tert-butyl 2-(benzamidooxy)-2-methylpropanoate | 211812-14-5

• 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: tert-butyl 2-(benzamidooxy)-2-methylpropanoate
• 英文别名: Tert-butyl 2-benzamidooxy-2-methylpropanoate
• CAS: 211812-14-5
• 化学式: C₁₅H₂₁NO₄
• 分子量: 279.336
• InChiKey: WKXCUXOEOIPOGS-UHFFFAOYSA-N

物化性质

• 密度：
  1.094±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  64.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  tert-butyl 2-(benzamidooxy)-2-methylpropanoate 在 lithium hydroxide 、 4-甲基苯磺酸吡啶 、 potassium carbonate 、 亚硝酰氯 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 反应 16.0h， 生成 Tert-butyl 2-(2-methoxypropan-2-ylperoxy)-2-methylpropanoate
  参考文献：
  名称：

  Preparation of Unsymmetrically Labeled Hydroperoxides. A Hydroxamate Ester−Nitrosation Approach

  摘要：

  Reaction of O-tertiary alkyl arylhydroxamate esters with nitrosyl chloride gives O-tertiary alkyl aryl peresters that can be hydrolyzed to the hydroperoxide. If the hydroxamate ester carbonyl oxygen or nitrosyl chloride is labeled with O-18, the label appears in the product hydroperoxide's terminal oxygen. This strategy, which derives from the pioneering work of Koenig, permits the preparation of a variety of(2-O-18) hydroperoxides, including tertiary alkyl and cumyl hydroperoxides. tert-Butyl alpha-hydroperoxyisobutyrate, 27, prepared in this way with an O-18 label in the terminal oxygen, serves as a useful precursor for the preparation of other unsymmetrically labeled peroxides and hydroperoxides. Hydroperoxide 27 is protected as a perketal with 2-methoxypropene, and a six-step sequence involving Dibal-H reduction, oxidation (PDC), and Wittig chemistry provides the allylic hydroperoxide 12 that is used in mechanistic studies. Hydroxamate esters that give peresters prone to undergo the Criegee rearrangement upon reaction with NOCl do not give useful yields of product hydroperoxides in the transformation and one hydroxamate ester 17 that reacts via an allylalkoxyl radical gives epoxides 20a and 20b as the major isolable products of reaction.

  DOI：

  10.1021/jo980654e
• 作为产物：
  描述：

  2-溴代异丁酸叔丁酯 、 苯甲羟肟酸 在 potassium hydroxide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 17.33h， 以72%的产率得到tert-butyl 2-(benzamidooxy)-2-methylpropanoate
  参考文献：
  名称：

  通过氧化α-酰胺基氧基酸的酰胺基自由基：未活化烯烃的无过渡金属的氨基氟化

  摘要：

  给出了未活化的烯烃和苯乙烯的三组分无过渡金属的氨基氟化。引入α-酰胺基氧基酸是一种高效且易于获得的mid基自由基前体，它们被光激发有机敏化剂（Mes-Acr-Me）氧化为相应的羧基。依次发生的CO 2和醛/酮裂解会导致一个以N为中心的自由基加成烯烃。商业Selectfluor用于通过氟原子转移捕获加合物自由基。这种转变具有很高的官能团耐受性，广泛的底物范围和实用的温和条件。力学研究支持级联的根本性质。

  DOI：

  10.1002/anie.201804966

文献信息

• Anti‐Markovnikov Radical Hydro‐ and Deuteroamidation of Unactivated Alkenes
  作者：Heng Jiang、Armido Studer

  DOI：10.1002/chem.201901566

  日期：2019.5.23

  Radical anti‐Markovnikov hydro‐ and deuteroamidation of unactivated alkenes was achieved by merging photoredox and thiol catalysis. Reactions proceed by addition of the electrophilic CbzHN‐radical (Cbz=carbobenzyloxy), readily generated by single‐electron‐transfer (SET) oxidation of an α‐Cbz‐amino‐oxy acid to an alkene. The adduct radical is reduced by thiophenol added as an organic polarity reversal

