ethyl 2-azido-3-oxo-1H-indene-2-carboxylate | 210166-59-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚满类
• 英文名称: ethyl 2-azido-3-oxo-1H-indene-2-carboxylate
• CAS: 210166-59-9
• 化学式: C₁₂H₁₁N₃O₃
• 分子量: 245.238
• InChiKey: KFOWIVFEBUPGDM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  57.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  ethyl 2-azido-3-oxo-1H-indene-2-carboxylate 在 rosenmund catalyst 、 氢气 作用下， 以 异丙醇 为溶剂， 40.0 ℃ 、101.33 kPa 条件下， 以92 %的产率得到ethyl 2-amino-1-oxoindanecarboxylate
  参考文献：
  名称：

  α-氨基-β-氧代酯向 δ-丁内酰胺的环转化

  摘要：

  通过环转化获得内酰胺：通过用 Zn−AcOH 还原环状 α-叠氮基-β-氧代环戊烷羧酸酯，获得在 δ 位具有环外酯部分的 δ-丁内酰胺。环的转变在还原条件下很容易进行，这是一个前所未有的过程。

  DOI：

  10.1002/ejoc.202300757
• 作为产物：
  描述：

  乙基1-氧亚基-2,3-二氢-1H-茚-2-甲酸基酯 在 叠氮基三甲基硅烷 、 过氧化脲素 、 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine hydroiodide 作用下， 以 乙腈 为溶剂， 反应 0.25h， 以98%的产率得到ethyl 2-azido-3-oxo-1H-indene-2-carboxylate
  参考文献：
  名称：

  碘化胍/脲过氧化氢与三甲基硅烷基叠氮化物催化β-二羰基化合物的叠氮化

  摘要：

  我们提出了一种高效的合成方法，该方法由胍基次碘酸盐催化，由β-二羰基化合物和叠氮化三甲基硅烷基化物合成α-叠氮基-β-二羰基化合物。该反应可以在环境温度（最高40°C）的空气中进行，并且对水分不敏感。底物的适用范围很广，包括环状和线性的β-二羰基化合物，α-叠氮化物的产率为55％–99％。

  DOI：

  10.1016/j.tet.2016.07.015

文献信息

• Guanidinium iodide/urea hydrogen peroxide-catalyzed azidation of β-dicarbonyl compounds with trimethylsilyl azide
  作者：Koji Yasui、Kohei Kojima、Takanari Kato、Minami Odagi、Masaru Kato、Kazuo Nagasawa

  DOI：10.1016/j.tet.2016.07.015

  日期：2016.9

  We present an efficient synthesis of α-azido-β-dicarbonyl compounds from β-dicarbonyl compounds and trimethylsilyl azide, catalyzed by guanidinium hypoiodite. The reaction can be run in air at ambient temperature (up to 40 °C) and is not sensitive to moisture. The substrate scope is broad, including cyclic and linear β-dicarbonyl compounds, and the α-azide products are obtained in 55%–99% yield.

  我们提出了一种高效的合成方法，该方法由胍基次碘酸盐催化，由β-二羰基化合物和叠氮化三甲基硅烷基化物合成α-叠氮基-β-二羰基化合物。该反应可以在环境温度（最高40°C）的空气中进行，并且对水分不敏感。底物的适用范围很广，包括环状和线性的β-二羰基化合物，α-叠氮化物的产率为55％–99％。
• Sulfonyl‐PYBOX Ligands Enable Kinetic Resolution of α‐Tertiary Azides by CuAAC
  作者：Yi Gong、Cai Wang、Feng Zhou、Kui Liao、Xi‐Yu Wang、Ying Sun、Yan‐Xue Zhang、Zhi Tu、Xin Wang、Jian Zhou

  DOI：10.1002/anie.202301470

  日期：——

  We report the first highly selective kinetic resolution of racemic α-chiral azides by Cu-catalyzed azide-alkyne cycloadditions (CuAAC), providing facile access to chiral α-tertiary azides and 1,2,3-triazoles with newly developed PYBOX ligands with a C4 sulfonyl group. The key role of the C4 sulfonyl in tuning the electronic and steric properties of the chiral catalysts to enhance enantiomer discrimination

