4-methyl-5-oxo-2-(4-methoxyphenyl)-4,5-dihydrooxazole-4-carboxylic acid phenyl ester | 627877-80-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚酯
• 英文名称: 4-methyl-5-oxo-2-(4-methoxyphenyl)-4,5-dihydrooxazole-4-carboxylic acid phenyl ester
• 英文别名: phenyl (4S)-2-(4-methoxyphenyl)-4-methyl-5-oxo-1,3-oxazole-4-carboxylate
• CAS: 627877-80-9
• 化学式: C₁₈H₁₅NO₅
• 分子量: 325.321
• InChiKey: UVQAQBGBVZIMFN-SFHVURJKSA-N

物化性质

• 沸点：
  450.1±55.0 °C(Predicted)
• 密度：
  1.25±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  24
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  74.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  苯甲醇 、 4-methyl-5-oxo-2-(4-methoxyphenyl)-4,5-dihydrooxazole-4-carboxylic acid phenyl ester 在 三丁基膦 、 苯甲酸 作用下， 以 二氯甲烷 为溶剂， 以85%的产率得到2-(4-methoxybenzoylamino)-2-methyl-malonic acid benzyl ester phenyl ester
  参考文献：
  名称：

  Development of Chiral Nucleophilic Pyridine Catalysts:  Applications in Asymmetric Quaternary Carbon Synthesis

  摘要：

  TADMAP (1a), a new chiral DMAP catalyst, has been designed to place a C(3)-benzylic trityl group over one face of the pyridine ring, while a C(3)-benzylic acetoxy group creates a chirotopic environment on the other face. TADMAP was prepared in four steps (37% overall) from triphenylacetic acid and (dimethylamino)pyridine and was resolved using camphorsulfonic acid. TADMAP catalyzes the enantioselective rearrangement from oxazolyl phenyl carbonates 4 to azlactones 5, from furanyl phenyl carbonate 8 to the furanone 9, from the benzofuranyl carbonates 11a and 11b to benzofuranones 12a and 12b, and from the indolyl carbonates 11c and 11d to oxindoles 12c and 12d. The products are formed in good yield and, in most cases, with practical levels of enantiomer excess at the newly formed quaternary carbon.

  DOI：

  10.1021/ja037223k
• 作为产物：
  描述：

  DL-N-(4-methoxybenzoyl)alanine 在 乙酸酐 、 三乙胺 、 acetic acid (1S)-1-(4-dimethylaminopyridin-3-yl)-2,2,2-triphenylethyl ester 作用下， 以 四氢呋喃 、 2-甲基-2-丁醇 为溶剂， 反应 13.0h， 生成 4-methyl-5-oxo-2-(4-methoxyphenyl)-4,5-dihydrooxazole-4-carboxylic acid phenyl ester
  参考文献：
  名称：

  对映选择性 TADMAP 催化羧基迁移反应合成立体季碳

  摘要：

  手性亲核催化剂 TADMAP [1, 3-(2,2,2-三苯基-1-乙酰氧基乙基)-4-(二甲氨基)吡啶]已由 3-锂硫-4-(二甲氨基)吡啶 (5) 和三苯乙醛 (3)，然后进行酰化和拆分。TADMAP 催化恶唑基、呋喃基和苯并呋喃基烯醇碳酸酯的羧基迁移，具有良好到极好的对映选择水平。恶唑反应特别有效，用于制备含有季不对称碳的手性内酰胺 (23) 和内酯 (30)。吲哚系列中 TADMAP 催化的羧基迁移相对较慢，并且具有不一致的对映选择性。建模研究 (B3LYP/6-31G*) 已用于定性关联催化剂构象、反应性和对映选择性。

  DOI：

  10.1021/ja056150x

文献信息

• A step-economic and one-pot access to chiral C^α-tetrasubstituted α-amino acid derivatives <i>via</i> a bicyclic imidazole-catalyzed direct enantioselective <i>C</i>-acylation
  作者：Mo Wang、Muxing Zhou、Lu Zhang、Zhenfeng Zhang、Wanbin Zhang

  DOI：10.1039/d0sc00808g

  日期：——

  Cα-Tetrasubstituted α-amino acids are ubiquitous and unique structural units in bioactive natural products and pharmaceutical compounds. The asymmetric synthesis of these molecules has attracted a lot of attention, but a more efficient method is still greatly desired. Here we describe the first sequential four-step acylation reaction for the efficient synthesis of chiral Cα-tetrasubstituted α-amino acid derivatives

