2-苄基乙酰乙酸叔丁酯 | 87769-52-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 中文名称: 2-苄基乙酰乙酸叔丁酯
• 英文名称: tert-butyl 2-benzylacetoacetate
• 英文别名: tert-butyl 2-benzyl-3-oxobutanoate；2-Benzyl-acetessigsaeure-tert.-butylester
• CAS: 87769-52-6
• 化学式: C₁₅H₂₀O₃
• 分子量: 248.322
• InChiKey: AYIKXYLCFDRJRR-UHFFFAOYSA-N

物化性质

• 沸点：
  329.5±22.0 °C(Predicted)
• 密度：
  1.039±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-苄基乙酰乙酸叔丁酯 在 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以99%的产率得到2-苄基-3-氧代丁酸
  参考文献：
  名称：

  Cyclization of Arylacetoacetates to Indene and Dihydronaphthalene Derivatives in Strong Acids. Evidence for Involvement of Further Protonation of O,O-Diprotonated β-Ketoester, Leading to Enhancement of Cyclization

  摘要：

  The chemical features, such as substrate stability, product distribution, and substrate generality, and the reaction mechanism of Bronsted superacid-catalyzed cyclization reactions of aromatic ring-containing acetoacetates (beta-ketoesters) were examined in detail. While two types of carbonyl cyclization are possible, i.e., keto cyclization and ester cyclization, the former was found to take place exclusively. The reaction constitutes an efficient method to synthesize indene and 3,4-dihydronapthalene derivatives. Acid-base titration monitored with C-13 NMR spectroscopy showed that the acetoacetates are fully O-1,O-3-diprotonated at H-0 = -11. While the five-membered ring cyclization of the arylacetoacetates proceeded slowly at H-0 = -11, a linear increase in the rate of the cyclization was found with increasing acidity in the high acidity region of H-0 = -11.8 to -13.3. Therefore, the O-1,O-3-diprotonated acetoacetates exhibited some cyclizing reactivity, but they are not the reactive intermediates responsible for the acceleration of the cyclization in the high acidity region. The reactive cationic species might be formed by further protonation (or protosolvation) of the O-1,O-3-diprotonated acetoacetates; i.e., they may be tricationic species. Thermochemical data on the acid-catalyzed cyclization of the arylacetoacetates showed that the activation energy is decreased significantly as compared with that of the related acid-catalyzed cyclization reaction of a compound bearing a single functional group, such as a ketone. These findings indicate that intervention of the trication contributes to the activation of the cyclization of arylacetoacetates in strong acid, and the electron-withdrawing nature of the O-protonated ester functionality significantly increases the electrophilicity of the ketone moiety.

  DOI：

  10.1021/ja908749u
• 作为产物：
  描述：

  2-Benzyliden-acetessigsaeure-tert-butylester 在 palladium on activated charcoal 氢气 作用下， 以 甲醇 为溶剂， 反应 24.0h， 以87%的产率得到2-苄基乙酰乙酸叔丁酯
  参考文献：
  名称：

  作为乙炔的一般合成，烯醇三氟甲磺酸酯的脱羧消除。

  摘要：

  通过溶解在三氟乙酸中，可以将叔丁基β-酮二酸酯和β-酮酸酯的烯醇三氟甲磺酸酯4、8、12、17和20水解成相应的羧酸。二羧酸经过适度的脱羧消除，在室温下在碳酸氢钠水溶液中得到炔酸4和9。类似地，一元羧酸通过在丙酮中与碳酸钾一起回流而得到末端和中链乙炔13、18、21和24。乙炔上的取代基之一可以是甲基，伯烷基，仲烷基或乙炔基，另一个可以是羧酸，氢或伯烷基，但是当一个取代基是叔丁基时，不能制备烯醇三氟甲磺酸酯。 ，

  DOI：

  10.1039/b401435a

文献信息

• A Mild and Regioselective Method for α-Bromination of β-Keto Esters and 1,3-Diketones Using Bromodimethylsulfonium Bromide (BDMS)
  作者：Abu T. Khan、Md Ashif Ali、Papori Goswami、Lokman H. Choudhury

  DOI：10.1021/jo061501r

  日期：2006.11.1

  Bromodimethylsulfonium bromide has been found to be an effective and regioselective reagent for α-monobromination of β-keto esters and 1,3-diketones. A wide variety of β-keto esters and 1,3-diketones undergo chemoselective α-monobromination with excellent yields at 0−5 °C or room temperature. The notable advantages of this protocol are no need of chromatographic separation, use of less hazardous reagent