  我们报告了通过 Cu 催化的叠氮化物-炔烃环加成 (CuAAC) 对外消旋 α-手性叠氮化物的首次高选择性动力学拆分，提供了通过新开发的 PYBOX 配体轻松获得手性 α-叔叠氮化物和 1,2,3-三唑C4磺酰基。DFT 计算合理化了 C4 磺酰基在调节手性催化剂的电子和空间特性以增强对映异构体区分方面的关键作用。
• Reactions of Benzocyclic β-Keto Esters with Tosyl and 4-Nitrophenyl Azide. Structural Influence of Dicarbonyl Substrate and Azide Reagent on Distribution of Diazo, Azide and Ring-Contraction Products
  作者：Luisa Benati、Gianluca Calestani、Daniele Nanni、Piero Spagnolo

  DOI：10.1021/jo980223w

  日期：1998.7.1

  The reactions of beta-keto esters derived from 1- and 2-indanone, 1- and 2-tetralone, and benzosuberone with toluene-4-sulfonyl- (tosyl) and 4-nitrobenzenesulfonyl azide (PNBSA) in the presence of Et3N have been investigated in order to evaluate the influence of both dicarbonyl substrate and azide reagent on the product distribution. With tosyl azide the keto esters derived from both 2-benzocycloalkanones exhibit deacylating diazo transfer, but those derived from the 1-benzocycloalkanones undergo additional azido transfer to a significant or even exclusive extent. The finding is mainly explained in terms of the lesser reactivity of the conjugate aryl ketone than alkyl ketone moiety. This would discourage cyclization of the initial sulfonyltriazenyl anion-the presumable azide precursor-to the triazoline adduct, in turn envisaged as the diazo progenitor. With PNBSA both indanones smoothly undergo diazo transfer, whereas their higher homologues lead to ring-contraction products ascribable to corresponding triazolines that curiously prefer to suffer Favorskii-type ring fragmentation. Evidence has been obtained that tosyl azide acts as a azide-transfer reagent superior to PNBSA. A possible explanation of this fact is discussed. An X-ray crystal structure analysis of the phthalazine compound 18 (Ar = 4-Me-C6H4) has been performed.
• Radical Chain Reactions of α-Azido-β-keto Esters with Tributyltin Hydride. A Novel Entry to Amides and Lactams through Regiospecific Nitrogen Insertion
  作者：Luisa Benati、Daniele Nanni、Corrado Sangiorgi、Piero Spagnolo

  DOI：10.1021/jo990837g

  日期：1999.10.1

  A variety of acyclic and carbocyclic alpha-azido-beta-keto esters have been readily prepared from the parent dicarbonyl compounds, and their radical chain reactions with tributyltin hydride have been investigated. These reactions normally result in efficient production of alkoxycarbonyl-substituted amides and lactams and thence provide a new, useful method for regiospecific nitrogen insertion of keto ester compounds. The likely mechanism entails initial addition of tributylstannyl radical to the azido moiety to give a stannylaminyl radical, which readily undergoes intramolecular three-membered cyclization onto the ketone group to form an alkoxyl radical. The alkoxyl radical then undergoes regiospecific beta-scissian to form a stable ring-opened radical that is eventually reduced by tributyltin hydride to propagate the chain. With certain substrates, concomitant deazidation occurs to an important extent. This process, which is unusually observed in radical reactions of alkyl azides, is ascribed to addition of the stannyl radical to the terminal azido nitrogen; subsequent fragmentation of the ensuing 1,3-triazenyl adduct gives stannyl azide and a deazidated alkyl radical, resonance-stabilized by the adjacent carbonyl groups. The radical reactions of 2-azido-2-(ethoxy-carbonyl)-1-tetralone with allyltributylstannane and allyltriphenylstannane have also been investigated with the (missed) aim to achieve nitrogen insertion and concomitant allylation.
• Ring Transformation of α‐Amino‐β‐oxoesters to δ‐Butyrolactams
  作者：Daniel Krieger、Jens Christoffers

  DOI：10.1002/ejoc.202300757

  日期：2023.10.16

  Lactams by Ring Transformation: δ-Butyrolactams with an exocyclic ester moiety in the δ-position were accessed by reduction of cyclic α-azido-β-oxocyclopentane carboxylates with Zn−AcOH. The ring transformation proceeded readily under the conditions of the reduction which is an unprecedented process.

  通过环转化获得内酰胺：通过用 Zn−AcOH 还原环状 α-叠氮基-β-氧代环戊烷羧酸酯，获得在 δ 位具有环外酯部分的 δ-丁内酰胺。环的转变在还原条件下很容易进行，这是一个前所未有的过程。