAC抑制活性的3-螺7-异羟肟酸四氢萘的全合成。
• Stereoselective reduction of α-iodospirolactones. Total synthesis of (±)-liguloxide.
  作者：Eun Lee、Dae Sung Lee、Yoon Whan Choi、Kwang Ho Lee

  DOI：10.1016/s0040-4039(00)61015-8

  日期：1992.10

  Radical-mediated reduction of α-methyl-α-iodospirolactones yielded trans-α-methylspirolactones selectively. This reaction was used in the total synthesis of (±)-liguloxide.

  自由基介导的α-甲基-α-碘螺内酯的还原选择性地产生了反式-α-甲基螺内酯。该反应用于（±）-木糖醇的全合成。
• An Organotrifluoroborate-Based Convergent Total Synthesis of the Potent Cancer Cell Growth Inhibitory Depsipeptides Kitastatin and Respirantin
  作者：Ramsay E. Beveridge、Robert A. Batey

  DOI：10.1021/ol500484f

  日期：2014.5.2

  The total syntheses of the highly cytotoxic neo-antimycin macrocyclic depsipeptide natural products kitastatin and respirantin have been accomplished in a convergent manner using MNBA promoted esterifications and an efficient C- and N-terminus bis-deprotection/HATU promoted macrolactamization. The first examples of using a prenyltrifluoroborate reagent in additions to carbonyl groups are disclosed

  使用MNBA促进的酯化作用以及有效的C和N端双去保护/ HATU促进的大内酰胺化作用，以收敛的方式完成了高度细胞毒性的新抗霉素大环二肽天然肽kitastatin和respirantin的总合成。公开了除羰基外还使用异戊烯基三氟硼酸酯试剂的第一个实例，包括非对映选择性的多克级蒙脱石K10催化的N- Boc- 1-亮氨酸的烯丙基化，以安装结构上独特的宝石-二甲基-β-酮-酯片段。