2-苯并恶唑基丙酸叔丁酯 | 1026735-83-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并恶唑类
• 中文名称: 2-苯并恶唑基丙酸叔丁酯
• 英文名称: tert-butyl 2-benzoxazolylpropanoate
• 英文别名: Tert-butyl 3-(1,3-benzoxazol-2-yl)propanoate
• CAS: 1026735-83-0
• 化学式: C₁₄H₁₇NO₃
• 分子量: 247.294
• InChiKey: YHPUFPMVYTZMSR-UHFFFAOYSA-N

物化性质

• 沸点：
  341.5±25.0 °C(Predicted)
• 密度：
  1.132±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  52.3
• 氢给体数：
  0
• 氢受体数：
  4

上下游信息

• 上游原料

  中文名称	英文名称	CAS号	化学式	分子量
  2-甲基苯并唑	2-methyl-1,3-benzoxazole	95-21-6	C8H7NO	133.15

• 下游产品

  中文名称	英文名称	CAS号	化学式	分子量
  3-(1,3-苯并噁唑-2-基)丙酸	2-benzoxazolyl propanoic acid	78757-00-3	C10H9NO3	191.186

反应信息

• 作为反应物：
  描述：

  2-苯并恶唑基丙酸叔丁酯 在 sodium hydroxide 、 水 作用下， 以 甲醇 为溶剂， 反应 0.5h， 以65%的产率得到3-(1,3-苯并噁唑-2-基)丙酸
  参考文献：
  名称：

  Cycloaddition reactions of pyridinium and related azomethine ylides

  摘要：

  The Rh(H)-catalyzed reaction of alpha-diazoacetophenone in the presence of 2-(methylthio)pyridine and dimethyl acetylenedicarboxylate gave 3-benzoyl-1,2-dicarbomethoxy-3,5-dihydro-5-(methylthio)-indolizine. The formation of the cycloadduct proceeds via a pyridinium ylide formed by attack of the nitrogen lone pair on the electrophilic keto carbenoid. A related cyclization occurred using 1-diazo-3-[(2-pyridyl)thio]-2-propanone. The Rh(II)-catalyzed reaction of 1-(3'-diazoacetonyl)-2-pyridone with DMAD was also found to give cycloadducts derived from an azomethine ylide. The initial reaction involves generation of the expected carbonyl ylide dipole by intramolecular cyclization of the keto carbenoid onto the oxygen atom of the amide group. A subsequent proton exchange generates the thermodynamically more stable azomethine ylide which is trapped by DMAD. Azomethine ylide cycloadducts derived from keto carbenoid cyclization onto a thiobenzoxazole are also formed. When 1-diazo-3-[(2-benzoxazolyl)thio]-2-propanone was used, the initially formed cycloadduct underwent a subsequent 1,3-sigmatropic thio shift. An analogous cyclization occurred using 2-(4-diazo-3-oxobutyl)benzoxazole. In addition to undergoing dipolar cycloaddition, the highly stabilized dipole formed from this benzoxazole loses a proton to produce a cyclic ketene N,O-acetal. This compound reacts further with DMAD to eventually produce a novel phenolic lactam whose structure was established by an X-ray crystal structure analysis.

  DOI：

  10.1021/jo00057a029
• 作为产物：
  描述：

  2-甲基苯并唑 、 溴乙酸叔丁酯 生成 2-苯并恶唑基丙酸叔丁酯
  参考文献：
  名称：

  Cycloaddition reactions of pyridinium and related azomethine ylides

  摘要：

  The Rh(H)-catalyzed reaction of alpha-diazoacetophenone in the presence of 2-(methylthio)pyridine and dimethyl acetylenedicarboxylate gave 3-benzoyl-1,2-dicarbomethoxy-3,5-dihydro-5-(methylthio)-indolizine. The formation of the cycloadduct proceeds via a pyridinium ylide formed by attack of the nitrogen lone pair on the electrophilic keto carbenoid. A related cyclization occurred using 1-diazo-3-[(2-pyridyl)thio]-2-propanone. The Rh(II)-catalyzed reaction of 1-(3'-diazoacetonyl)-2-pyridone with DMAD was also found to give cycloadducts derived from an azomethine ylide. The initial reaction involves generation of the expected carbonyl ylide dipole by intramolecular cyclization of the keto carbenoid onto the oxygen atom of the amide group. A subsequent proton exchange generates the thermodynamically more stable azomethine ylide which is trapped by DMAD. Azomethine ylide cycloadducts derived from keto carbenoid cyclization onto a thiobenzoxazole are also formed. When 1-diazo-3-[(2-benzoxazolyl)thio]-2-propanone was used, the initially formed cycloadduct underwent a subsequent 1,3-sigmatropic thio shift. An analogous cyclization occurred using 2-(4-diazo-3-oxobutyl)benzoxazole. In addition to undergoing dipolar cycloaddition, the highly stabilized dipole formed from this benzoxazole loses a proton to produce a cyclic ketene N,O-acetal. This compound reacts further with DMAD to eventually produce a novel phenolic lactam whose structure was established by an X-ray crystal structure analysis.

