ethyl α-tosyloxyacetoacetate

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: ethyl α-tosyloxyacetoacetate
• 英文别名: ethyl 3-oxo-2-(tosyloxy)butanoate；ethyl 2-tosyloxyacetoacetate；Ethyl 2-(4-methylphenyl)sulfonyloxy-3-oxobutanoate；ethyl 2-(4-methylphenyl)sulfonyloxy-3-oxobutanoate
• 化学式: C₁₃H₁₆O₆S
• 分子量: 300.332
• InChiKey: WMXSITJSOPWTTK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  20
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  95.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  tert-butyl methyl(tosyloxy)carbamate 在 甲烷磺酸 、 三氟乙酸 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 27.0h， 生成 ethyl α-tosyloxyacetoacetate
  参考文献：
  名称：

  Direct α-Oxytosylation of Carbonyl Compounds:  One-Pot Synthesis of Heterocycles

  摘要：

  N-Methyl-O-tosylhydroxylamine is an effective reagent for the direct alpha-oxytosylation of carbonyl compounds. The reactions proceed smoothly at room temperature in the presence of both moisture and air and functional group tolerance in the substrate is good. With nonsymmetrical substrates regioselectivity for primary over secondary centers is observed and complete regiospecificity for primary over tertiary centers is obtained. Addition of a bis-heteronucleophile directly to the crude reaction mixture in a one-pot process leads to the corresponding heterocyclic product.

  DOI：

  10.1021/ol701774y

文献信息

• Evolution of <i>N</i> ‐Heterocycle‐Substituted Iodoarenes (NHIAs) to Efficient Organocatalysts in Iodine(I/III)‐Mediated Oxidative Transformations
  作者：Andreas Boelke、Boris J. Nachtsheim

  DOI：10.1002/adsc.201901356

  日期：2020.1.7

  The reactivity of ortho‐functionalized N‐heterocycle‐substituted iodoarenes (NHIAs) as organocatalysts in iodine(I/III)‐mediated oxidations was systematically investigated in the α‐tosyloxylation of ketones as the model reaction. During a systematic catalyst evolution, it was found that NH‐triazoles and benzoxazoles have the most significant positive influence on the reactivity of the central iodine

  的反应性的邻位-官能化ñ -杂环取代iodoarenes（NHIAs），如碘（I / III）介导的氧化反应是在系统地研究有机催化剂α酮作为模型反应的-tosyloxylation。在系统的催化剂进化过程中，发现NH-三唑和苯并恶唑对中心碘原子的反应性具有最显着的积极影响。催化剂的进一步改进集中在芳烃的取代模式上，显示出显着的邻位效应。通过引入一个o- OMe基团，我们能够生成一种新型的NHIA，其催化效率目前还没有发现。这种新的催化剂不仅易于合成，而且还可以报告的最低催化剂负载量仅为1 mol％时，羰基化合物的α-甲苯磺酰氧基化。最后，该碘（I）催化剂的性能已在联苯的分子内氧化偶合和氧化重排中得到了成功证明。
• Various α-Oxygen Functionalizations of β-Dicarbonyl Compounds Mediated by the Hypervalent Iodine(III) Reagent<i>p</i>-Iodotoluene Difluoride with Different Oxygen-Containing Nucleophiles
  作者：Jun Yu、Jun Tian、Chi Zhang

  DOI：10.1002/adsc.200900737

  日期：2010.2.15

  for the effective introduction of various oxygen-containing functionalities including tosyloxy, mesyloxy, acetoxy, phosphoryloxy, methoxy, ethoxy and isopropoxy at the α-position of β-dicarbonyl compounds. These transformations can be readily realized by the use of the combined reagent of p-iodotoluene difluoride and various oxygen-containing nucleophilic compounds such as p-toluenesulfonic acid, methanesulfonic

