Oxiranecarboxylic acid, 3-methyl-, 1,1-dimethylethyl ester, trans- | 119162-95-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 环氧化物
• 英文名称: Oxiranecarboxylic acid, 3-methyl-, 1,1-dimethylethyl ester, trans-
• 英文别名: tert-butyl-trans-3-methyloxirane-2-carboxylate；tert-butyl 3-methyloxiranecarboxylate
• CAS: 119162-95-7；136805-89-5；136805-90-8
• 化学式: C₈H₁₄O₃
• 分子量: 158.197
• InChiKey: QSBKMSHYBYXFAB-NTSWFWBYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.12
• 重原子数：
  11.0
• 可旋转键数：
  1.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  38.83
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为产物：
  描述：

  tert-Butyl 2-<<(p-nitrophenyl)sulfonyl>oxy>acetoacetate 在 sodium tetrahydroborate 、 三乙胺 作用下， 以 乙醇 、 乙腈 为溶剂， 生成 Oxiranecarboxylic acid, 3-methyl-, 1,1-dimethylethyl ester, trans-
  参考文献：
  名称：

  Synthesis and reactions of 3-hydroxy-2-nosyloxy esters produced by the stereoselective reduction of 2-nosyloxy-3-keto esters

  摘要：

  The reduction of 2-nosyloxy-3-keto esters is an effective method for the preparation of 3-hydroxy-2-nosyloxy esters. The reduction is stereoselective for the syn isomer. The anti isomer can be produced as the major product by the addition of p-nitrobenzenesulfonyl peroxide to ketene bis-silyl acetal derivatives of 3-hydroxy esters. The diastereomers are separable chromatographically and can be converted stereospecifically to glycidic esters and 2-azido-3-hydroxy esters. As such they appear to have excellent potential as versatile synthetic intermediates for the synthesis of 1,2,3-trifunctional substances.

  DOI：

  10.1021/jo00024a013

文献信息

• A stereocontrolled approach to electrophilic epoxides
  作者：Otto Meth-Cohn、Clive Moore、Heinrich C. Taljaard

  DOI：10.1039/p19880002663

  日期：——

  Lithium t-butyl hydroperoxide (easily generated by addition of an alkyl-lithium to anhydrous t-butyl hydroperoxide in THF solution) is a powerful reagent for the epoxidation of electrophilic alkenes at –20 to 0 °C under full stereocontrol.

  叔丁基氢过氧化物锂（通过在无水THF溶液中的无水叔丁基氢过氧化物中添加烷基锂容易生成）是在完全立体控制下在–20至0°C下亲电烯烃环氧化的强大试剂。
• A powerful new stereo-controlled method for epoxidation of electrophilic alkenes
  作者：Carol Clark、Patricia Hermans、Otto Meth-Cohn、Clive Moore、Heinrich C. Taljaard、Gerda van Vuuren

  DOI：10.1039/c39860001378

  日期：——

  tetrahydrofuran are shown to epoxidise α,β-unsaturated esters and sulphones efficiently in a stereo- and regio-specific manner, while esters of chiral alcohols undergo diastereofacially selective epoxidation.

  无水四氢呋喃中的叔丁基氢过氧化物和烷基锂显示出以立体和区域特异性方式有效环氧化α，β-不饱和酯和砜，而手性醇的酯则经历了非对映选择性环氧化。
• EPOXIDATION OF α,β-UNSATURATED ESTERS BY DIMETHYLDIOXIRANE
  作者：A.L. Baumstark,、P.C. Vasquez,、M. Aly,、J.P. Sansone,

  DOI：10.1515/hc.2010.16.2-3.183

  日期：2010.6

  Abstract. Kinetic data for the epoxidation of a series of α,β-unsaturated esters, 2-10, by dimethyldioxirane in dried acetone are reported. These epoxidations are less sensitive to steric effects and occur with lower k2 values than those for simple alkenes. Relative reactivity could be modeled based on a spiro transition state mechanism. The density function calculations were in good agreement with

  摘要。报告了一系列 α,β-不饱和酯 2-10 用二甲基二环氧乙烷在干燥丙酮中环氧化的动力学数据。这些环氧化对空间效应不太敏感，并且比简单烯烃的 k2 值低。可以基于螺过渡态机制对相对反应性进行建模。密度函数计算与 krei 值非常吻合，除了那些带有顺式 β 取代基的化合物。
• Highly Stereoselective Epoxidation of α-Methyl-γ-hydroxy-α,β-unsaturated Esters:  Rationalization and Synthetic Applications
  作者：Irakusne López、Santiago Rodríguez、Javier Izquierdo、Florenci V. González

  DOI：10.1021/jo0709955

  日期：2007.8.1

  The diastereoselectivity of the nucleophilic epoxidation of gamma-hydroxy-alpha, beta-unsaturated esters having a methyl substituent at the alpha- or beta-position was investigated. Epoxidation of the alpha-methyl-substituted enoate was highly stereoselective, giving rise to the syn isomer. This finding was used to perform an enantioselective synthesis of a natural product having a beta-hydroxy-alpha-methylene-gamma-butyrolactone motif. The nucleophilic epoxidation of enoates was found to be irreversible. Models to explain the observed stereoselectivities are proposed.