carbonic acid allyl ester 2-oxo-2-phenyl-ethyl ester | 925462-31-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: carbonic acid allyl ester 2-oxo-2-phenyl-ethyl ester
• 英文别名: allyl 2-oxo-2-phenylethyl carbonate；Phenacyl prop-2-enyl carbonate
• CAS: 925462-31-3
• 化学式: C₁₂H₁₂O₄
• 分子量: 220.225
• InChiKey: QJHNYSOZFKJVBP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  16
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  carbonic acid allyl ester 2-oxo-2-phenyl-ethyl ester 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 三乙胺 作用下， 以 1,4-二氧六环 、 二氯甲烷 为溶剂， 反应 0.42h， 生成 (S)-(-)-2-phenyl-2-trimethylsilanyloxy-pent-4-enal
  参考文献：
  名称：

  Enantioselective Synthesis of α-Tertiary Hydroxyaldehydes by Palladium-Catalyzed Asymmetric Allylic Alkylation of Enolates

  摘要：

  Chiral alpha-tertiary hydroxyaldehydes are very versatile building blocks in synthetic chemistry. Herein, we report the first examples of a catalytic asymmetric protocol for the synthesis of such compounds from readily available alpha-halo or alpha-hydroxy ketones or enol silyl ethers with excellent yields and nantioselectivity. Its synthetic utility is demonstrated in the short, efficient formal synthesis of (S)-oxybutynin. In this process, the chiral ligand controls the regioselectivity as well as the enantioselectivity.

  DOI：

  10.1021/ja067342a
• 作为产物：
  描述：

  2-羟基苯乙酮 、 氯甲酸烯丙酯 在 吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以85%的产率得到carbonic acid allyl ester 2-oxo-2-phenyl-ethyl ester
  参考文献：
  名称：

  Enantioselective Synthesis of α-Tertiary Hydroxyaldehydes by Palladium-Catalyzed Asymmetric Allylic Alkylation of Enolates

  摘要：

  Chiral alpha-tertiary hydroxyaldehydes are very versatile building blocks in synthetic chemistry. Herein, we report the first examples of a catalytic asymmetric protocol for the synthesis of such compounds from readily available alpha-halo or alpha-hydroxy ketones or enol silyl ethers with excellent yields and nantioselectivity. Its synthetic utility is demonstrated in the short, efficient formal synthesis of (S)-oxybutynin. In this process, the chiral ligand controls the regioselectivity as well as the enantioselectivity.

  DOI：

  10.1021/ja067342a

文献信息

• Ligand Controlled Highly Regio- and Enantioselective Synthesis of α-Acyloxyketones by Palladium-Catalyzed Allylic Alkylation of 1,2-Enediol Carbonates
  作者：Barry M. Trost、Jiayi Xu、Thomas Schmidt

  DOI：10.1021/ja8038954

  日期：2008.9.10

  The palladium catalyzed decarboxylative asymmetric allylic alkylation of allyl 1,2-enediol carbonates 1 can decompose to either alpha-hydroxyketones 3 or alpha-hydroxyaldehydes 4. The product distribution is largely controlled by the ligand. Using Lnaph in DME we exclusively obtained the ketone product in good to excellent yields and high enantiomeric excesses. The reaction proceeds under extremely

  钯催化的 1,2-烯二醇碳酸酯 1 的脱羧不对称烯丙基烷基化可分解为 α-羟基酮 3 或 α-羟基醛 4。产物分布在很大程度上受配体控制。在 DME 中使用 Lnaph，我们专门获得了产率良好至极好的和高对映体过量的酮产品。反应在极其温和的条件下进行，因此我们可以有广泛的 OR 选择。除了常用的保护基团如 OAc 和 OPiv 外，还可以使用更多功能化的基团，如甲基丁-2-烯酰基，其下游过程可以提供其他合成有趣的结构。
• US6392089B1
  申请人：——

  公开号：US6392089B1

  公开（公告）日：2002-05-21
• Enantioselective Synthesis of α-Tertiary Hydroxyaldehydes by Palladium-Catalyzed Asymmetric Allylic Alkylation of Enolates
  作者：Barry M. Trost、Jiayi Xu、Markus Reichle

  DOI：10.1021/ja067342a

  日期：2007.1.1

  Chiral alpha-tertiary hydroxyaldehydes are very versatile building blocks in synthetic chemistry. Herein, we report the first examples of a catalytic asymmetric protocol for the synthesis of such compounds from readily available alpha-halo or alpha-hydroxy ketones or enol silyl ethers with excellent yields and nantioselectivity. Its synthetic utility is demonstrated in the short, efficient formal synthesis of (S)-oxybutynin. In this process, the chiral ligand controls the regioselectivity as well as the enantioselectivity.