  DOI：

  10.1021/jo00057a029

文献信息

• Rh(I)–Bisphosphine-Catalyzed Asymmetric, Intermolecular Hydroheteroarylation of α-Substituted Acrylate Derivatives
  作者：Claire M. Filloux、Tomislav Rovis

  DOI：10.1021/ja511445x

  日期：2015.1.14

  Asymmetric hydroheteroarylation of alkenes represents a convenient entry to elaborated heterocyclic motifs. While chiral acids are known to mediate asymmetric addition of electron-rich heteroarenes to Michael acceptors, very few methods exploit transition metals to catalyze alkylation of heterocycles with olefins via a C–H activation, migratory insertion sequence. Herein, we describe the development

  烯烃的不对称氢杂芳基化代表了复杂杂环基序的便捷进入。虽然已知手性酸可以介导富电子杂芳烃向 Michael 受体的不对称加成，但很少有方法利用过渡金属通过 C-H 活化、迁移插入序列催化杂环与烯烃的烷基化。在此，我们描述了α-取代丙烯酸酯与苯并恶唑的不对称分子间氢杂芳基化反应的发展。该反应以中等至优异的产率和良好至优异的对映选择性提供2-取代的苯并恶唑。值得注意的是，一系列机制研究似乎与涉及 Rh(I)-烯醇化物对映选择性质子化的途径相矛盾，尽管事实上在芳基硼酸与甲基丙烯酸酯衍生物的相关加成中几乎一致地调用了这种机制。相反，有证据表明，迁移插入或β-氢化物消除具有对映决定性，Rh(I)-烯醇化物异构化为Rh(I)-杂苄基物质可将所得的α-立构中心与差向异构化隔离开来。庞大的配体 CTH-(R)-Xylyl-P-Phos 对于反应性和对映选择性至关重要，因为它可能会阻止苯并恶唑底物或中间体与循
• Padwa Albert, Austin David J., Precedo Laura, Zhi Lin, J. Org. Chem., 58 (1993) N 5, S 1144-1150
  作者：Padwa Albert, Austin David J., Precedo Laura, Zhi Lin

  DOI：——

  日期：——
• Cycloaddition reactions of pyridinium and related azomethine ylides
  作者：Albert Padwa、David J. Austin、Laura Precedo、Lin Zhi

  DOI：10.1021/jo00057a029

  日期：1993.2

  The Rh(H)-catalyzed reaction of alpha-diazoacetophenone in the presence of 2-(methylthio)pyridine and dimethyl acetylenedicarboxylate gave 3-benzoyl-1,2-dicarbomethoxy-3,5-dihydro-5-(methylthio)-indolizine. The formation of the cycloadduct proceeds via a pyridinium ylide formed by attack of the nitrogen lone pair on the electrophilic keto carbenoid. A related cyclization occurred using 1-diazo-3-[(2-pyridyl)thio]-2-propanone. The Rh(II)-catalyzed reaction of 1-(3'-diazoacetonyl)-2-pyridone with DMAD was also found to give cycloadducts derived from an azomethine ylide. The initial reaction involves generation of the expected carbonyl ylide dipole by intramolecular cyclization of the keto carbenoid onto the oxygen atom of the amide group. A subsequent proton exchange generates the thermodynamically more stable azomethine ylide which is trapped by DMAD. Azomethine ylide cycloadducts derived from keto carbenoid cyclization onto a thiobenzoxazole are also formed. When 1-diazo-3-[(2-benzoxazolyl)thio]-2-propanone was used, the initially formed cycloadduct underwent a subsequent 1,3-sigmatropic thio shift. An analogous cyclization occurred using 2-(4-diazo-3-oxobutyl)benzoxazole. In addition to undergoing dipolar cycloaddition, the highly stabilized dipole formed from this benzoxazole loses a proton to produce a cyclic ketene N,O-acetal. This compound reacts further with DMAD to eventually produce a novel phenolic lactam whose structure was established by an X-ray crystal structure analysis.