  Ç α -Tetrasubstitutedα氨基酸是生物活性天然产物和药物化合物普遍存在的，并且独特的结构单元。这些分子的不对称合成引起​​了很多关注，但是仍然非常需要一种更有效的方法。在这里，我们描述了用于手性C的有效合成的第一顺序四步酰化反应α -tetrasubstitutedα氨基从简单的酸衍生物Ñ -acylated氨基酸通过使用单一亲核催化剂的自动串联催化。通过直接对映选择性C-酰化提高了合成效率。该方法得出相应的Cα具有优良对映选择性（高达99％ee）的-四取代α-氨基酸衍生物。这种循序渐进，一锅又自动串联的策略可以轻松访问重要的手性结构单元，例如肽，丝氨酸和恶唑啉，它们经常用于药物和合成化学中。
• Chiral Bicycle Imidazole Nucleophilic Catalysts: Rational Design, Facile Synthesis, and Successful Application in Asymmetric Steglich Rearrangement
  作者：Zhenfeng Zhang、Fang Xie、Jia Jia、Wanbin Zhang

  DOI：10.1021/ja109069k

  日期：2010.11.17

  A new type of chiral bicycle imidazole nucleophilic catalyst was rationally designed, facilely synthesized, and successfully applied in an asymmetric Steglich rearrangement with good to excellent yield and enantioselectivity at ambient temperature. Moreover, it can be easily recycled with almost no reduction of catalytic efficiency. This is the first example for the successful chiral imidazole nucleophilic

  一种新型手性双环咪唑亲核催化剂经过合理设计、简便合成，并成功应用于不对称 Steglich 重排，在室温下具有良好的产率和对映选择性。此外，它可以轻松回收，几乎不会降低催化效率。这是没有氢键辅助的手性咪唑亲核催化剂成功的第一个例子。
• A Dual-Catalysis Approach to the Asymmetric Steglich Rearrangement and Catalytic Enantioselective Addition of <i>O</i>-Acylated Azlactones to Isoquinolines
  作者：Chandra Kanta De、Nisha Mittal、Daniel Seidel

  DOI：10.1021/ja208156z

  日期：2011.10.26

  A dual-catalysis approach, namely the combination of an achiral nucleophilic catalyst and a chiral anion-binding catalyst, was applied to the Steglich rearrangement to provide α,α-disubstituted amino acid derivatives in a highly enantioselective fashion. Replacement of the nucleophilic co-catalyst for isoquinoline resulted in a divergent reaction pathway and an unprecedented transformation of O-acylated

  双催化方法，即非手性亲核催化剂和手性阴离子结合催化剂的组合，应用于 Steglich 重排，以高度对映选择性的方式提供 α,α-二取代氨基酸衍生物。替代异喹啉的亲核助催化剂导致了不同的反应途径和 O-酰化吖内酯的前所未有的转化。该策略提供了高度取代的 α,β-二氨基酸衍生物，具有出色的立体控制水平。
• Synthesis and Catalytic Properties of 4-Aryl-2,3-dihydro-4<i>H</i>-pyrimido[2,3-<i>b</i>]benzothiazoles for Asymmetric Acyl or Carboxyl Group Transfer Reactions
  作者：Baby Viswambharan、Tatsuya Okimura、Satoko Suzuki、Sentaro Okamoto

  DOI：10.1021/jo200984n

  日期：2011.8.19

  4-Aryl-2,3-dihydro-4H-pyrimido[2,3-b]benzothiazoles (4-Ar-DHPBs) were synthesized and their catalytic activity and selectivity in kinetic resolution of a secondary alcohol as well as in the Steglich rearrangement and related reactions were evaluated. 4-Aryl-DHPBs showed low enantioselectivity in the acylative kinetic resolution of 1-phenylethanol. Conversely, they catalyzed the Steglich rearrangement

  合成了4-Aryl-2,3-dihydro-4 H -pyrimido [2,3- b ]苯并噻唑（4-Ar-DHPBs），它们在仲醇动力学和Steglich动力学拆分中具有催化活性和选择性重排和相关反应进行了评估。4-芳基-DHPB在1-苯基乙醇的酰基动力学拆分中显示出低的对映选择性。相反，他们以适中至优异的对映选择性催化了Steglich重排，证明了通过在DHPB的4位上引入取代基进行远程立体控制的可能性。
• Isothiourea-Mediated Asymmetric O- to C-Carboxyl Transfer of Oxazolyl Carbonates: Structure-Selectivity Profiles and Mechanistic Studies
  作者：Caroline Joannesse、Craig P. Johnston、Louis C. Morrill、Philip A. Woods、Madeleine Kieffer、Tobias A. Nigst、Herbert Mayr、Tomas Lebl、Douglas Philp、Ryan A. Bragg、Andrew D. Smith

  DOI：10.1002/chem.201102847

  日期：2012.2.20

  The structural motif within a series of tetrahydropyrimidine‐based isothioureas necessary for generating high asymmetric induction in the asymmetric Steglich rearrangement of oxazolyl carbonates is fully explored, with crossover and dynamic 19F NMR experiments used to develop a mechanistic understanding of this transformation.

  充分探索了一系列四氢嘧啶基异硫脲中的结构基序，这些结构对于恶唑碳酸酯的不对称Steglich重排产生高不对称诱导是必要的，并使用交叉和动态19 F NMR实验来发展对该转变的机理理解。