  p -Iodotoluene二氟乙烯（p -Tol-IF 2）已被发现是一种一般用于有效地引入各种含氧官能团包括甲苯磺酰氧基，甲磺酰氧基，乙酰氧基，磷酰甲氧基，乙氧基和异丙氧基在α位的试剂β-二羰基化合物。通过使用对-碘甲苯二氟化物和各种含氧亲核化合物如对甲苯磺酸，甲磺酸，乙酸，磷酸二苯酯，甲醇，乙醇和丙-2-醇的组合试剂，可以轻松实现这些转化。分别在温和的条件下。并且，原位生成的高价碘（III）物种通过在这种转化中，对-碘甲苯二氟化物与相应的含氧亲核试剂之间的配体交换被认为是真正的氧化剂。
• α-Tosyloxylation of ketones with ion-supported[hydroxy(tosyloxy)iodo] benzene
  作者：Feng Su、Jizhen Zhang、Guangyu Jin、Tao Qiu、Dejian Zhao、Hongbin Jia

  DOI：10.3184/030823409x12590815399135

  日期：2009.12

  room-temperature ionic liquid (RTIL) supported [hydroxy(tosyloxy)iodo]benzene (ion-supported HTIB) reagent was synthesised by three kinds of effective methods in high yields, which combined the advantages of ionic liquids and the hypervalent iodine. Ion-supported HTIB was an effective reagent for one-step conversion of ketones to the corresponding α-tosyloxylated ketones in the ionic liquid [emim]BF4or acetonitrile

  结合离子液体和高价碘的优点，采用三种有效的方法以高产率合成了一种新型的室温离子液体（RTIL）负载[羟基（甲苯磺酰氧基）碘]苯（离子负载HTIB）试剂。离子负载的 HTIB 是一种有效的试剂，用于在微波下将酮一步转化为离子液体 [emim]BF4 或乙腈中相应的 α-甲苯磺酰氧基化酮。转化反应后，试剂转化为离子负载的碘苯，易于回收和再生而不会损失活性。
• A Novel One-Pot Method for α-Tosyloxylation of Ketones Using a Catalytic Amount of Ammonium Iodide
  作者：Jie Yan、Jiantao Hu、Min Zhu、Yuan Xu

  DOI：10.1055/s-0031-1289750

  日期：2012.4

  A novel one-pot procedure was designed for the preparation of various α-tosyloxy ketones in good yields by the reaction of ketones with m-chloroperoxybenzoic acid and p-toluenesulfonic acid monohydrate in the presence of catalytic amounts of ammonium iodide and benzene in a mixture of acetonitrile and 2,2,2-trifluo­roethanol (8:2) at room temperature for 24 hours. α-tosyloxylation - α-tosyloxy ketones

  一种新的单罐方法被设计为通过与酮的反应制备以良好的收率各种α-甲苯磺酰氧基酮的米氯过氧酸和p -甲苯磺酸一水合物在催化量的碘化铵和苯的存在在混合物中在室温下将乙腈和2,2,2-三氟乙醇（8：2）混合24小时。 α-甲苯磺酰化-α-甲苯磺酰酮-高价碘中间体-碘化铵
• [EN] NEW INTERMEDIATE COMPOUND FOR PREPARING VITAMIN B6<br/>[FR] NOUVEAU COMPOSÉ INTERMÉDIAIRE POUR LA PRÉPARATION DE VITAMINE B6
  申请人：DSM IP ASSETS BV

  公开号：WO2013163889A1

  公开（公告）日：2013-11-07

  Provided is a new intermediate compound for preparing vitamin B6, which can be used to synthesize the known intermediate compound for preparing vitamin B6, 4-methyloxazole-5-carboxyLate. Further provided is a process for preparing the new intermediate compound and a process for preparing the known intermediate compound 4-methyloxazole-5-carboxylate from the new intermediate compound.

  提供了一种新的中间化合物，用于制备维生素B6，可用于合成用于制备维生素B6的已知中间化合物4-甲氧咪唑-5-羧酸。进一步提供了制备新中间化合物的方法以及从新中间化合物制备已知中间化合物4-甲氧咪唑-5-羧酸的方法。