  已经发现溴代二甲基溴化for是对β-酮酸酯和1,3-二酮进行α-单溴化的有效和区域选择性的试剂。各种各样的β-酮酸酯和1,3-二酮在0-5°C或室温下经历化学选择性的α-单溴化反应，并具有优异的收率。该方案的显着优点是不需要色谱分离，不需要使用比分子溴少的危险试剂，并且不需要添加碱，路易斯酸或其他催化剂。
• B(C₆F₅)₃-catalyzed O–H insertion reactions of diazoalkanes with phosphinic acids
  作者：Yangyang Zhang、Xinzhi Zhang、Jincheng Zhao、Jun Jiang

  DOI：10.1039/d1ob01035b

  日期：——

  A highly efficient base-, metal-, and oxidant-free catalytic O–H insertion reaction of diazoalkanes and phosphinic acids in the presence of B(C6F5)3 has been developed. This powerful methodology provides a green approach towards the synthesis of a broad spectrum of α-phosphoryloxy carbonyl compounds with good to excellent yields (up to 99% yield). The protocol features the advantages of operational

  在 B(C 6 F 5 ) 3存在下，重氮烷烃和次膦酸的高效无碱、无金属和无氧化剂催化 O-H 插入反应已被开发出来。这种强大的方法为合成广谱 α-磷酰氧基羰基化合物提供了一种绿色方法，收率从高到高（收率高达 99%）。该协议具有操作简单、原子经济性高、实用性强、易于扩展和环境友好等优点。
• Aerobic α-hydroxylation of β-keto esters and amides by co-catalysis of SmI3 and I2 under mild base-free conditions
  作者：Shun-Ming Yu、Kai Cui、Fei Lv、Zhen-Yu Yang、Zhu-Jun Yao

  DOI：10.1016/j.tetlet.2016.05.052

  日期：2016.6

  A clean base-free α-hydroxylation of β-keto esters and amides has been developed, in which air was used as the oxygen source and SmI3 and I2 were applied as the catalysts, affording the corresponding α-hydroxylated 1,3-dicarbonyl products in good to excellent yields under mild conditions. Mechanism discussion shows that both oxygen atoms of dioxygen are utilized and incorporated into the product through

  已经开发出清洁的无碱的β-酮酯和酰胺的α-羟基化反应，其中空气用作氧气源，SmI 3和I 2被用作催化剂，得到相应的α-羟基化的1,3-在温和条件下，二羰基产品的收率好至极好。机理讨论表明，双氧的两个氧原子都被利用，并通过独特的自由基过程掺入产物中。
• Ethynyl-1,2-benziodoxol-3(1 H)-one (EBX): An Exceptional Reagent for the Ethynylation of Keto, Cyano, and Nitro Esters
  作者：Davinia Fernández González、Jonathan P. Brand、Jérôme Waser

  DOI：10.1002/chem.201001539

  日期：2010.8.16

  Hot alkyne! The in situ generation of ethynyl‐1,2‐benziodoxol‐3(1H)‐one (EBX) from a silyl‐protected reagent by using TBAF is reported. EBX displayed exceptional acetylene transfer ability onto stabilized enolates (see scheme), even at −78 °C. The mild reaction conditions allowed the first ethynylation reactions of linear keto, cyano, and nitro esters in high yields to give all‐carbon quaternary centers

  热炔！据报道，使用TBAF从甲硅烷基保护的试剂原位生成乙炔基1,2-苯并恶唑醇-3（1 H）-one（EBX）。即使在-78°C下，EBX仍具有出色的乙炔转移能力，可将其转移到稳定的烯醇化物上（参见方案）。温和的反应条件使线性酮基，氰基和硝基酯的首次乙炔化反应可以高收率生成，在选择性还原硝基后，生成全碳季中心或非天然氨基酸。
• Catalytic Enantioselective Protonation/Nucleophilic Addition of Diazoesters with Chiral Oxazaborolidinium Ion Activated Carboxylic Acids
  作者：Ki-Tae Kang、Seung Tae Kim、Geum-Sook Hwang、Do Hyun Ryu

  DOI：10.1002/anie.201612655

  日期：2017.3.27

  A new chiral Brønsted acid derived from carboxylic acid and a chiral oxazaborolidinium ion (COBI), as an activator, is introduced. This acid was successfully applied as a catalyst for the highly enantioselective protonation/nucleophilic addition of diazoesters with carboxylic acids.

  引入了一种新的手性布朗斯台德酸，其衍生自羧酸和手性恶唑硼烷鎓离子（COBI）作为活化剂。该酸已成功地用作重氮酸酯与羧酸的高度对映选择性质子化/亲核加成的催化剂。