  通过结合光氧化还原和硫醇催化，实现未活化烯烃的自由基抗马尔科夫尼科夫加氢和氘代氨基酰胺化反应。反应通过添加亲电子的CbzHN自由基（Cbz =羰基苄氧基）进行，该过程很容易通过α-Cbz-氨基氧基酸的单电子转移（SET）氧化反应生成烯烃。加成物自由基被作为有机极性反转助催化剂加入的苯硫酚还原，后者介导H从H 2 O转移至烷基自由基中间体。因此，通过使用D 2，以优异的D掺入实现了烯烃的氘代氨基酰胺化。O为化学计量形式的自由基还原剂。该反应具有低氧化还原催化剂负载量，出色的抗马尔可夫尼科夫选择性，并且不需要使用大量的过量烯烃。通过这种方法可以得到各种Cbz保护的伯胺，包括β氘代的胺。
• Transition‐Metal‐Free Three‐Component Radical 1,2‐Amidoalkynylation of Unactivated Alkenes
  作者：Heng Jiang、Armido Studer

  DOI：10.1002/chem.201805490

  日期：——

  A transition‐metal‐free radical 1,2‐amidoalkynylation of unactivated alkenes is presented. α‐Amido‐oxy acids were used as amidyl radical precursors, which were oxidized by an organic photoredox catalyst (4CzlPN). The electrophilic N‐radicals chemoselectively reacted with various aliphatic alkenes and the adduct radicals were then trapped by ethynylbenziodoxolone (EBX) reagents to eventually provide

  给出了未活化烯烃的过渡金属自由基1,2-酰胺基炔化反应。α-酰胺基氧基酸用作酰胺基自由基前体，它们被有机光氧化还原催化剂（4CzlPN）氧化。亲电性N自由基与各​​种脂肪族烯烃发生化学选择性反应，然后加成基被乙炔基苯并恶唑啉酮（EBX）试剂捕获，最终提供了酰胺基烷基化产物。这些在实际温和条件下进行的转化显示出较高的官能团耐受性和广泛的底物范围。机理研究支持了这些级联的激进性质。
• Amidyl Radicals by Oxidation of α‐Amido‐oxy Acids: Transition‐Metal‐Free Amidofluorination of Unactivated Alkenes
  作者：Heng Jiang、Armido Studer

  DOI：10.1002/anie.201804966

  日期：2018.8.13

  three‐component transition‐metal‐free amidofluorination of unactivated alkenes and styrenes is presented. α‐Amido‐oxy acids are introduced as efficient and easily accessible amidyl radical precursors that are oxidized by a photoexcited organic sensitizer (Mes‐Acr‐Me) to the corresponding carboxyl radical. Sequential CO2 and aldehyde/ketone fragmentation leads to an N‐centered radical that adds to an

  给出了未活化的烯烃和苯乙烯的三组分无过渡金属的氨基氟化。引入α-酰胺基氧基酸是一种高效且易于获得的mid基自由基前体，它们被光激发有机敏化剂（Mes-Acr-Me）氧化为相应的羧基。依次发生的CO 2和醛/酮裂解会导致一个以N为中心的自由基加成烯烃。商业Selectfluor用于通过氟原子转移捕获加合物自由基。这种转变具有很高的官能团耐受性，广泛的底物范围和实用的温和条件。力学研究支持级联的根本性质。
• Preparation of Unsymmetrically Labeled Hydroperoxides. A Hydroxamate Ester−Nitrosation Approach
  作者：Ned. A. Porter、Sarah E. Caldwell、Jennifer R. Lowe

  DOI：10.1021/jo980654e

  日期：1998.8.1

  Reaction of O-tertiary alkyl arylhydroxamate esters with nitrosyl chloride gives O-tertiary alkyl aryl peresters that can be hydrolyzed to the hydroperoxide. If the hydroxamate ester carbonyl oxygen or nitrosyl chloride is labeled with O-18, the label appears in the product hydroperoxide's terminal oxygen. This strategy, which derives from the pioneering work of Koenig, permits the preparation of a variety of(2-O-18) hydroperoxides, including tertiary alkyl and cumyl hydroperoxides. tert-Butyl alpha-hydroperoxyisobutyrate, 27, prepared in this way with an O-18 label in the terminal oxygen, serves as a useful precursor for the preparation of other unsymmetrically labeled peroxides and hydroperoxides. Hydroperoxide 27 is protected as a perketal with 2-methoxypropene, and a six-step sequence involving Dibal-H reduction, oxidation (PDC), and Wittig chemistry provides the allylic hydroperoxide 12 that is used in mechanistic studies. Hydroxamate esters that give peresters prone to undergo the Criegee rearrangement upon reaction with NOCl do not give useful yields of product hydroperoxides in the transformation and one hydroxamate ester 17 that reacts via an allylalkoxyl radical gives epoxides 20a and 20b as the major isolable products of reaction.