methyl 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: methyl α-tosyloxyacetoacetate
• 英文别名: metyhyl α-tosyloxyacetoacetate；Methyl 2-(4-methylphenyl)sulfonyloxy-3-oxobutanoate
• 化学式: C₁₂H₁₄O₆S
• 分子量: 286.306
• InChiKey: ADSUTZZLKZGTNK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  95.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  ethyl 5-acetoxy-5-phenylpent-2,3-dienoate 、 methyl α-tosyloxyacetoacetate 在 sodium carbonate 、 三苯基膦 作用下， 以 甲苯 为溶剂， 反应 12.0h， 以50%的产率得到C₁₈H₁₈O₄
  参考文献：
  名称：

  Phosphine-Promoted Divergent Annulations of δ-Acetoxy Allenoates with α-Hydroxy-β-carbonyl Ester Derivatives: Synthesis of Tetrasubstituted Cyclopentadienes and Benzenes

  摘要：

  The substrate-dependent annulations of (delta-acetoxy allenoates with alpha-hydroxy-beta-carbonyl ester derivatives are reported. 2-[(Methoxycarbonyl)oxy]malonate as a C1 partner is able to undergo (1 + 4) annulations with allenoates in the presence of a catalytic amount of phosphine, affording cyclopentadienes in good yields. However, (2 + 4) annulations of allenoates with 2-(tosyloxy)-3-ketoesters are instead observed with the assistance of stoichiometrical phosphine and base, leading to tetrasubstituted benzene products. In these two reactions, delta-acetoxy allenoate serves as a 1,4-disubstituted diene synthon.

  DOI：

  10.1021/acs.orglett.8b03808
• 作为产物：
  描述：

  β-氨基巴豆酸甲酯 、 1-[hydroxy(tosyloxy)iodo]-1H,1H-perfluoroethane 以 氯仿 为溶剂， 反应 2.0h， 生成 methyl α-tosyloxyacetoacetate
  参考文献：
  名称：

  环状烯胺的新型三氟乙基碘鎓盐及其热分解

  摘要：

  使1- [羟基（甲苯磺酰基氧基）碘] -2,2,2-三氟乙烷与环状烯胺酮反应，得到稳定的碘代甲苯磺酸盐。它们温和的热解提供了碘烯酮和甲苯磺酸2,2,2-三氟乙基酯。

  DOI：

  10.1016/s0040-4039(97)10232-5

文献信息

• PhI- and polymer-supported PhI-catalyzed oxidative conversion of ketones and alcohols to α-tosyloxyketones with m-chloroperbenzoic acid and p-toluenesulfonic acid
  作者：Yukiharu Yamamoto、Yuhta Kawano、Patrick H. Toy、Hideo Togo

  DOI：10.1016/j.tet.2007.03.091

  日期：2007.5

  Various ketones were converted to the corresponding α-tosyloxyketones with mCPBA and p-toluenesulfonic acid in the presence of a catalytic amount of iodobenzene. Moreover, secondary alcohols were directly converted to the corresponding α-tosyloxyketones using mCPBA and catalytic amounts of iodobenzene and potassium bromide, followed by treatment with p-toluenesulfonic acid in a one-pot manner. Poly(4-iodostyrene)

  各种酮转化成相应的α-tosyloxyketones与米CPBA和p在碘苯催化量的存在对甲苯磺酸。此外，使用m CPBA和催化量的碘代苯和溴化钾将仲醇直接转化为相应的α-甲苯磺酰氧基酮，然后以对-甲苯磺酸的一锅法处理。聚（4-碘苯乙烯）也可用作与酮相同的α-甲苯磺酰化反应的可回收催化剂
• Iodoarene-Mediated α-Tosyloxylation of Ketones with MCPBA and p-Toluenesulfonic Acid
  作者：Hideo Togo、Ayumi Tanaka、Katsuhiko Moriyama

  DOI：10.1055/s-0030-1260948

  日期：2011.8

  Alkyl aryl ketones and dialkyl ketones could be converted into the corresponding α-tosyloxy ketones by the reaction with MCPBA and p-toluenesulfonic acid monohydrate (PTSA˙H2O) in the presence of a catalytic amount of molecular iodine (I2) in a mixture of acetonitrile and 2,2,2-trifluoroethanol, although the yields were dependent on the ketones (method A). The same conversion of alkyl aryl ketones and dialkyl ketones into the corresponding α-­tosyloxy ketones could be smoothly carried out by the reaction with MCPBA and PTSA˙H2O in the presence of catalytic amounts of ­iodine and tert-butylbenzene in a mixture of acetonitrile and 2,2,2-trifluoroethanol (method B). In those reactions, p-iodotoluene and 4-tert-butyl-1-iodobenzene were formed at first in method A and method B, respectively, and then they were converted into p-[(hydroxy)(tosyloxy)]iodotoluene and 4-tert-butyl-1-[(hydroxy)(tosyloxy)iodo]benzene by the reaction with MCPBA and PTSA˙H2O. p-[(Hydroxy)(tosyloxy)]iodotoluene and 4-tert-butyl-1-[(hydroxy)-(tosyloxy)iodo]benzene worked as an α-tosyloxylation reagent of ketones.

