lithium isopropenolate | 67863-40-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: lithium isopropenolate
• 英文别名: acetone lithium enolate；lithium enolate of acetone；Lithioacetone；lithium;prop-1-en-2-olate
• CAS: 67863-40-5
• 化学式: C₃H₅LiO
• 分子量: 64.0131
• InChiKey: CEEFXENRXVKITH-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -3.12
• 重原子数：
  5
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  23.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  lithium isopropenolate 生成 [2-(3-oxobutanoyl)phenyl] acetate
  参考文献：
  名称：

  WATANABE T.; NAKASHITA Y.; KATAYAMA S.; YAMAUCHI M., J. CHEM. SOC. CHEM. COMMUNS , 1977, NO 14, 493-494

  摘要：

  DOI：
• 作为产物：
  描述：

  丙酮 在 正丁基锂 、 二异丙胺 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.0h， 生成 lithium isopropenolate
  参考文献：
  名称：

  Nucleophilic additions to ketenes by (trimethylsilyl)lithium and by enolates

  摘要：

  DOI：

  10.1021/jo00298a047

文献信息

• Enantioselective Multicomponent Synthesis of Fused 6-5 Bicyclic 2-Butenolides by a Cascade Heterobicyclisation Process
  作者：Marcos G. Suero、Raquel De la Campa、Laura Torre-Fernández、Santiago García-Granda、Josefa Flórez

  DOI：10.1002/chem.201102288

  日期：2012.6.4

  heterobicyclisation products is the result of the regioselective integration of the Grignard reagent as a propargyl fragment followed by a cascade CO/alkyne/CO insertion, ketene trapping and elimination sequence. By using lithium enolates of chiral N‐acetyl‐2‐oxazolidinones and the corresponding propargylic organocerium reagents, both enantiomers of these bicyclic heterocycles were efficiently prepared with

  铬的烷氧基（芳基/杂芳基）卡宾络合物与酮或酰亚胺烯醇锂的连续偶联，然后与3-取代的（H，TMS，PhCH 2，PhCH 2 CH 2，Me）炔丙基有机镁试剂偶联具有三个模块化点的新型羟基取代双环[4.3.0]-γ-亚烷基-2-丁烯内酯，可有效引入分子复杂性，包括均丙醇核心。这些五或六组分异双环化产物的选择性形成是格氏试剂作为炔丙基片段进行区域选择性整合，随后是级联的CO /炔烃/ CO插入，乙烯酮捕获和消除序列的结果。通过使用手性N的烯醇锂对乙酰基-2-恶唑烷酮和相应的炔丙基有机铈试剂，均以非常高的对映体纯度有效地制备了这些双环杂环的对映体。在结构上，这些稠合的双环丁烯内酯的特征是高度不饱和和氧化的核，并且它们在溶液中显示出很强的蓝色荧光。
• Controlling stereochemistry in polyketide synthesis: 1,3- vs. 1,2-asymmetric induction in methyl ketone aldol additions to β-super siloxy aldehydes
  作者：Patrick B. Brady、Brian J. Albert、Matsujiro Akakura、Hisashi Yamamoto

  DOI：10.1039/c3sc51183a

  日期：——

  The aldol addition of methyl ketones to β-siloxy and α-methyl β-siloxy aldehydes is described. Careful control of mechanistically distinct aldol reactions leverages 1,2- and 1,3-asymmetric induction, selectively forming syn and anti aldol adducts with excellent diastereocontrol. Experimental and theoretical investigations have provided insight to the factors governing diastereoselectivity.

  描述了将甲基酮醛醇缩合至β-甲硅烷氧基和α-甲基β-甲硅烷氧基醛。仔细控制机械上不同的羟醛反应可利用1,2-和1,3-不对称诱导，选择性地形成顺式和反式羟醛加合物，并具有出色的非对映控制性。实验和理论研究为控制非对映选择性的因素提供了见识。
• Automated synthesis of11C-β-hydroxybutyrate by enzymatic conversion of11C-acetoacetate using β-hydroxybutyrate dehydrogenase
  作者：Sébastien Tremblay、René Ouellet、François Bénard、Stephen C. Cunnane

  DOI：10.1002/jlcr.1504

  日期：2008.4

  1-[11C]-β-hydroxybutyrate was produced by conversion from 1-[11C]-acetoacetate using (D)-β-hydroxybutyrate dehydrogenase in the presence of nicotinamide adenine dinucleotide with purification by ion exchange column chromatography. Radiochemical yield at the end of the synthesis was 10% for a total synthesis time of 36 min. High-performance liquid chromatography analysis showed ≤4% impurities, principally unconverted acetoacetate. Residual tetrahydrofuran (34±11 ppm) and ethanol (77±30 ppm) were well under the tolerable limits for human studies. Copyright © 2008 John Wiley & Sons, Ltd.

