tert-butyl 2-oxocyclopentanecarboxylate | 84109-76-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: tert-butyl 2-oxocyclopentanecarboxylate
• 英文别名: tert-butyl 2-oxocyclopentane-1-carboxylate；cyclopentanone-2-carboxylic acid tert-butyl ester；2-(tert-butoxycarbonyl)cyclopentanone；Tert-butyl 2-oxo-cyclopentanecarboxylate
• CAS: 84109-76-2
• 化学式: C₁₀H₁₆O₃
• 分子量: 184.235
• InChiKey: OGIKPUCMXHEUMK-UHFFFAOYSA-N

物化性质

• 沸点：
  107-109 °C(Press: 14 Torr)
• 密度：
  1.068±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

安全信息

• 危险性防范说明：
  P261,P280,P301+P312,P302+P352,P305+P351+P338
• 危险性描述：
  H302,H315,H319,H335

反应信息

• 作为反应物：
  描述：

  tert-butyl 2-oxocyclopentanecarboxylate 在 sodium hydride 、 三氟乙酸 、 sodium iodide 作用下， 以 甲醇 、 甲苯 为溶剂， 反应 9.5h， 生成 2-(戊-2-炔基)环戊烷-1-酮
  参考文献：
  名称：

  A Quick and Efficient Route to 2-Substituted Cyclopentanones and Cyclohexanones

  摘要：

  DOI：

  10.1055/s-1983-30597
• 作为产物：
  描述：

  己二酰氯 在 sodium hydride 、 N,N-二甲基苯胺 、 叔丁醇 作用下， 以 乙醚 、 甲苯 为溶剂， 生成 tert-butyl 2-oxocyclopentanecarboxylate
  参考文献：
  名称：

  Asymmetric synthesis of (1R,2S,3R)-γ-methyl-cis-pentacin by a kinetic resolution protocol

  摘要：

  通过外消旋 3-甲基环戊烯-1-羧酸叔丁酯与同手性(S)-N-苄基-N-δ-甲基苄基酰胺锂的动力学解析，实现了(1R,2S,3R)-3-甲基-2-氨基环戊烷羧酸的不对称合成。

  DOI：

  10.1039/b209728c

文献信息

• The Amino Thiourea-Catalyzed Asymmetric Nucleophilic Reactions
  作者：Yoshiji Takemoto、Hideto Miyabe

  DOI：10.2533/chimia.2007.269

  日期：——

  Bifunctional amino thiourea-catalyzed asymmetric additions of several nucleophiles into electron-deficient unsaturated compounds such as nitroolefins, ?,?-unsaturated imides, imines, and azodicarboxylates are described. We discovered that bifunctional thioureas bearing a tertiary amino group significantly accelerated several nucleophilic addition reactions of active methylene compounds to electron-deficient double bonds. In these reactions, a strong hydrogen-bonding ability of the thiourea moiety as well as an appropriate Brønsted basicity of the tertiary amine is crucial for high enantioselectivity. This dual activation of both nucleophiles and electrophiles by the bifunctional thiourea expanded the applicability of the thiourea-catalyzed enantioselective reaction. In addition, these organocatalyzed asymmetric reactions were successfully applied to the concise asymmetric synthesis of natural products and medicinal candidates such as epibatidine, baclofen, and CP-99,994.

  双功能氨基硫脲催化的不对称加成反应将几种亲核试剂加入到电子不足的不饱和化合物中，如硝基烯烃、α，β-不饱和亚酰胺、亚胺和叠氮二羧酸酯。我们发现，含有三级胺基的双功能硫脲显著加速了活性亚甲基化合物与电子不足双键的几种亲核加成反应。在这些反应中，硫脲基团的强氢键能力以及三级胺的适当Brønsted碱性对高对映选择性至关重要。双功能硫脲对亲核试剂和电子亲电试剂的双重活化扩展了硫脲催化的不对称反应的适用范围。此外，这些有机催化的不对称反应成功应用于天然产物和药用候选化合物的简洁不对称合成，如蛙毒碱、氯硝西泮和CP-99,994。
• Highly Enantioselective Copper-Catalyzed Alkylation of β-Ketoesters and Subsequent Cyclization to Spirolactones/Bi-spirolactones
  作者：Qing-Hai Deng、Hubert Wadepohl、Lutz H. Gade

  DOI：10.1021/ja211859w

  日期：2012.2.15

  Cu-catalyzed enantioselective alkylation of β-ketoesters using alcohols for in situ preparation of alkylating reagents is reported. A number of functionalized β-ketoesters containing a quaternary carbon stereocenter are obtained with up to 99% ee. The alkylation products derived from 2-substituted allylic alcohols or their corresponding iodides can then be converted to spirolactones, bi-spirolactones

