phenacyl tert-butyl carbonate | 145586-78-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: phenacyl tert-butyl carbonate
• 英文别名: tert-butyl phenacyl carbonate；phenacyl t-butyl carbonate
• CAS: 145586-78-3
• 化学式: C₁₃H₁₆O₄
• 分子量: 236.268
• InChiKey: RJHIEYGCYNRRSM-UHFFFAOYSA-N

物化性质

• 沸点：
  324.0±25.0 °C(Predicted)
• 密度：
  1.107±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 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：

  phenacyl tert-butyl carbonate 在 9,10-二甲基蒽 作用下， 以 乙腈 为溶剂， 反应 2.0h， 以61%的产率得到叔丁醇
  参考文献：
  名称：

  Photoreleasable protecting groups on alcohols, phosphates and diacids and the use thereof

  摘要：

  酒精、磷酸酯和二酸衍生物可能通过辐射去保护，所使用的保护基是芳基酰基或杂环芳基酰基。

  公开号：

  US06392089B1
• 作为产物：
  描述：

  2-羟基苯乙酮 、 N-Boc-咪唑 以 四氢呋喃 为溶剂， 反应 2.0h， 以38%的产率得到phenacyl tert-butyl carbonate
  参考文献：
  名称：

  Photoreleasable protecting groups based on electron transfer chemistry. Donor sensitized release of phenacyl groups from alcohols, phosphates and diacids

  摘要：

  The electron transfer mediated photochemical release of alcohols, phosphates and diacids is examined. The alcohols can be protected as mixed phenacyl carbonate esters. Irradiation of mixtures containing electron donating sensitizers and phenacyl alkyl carbonate ester initiates a series of bond scission reactions that result in clean release of the corresponding alcohols. This was demonstrated for a variety of primary, secondary and tertiary hydroxyl groups, including the 5'-hydroxy group of thymidine. Sensitizers that were effective in promoting photolytic release include 9,10-dimethylanthracene and 9-methylcarbazole. GC/MS and NMR analysis of the by-products formed in these release reactions implicates the intermediacy of radical ion intermediates in these reactions. It is further demonstrated that the electron transfer sensitized release method can be extended to phosphate esters and di-functional acids. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(99)00754-1

文献信息

• Highly Enantioselective Three-Component Direct Mannich Reactions of Unfunctionalized Ketones Catalyzed by Bifunctional Organocatalysts
  作者：Qunsheng Guo、John Cong-Gui Zhao

  DOI：10.1021/ol303315c

  日期：2013.2.1

  stereoselective three-component direct Mannich reaction between aromatic aldehydes, p-toluenesulfonamide, and unfunctionalized ketones was achieved through an enolate mechanism for the first time with a bifunctional quinidine thiourea catalyst. The corresponding N-tosylated β-aminoketones were obtained in high yields and excellent diastereo- and enantioselectivities (up to >99:1 dr and >99% ee).

  芳香醛、对甲苯磺酰胺和未官能化酮之间的高度立体选择性三组分直接曼尼希反应首次通过烯醇机制与双官能奎尼丁硫脲催化剂实现。以高产率和出色的非对映选择性和对映选择性（高达 >99:1 dr 和 >99% ee）获得了相应的N-甲苯磺酰化 β-氨基酮。
• Asymmetric Dearomatization/Cyclization Enables Access to Polycyclic Chemotypes
  作者：Mikayo Hayashi、Lauren E. Brown、John A. Porco

  DOI：10.1002/ejoc.201601003

  日期：2016.10

  interaction. Dearomatized products were used in visible light-mediated photocycloadditions and oxidative free radical cyclizations to obtain novel polycyclic chemotypes including tricyclo[4.3.1.01,4]decan-10-ones, bicyclo[3.2.1]octan-8-ones and highly-substituted cycloheptanones.

  从简单的酰基间苯三酚支架获得对映体富集的多环化合物。使用 Trost 配体-钯 (0) 配合物实现了高度对映选择性脱芳构化。开发了一个计算 DFT 模型来合理化观察到的对映选择性，并揭示了关键的反应物-配体氢键相互作用。脱芳基产物用于可见光介导的光环加成和氧化自由基环化，以获得新的多环化学型，包括三环 [4.3.1.01,4] decan-10-ones、bicyclo[3.2.1]octan-8-ones 和高度取代的环庚酮。
• Pd-Catalyzed Tandem [5 + 2] Cycloaddition/Ring Contraction of Phthalide-Derived Alkenes and Vinylethylene Carbonates for the Construction of Benzo-[5,5]-spiroketal Lactones
  作者：Qiang Xiong、Ji Lu、Liu Shi、Guang-Yao Ran

  DOI：10.1021/acs.orglett.2c01114

  日期：2022.5.13

  An annulation of phthalide-derived activated alkenes is initially disclosed in this work. Specifically, we have developed an unprecedented [5 + 2] cycloaddition/ring-contraction tandem process of activated tetrasubstituted alkenes derived from phthalides or butyrolactone with vinylethylene carbonates under Pd(0) catalysis. Differing from the traditional spirolactonization strategy, this method renders

  最初在这项工作中公开了苯酞衍生的活化烯烃的环化。具体来说，我们开发了一种史无前例的 [5 + 2] 环加成/环收缩串联工艺，该工艺在 Pd(0) 催化下由邻苯二甲酸或丁内酯衍生的活化四取代烯烃与碳酸乙烯亚乙酯进行。与传统的螺内酯化策略不同，该方法为具有两个邻位四取代中心的苯并-[5,5]-螺缩酮内酯和[5,5]-螺缩酮内酯提供了一种有效且机械上不同的方法，具有高非对映选择性。
• Palladium-catalyzed reactions of ketone .alpha.-carbonates with norbornenes. An unusual cyclopropanation
  作者：Sensuke Ogoshi、Tsumoru Morimoto、Kenichi Nishio、Kouichi Ohe、Shinji Murai

  DOI：10.1021/jo00053a004

  日期：1993.1

  In the presence of a palladium(0) catalyst, ketone alpha-carbonates react with norbornene to give a cyclopropane derivative via an oxa-pi-allylpalladium intermediate.
• US6392089B1
  申请人：——

  公开号：US6392089B1

  公开（公告）日：2002-05-21