  1-[11C]-β-羟基丁酸盐通过（D）-β-羟基丁酸盐脱氢酶在烟酰胺腺嘌呤二核苷酸存在下，由1-[11C]-乙酰乙酸盐转化而制得，并通过离子交换柱层析进行纯化。合成结束时的放射化学产率为10%，总合成时间为36分钟。高效液相色谱分析显示杂质≤4%，主要是未转化的乙酰乙酸盐。残留的四氢呋喃（34±11 ppm）和乙醇（77±30 ppm）均远低于人体研究的可容忍限值。版权所有 © 2008 John Wiley & Sons, Ltd.
• Asymmetric Induction in Methyl Ketone Aldol Additions to α-Alkoxy and α,β-Bisalkoxy Aldehydes:  A Model for Acyclic Stereocontrol
  作者：David A. Evans、Victor J. Cee、Sarah J. Siska

  DOI：10.1021/ja061010o

  日期：2006.7.1

  systematic study of methyl ketone aldol additions under nonchelating conditions with α-alkoxy and α,β-bisalkoxy aldehydes is described. Additions to aldehydes containing a single α-alkoxy stereocenter generally provide the product diastereomers in accord with the Cornforth/polar Felkin-Anh models for carbonyl addition. Vicinal asymmetric induction is sensitive to the aldehyde α-alkyl substituent, but is relatively

  描述了在非螯合条件下与 α-烷氧基和 α,β-双烷氧基醛的甲基酮醛醇加成的系统研究。添加到含有单个 α-烷氧基立体中心的醛中通常会提供与用于羰基加成的 Cornforth/极性 Felkin-Anh 模型一致的产物非对映异构体。邻位不对称诱导对醛α-烷基取代基敏感，但对烷氧基保护基团的性质相对不敏感。除了含有额外的 β-烷氧基取代的立体中心的底物之外，醛的 π 面选择性表现出对 α-和 β-立体中心的相对构型的显着依赖性。α-和β-烷氧基取代基呈反关系的醛在大多数情况下表现出良好的非对映选择性，而具有顺式关系的α-和β-烷氧基取代基的醛出乎意料地得到产物混合物。提出了一种基于类似 Cornforth 的过渡态排列的立体化学模型。
• Highly efficient indium(<scp>iii</scp>)-mediated cyclisation of 5-hydroxy-1,3-diketones to 2,3-dihydro-4H-pyran-4-ones; mechanistic insights from in situFourier transform infrared spectroscopy
  作者：Philip C. Andrews、William J. Gee、Peter C. Junk、Harald Krautscheid

  DOI：10.1039/b919402a

  日期：——

  5-Hydroxy-1,3-diketones have been synthesised in a facile one-pot reaction from the treatment of acid chlorides with non-substituted ketones and LiHMDS. Subsequent cyclisation to 2,3-dihydro-4H-pyran-4-ones occurs rapidly and in high yield (89–99%) when mediated by anhydrous indium(III) chloride. A spectroscopic study of the reaction using in situ Fourier transform infrared (FTIR) spectroscopy has shown the reaction to be highly dependent on temperature, metal complex formation and InCl3 concentration. Since the reaction is deactivated by the precipitation of [InCl3·(H2O)3], the concurrent use of a stronger drying agent, such as molecular sieves 4 Å or anhydrous MgSO4, allows the reaction to be successfully carried out at relatively low loadings of InCl3 (1–10%). In their absence, the optimum reaction conditions were found to be a diketone : InCl3 ratio of 3 : 1 in toluene, and a reaction temperature of 80 °C.

  5-羟基-1,3-二酮通过将酸氯化物与非取代的酮和LiHMDS在简单的一锅反应中合成。随后在无水氯化铟(III)的催化下快速且高产率（89-99%）发生环化反应生成2,3-二氢-4H-吡喃-4-酮。对该反应的光谱学研究表明，反应高度依赖于温度、金属络合物的形成以及InCl3的浓度。由于反应会因[InCl3·(H2O)3]的沉淀而失活，因此同时使用更强的干燥剂，如4Å分子筛或无水MgSO4，可以使反应在相对低的InCl3负载（1-10%）下成功进行。在没有这些干燥剂的情况下，发现最佳反应条件为二酮与InCl3的摩尔比为3:1，溶剂为甲苯，反应温度为80°C。