  烷基芳基酮和二烷基酮可以通过与间氯过氧苯甲酸（MCPBA）和单水合对甲苯磺酸（PTSA·H2O）在催化量的碘分子（I2）存在下反应，在乙腈和2,2,2-三氟乙醇的混合物中，转化为相应的α-甲苯磺酰氧基酮，尽管产率取决于酮类（方法A）。烷基芳基酮和二烷基酮同样可以通过与MCPBA和PTSA·H2O在催化量的碘和叔丁基苯存在下反应，在乙腈和2,2,2-三氟乙醇的混合物中，顺利转化为相应的α-甲苯磺酰氧基酮（方法B）。在这些反应中，方法A和方法B分别首先形成对碘甲苯和4-叔丁基-1-碘苯，然后它们通过与MCPBA和PTSA·H2O反应转化为对[(羟基)(甲苯磺酰氧基)]碘甲苯和4-叔丁基-1-[(羟基)(甲苯磺酰氧基)碘]苯。对[(羟基)(甲苯磺酰氧基)]碘甲苯和4-叔丁基-1-[(羟基)(甲苯磺酰氧基)碘]苯作为酮的α-甲苯磺酰氧化试剂。
• 4-MeC6H4I-Mediated Efficient α-Tosyloxylation of Ketones with Oxone® and p-Toluenesulfonic Acid in Acetonitrile
  作者：Hideo Togo、Ayumi Tanaka

  DOI：10.1055/s-0029-1218370

  日期：2009.12

  Various alkyl aryl ketones, dialkyl ketones, and cycloheptanone were efficiently converted into the corresponding α-tosyl­oxy ketones in good yields by using Oxone® and p-toluenesulfonic acid monohydrate in the presence of p-iodotoluene in acetonitrile. 4-Methoxyacetophenone and 2-acetylthiophene bearing an electron-rich aromatic group could be also converted into the corresponding α-tosyloxyketones smoothly in good yields with the present method. Here, p-iodotoluene works as catalyst and p-[(hydroxy)(tosyloxy)]iodotoluene is formed in situ as a reactive species for the α-tosyloxylation of ketones. However, one equivalent of p-iodotoluene was required to obtain α-tosyloxyketones in good yields and was recovered in 80-20% yields, depending on the reaction conditions.

  通过在乙腈中使用Oxone®和p-甲苯磺酸一水合物，并在p-碘甲苯的存在下，各种烷基芳香酮、二烷基酮和环庚酮高效地转化为相应的α-甲苯磺酰氧基酮，产率良好。带有富电子芳香基团的4-甲氧基苯乙酮和2-乙酰基噻吩也可以用当前方法顺利地转化为相应的α-甲苯磺酰氧基酮，产率良好。在这里，p-碘甲苯作为催化剂，并且原位生成p-[(羟基)(甲苯磺酰氧基)]碘甲苯作为酮的α-甲苯磺酰氧化反应的活性物质。然而，为了获得良好的α-甲苯磺酰氧基酮产率，需要等量的p-碘甲苯，并且根据反应条件的不同，其回收率为80-20%。
• Solvent-free synthesis of 1-(p-toluenesulfonyloxy)-1,2-benziodoxol-3(1H)-one from Dess–Martin periodinane and its synthetic utility for α-tosyloxylation of ketones
  作者：Nandkishor N. Karade、Girdharilal B. Tiwari、Sandeep V. Shinde、Sumeet V. Gampawar、Jeevan M. Kondre

  DOI：10.1016/j.tetlet.2008.03.119

  日期：2008.5

  The solvent-free synthesis of 1-(p-toluenesulfonyloxy)-1,2-benziodoxol-3(1H)-one is reported from Dess–Martin periodinane and p-toluenesulfonic acid monohydrate using a grinding technique and is subsequently utilized for the α-tosyloxylation of a range of enolisable ketones.

  Dess-Martin高碘烷和对-甲苯磺酸一水合物使用研磨技术报道了1-（对甲苯磺酰氧基）-1,2-苯并恶多酚-3（1 H）-one的无溶剂合成，随后用于研磨。一系列可固化酮的α-甲苯磺酰化。
• Novel Preparation of Polymer-Supported Iodobenzene and Its Synthetic Utility as a Recyclable Reagent with m-Chloroperbenzoic Acid
  作者：Hideo Togo、Yuhsuku Suzuki

  DOI：10.1055/s-0029-1218795

  日期：2010.7

  Three novel polymer-supported iodobenzene compounds A0, A6, and A10 were prepared from the reaction of commercially available cross-linked poly(p-chloromethyl)styrene with m-iodobenzylalcohol, 6-(m-iodobenzyloxy)-1-hexanol, and 10-(m-iodobenzyloxy)-1-decanol. Their catalytic reactivity and reusability for the oxidative α-tosyloxylation of ketones and the cyclization of N-methoxy-2-arylethanesulfonamides

  三种新型聚合物负载的碘苯化合物A 0，A 6和A 10从可商购的交联聚（的反应制备p氯甲基）苯乙烯与米-iodobenzylalcohol，6-（米-iodobenzyloxy）-1-己醇和10-（米-iodobenzyloxy）-1-癸醇。它们对酮的氧化α-对甲苯磺酰和的环化催化活性和可重用性Ñ在存在甲氧基-2- arylethanesulfonamides米氯过苯甲酸（米CPBA）被证实提供α-tosyloxyketones和Ñ-甲氧基-3,4-二氢-2,1-苯并噻嗪-2,2-二氧化物的收率很高。 聚合物支撑的Φ -再循环米CPBA - α-tosyloxyketone -酮- ñ -甲氧基-3,4-二氢-2,1-苯并噻嗪2,2-二氧化物-催化剂