ethyl 1-oxo-1,2,3,4-tetrahydro-3-isoquinolinecarboxylate

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: ethyl 1-oxo-1,2,3,4-tetrahydro-3-isoquinolinecarboxylate
• 英文别名: Ethyl 1-oxo-1,2,3,4-tetrahydroisoquinoline-3-carboxylate；ethyl 1-oxo-3,4-dihydro-2H-isoquinoline-3-carboxylate
• 化学式: C₁₂H₁₃NO₃
• mdl: MFCD21608035
• 分子量: 219.24
• InChiKey: SWDLVVJLTXRNTD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.333
• 拓扑面积：
  55.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  乙基1-氧亚基-2,3-二氢-1H-茚-2-甲酸基酯 在 正丁基锂 、 sodium azide 、 rosenmund catalyst 、 氢气 、 碘 、 二异丙胺 作用下， 以 四氢呋喃 、 水 、 二甲基亚砜 、 异丙醇 为溶剂， 23.0~40.0 ℃ 、101.33 kPa 条件下， 反应 10.25h， 生成 ethyl 1-oxo-1,2,3,4-tetrahydro-3-isoquinolinecarboxylate
  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

文献信息

• 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。