  报道了使用醇对 β-酮酯进行 Cu 催化的对映选择性烷基化，用于原位制备烷基化试剂。获得了许多含有季碳立体中心的官能化 β-酮酯，ee 高达 99%。然后可以将衍生自 2-取代烯丙醇或其相应碘化物的烷基化产物转化为螺内酯、双螺内酯和相关的手性目标产物。
• Organocatalytic enantioselective allylic alkylation of MBH carbonates with β-keto esters
  作者：M. Kamlar、S. Hybelbauerová、I. Císařová、J. Veselý

  DOI：10.1039/c4ob00682h

  日期：——

  The highly stereoselective allylic alkylation of Morita–Baylis–Hillman carbonates with β-ketoesters catalysed by β-ICD is described. The corresponding products containing two adjacent quaternary and tertiary carbon centers were obtained in good yields with high diastereoselectivity (up to 10 : 1 dr) and enantioselectivity (up to 95% ee).

  描述了由β-ICD催化的Morita-Baylis-Hillman碳酸盐与β-酮酸酯的高度立体选择性烯丙基烷基化。得到具有两个高的非对映选择性（高达10∶1dr）和对映选择性（高达95％ee）的高产率的含有两个相邻的季碳和叔碳中心的相应产物。
• <i>N</i>-Alkynylthio Phthalimide: A Shelf-Stable Alkynylthio Transfer Reagent for the Synthesis of Alkynyl Thioethers
  作者：Wen-Chao Gao、Yu-Zhu Shang、Hong-Hong Chang、Xing Li、Wen-Long Wei、Xin-Zhang Yu、Rong Zhou

  DOI：10.1021/acs.orglett.9b02174

  日期：2019.8.2

  electrophilic alkynylthiolating reagent, called N-alkynylthio phthalimide, is designed and synthesized herein. This electrophilic sulfenylating reagent can be easily prepared in three steps from commercially available phthalimide and corresponding silver acetylide. Furthermore, the N-alkynylthio phthalimides are demonstrated to be efficient alkynylthio transfer reagents that can react with various C-nucleophiles

  本文设计合成了一种新型的亲电性炔基硫代试剂N-炔基硫代邻苯二甲酰亚胺。该亲电子的亚硫酰化试剂可以容易地以三步法由市售的邻苯二甲酰亚胺和相应的乙炔化银制备。此外，N-炔硫基邻苯二甲酰亚胺被证明是有效的炔硫基转移试剂，可以与各种C-亲核试剂反应，包括β-酮酸酯，芳基硼酸和Grignard试剂，可在温和条件下提供多种炔基硫醚。
• [EN] ASYMMETRIC MICHAEL AND ALDOL ADDITION USING BIFUNCTIONAL CINCHONA-ALKALOID-BASED CATALYSTS<br/>[FR] ADDITIONS ASYMETRIQUES DE MICHAEL ET D'ALDOL UTILISANT DES CATALYSEURS BIFONCTIONNELS A BASE DE CINCHONINE
  申请人：UNIV BRANDEIS

  公开号：WO2005121137A1

  公开（公告）日：2005-12-22

  One aspect of the present invention relates to quinine-based and quinidine-based catalysts. Another aspect of the invention relates to a method of preparing a derivatized quinine-based or quinidine-based catalyst comprising 1) reacting quinine or quinidine with 5 base and a compound that has a suitable leaving group, and 2) converting the ring methoxy group to a hydroxy group. Another aspect of the present invention relates to a method of preparing a chiral, non-racemic compound from a prochiral electron-deficient alkene or azo compound or prochiral aldehyde or prochiral ketone, comprising the step of: reacting a prochiral electron-deficient alkene or azo compound or prochiral aldehyde or prochiral 10 ketone with a nucleophile in the presence of a catalyst; thereby producing a chiral, non racemic compound; wherein said catalyst is a derivatized quinine or quinidine. Another aspect of the present invention relates to a method of kinetic resolution, comprising the step of reacting racemic chiral alkene with a nucleophile in the presence of a derivatized quinine or quinidine.

  本发明的一个方面涉及基于奎宁和奎宁的催化剂。发明的另一个方面涉及一种制备衍生奎宁或奎宁催化剂的方法，包括1）将奎宁或奎宁与5碱和具有适当离去基团的化合物反应，以及2）将环甲氧基转化为羟基。本发明的另一个方面涉及一种从前手性电子亏缺烯烃或偶氮化合物或前手性醛或前手性酮制备手性、非拉克米化合物的方法，包括以下步骤：在催化剂存在下，将前手性电子亏缺烯烃或偶氮化合物或前手性醛或前手性酮与亲核试剂反应；从而产生手性、非拉克米化合物；其中所述催化剂是衍生奎宁或奎宁。本发明的另一个方面涉及一种动力学分辨的方法，包括在衍生奎宁或奎宁存在下，将拉克米手性烯烃与亲核试剂反应的步骤。