1-Bromo-2-oxo-cyclooctanecarboxylic acid ethyl ester | 91214-58-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-Bromo-2-oxo-cyclooctanecarboxylic acid ethyl ester
• 英文别名: ethyl 1-bromo-2-oxocyclooctane-1-carboxylate
• CAS: 91214-58-3
• 化学式: C₁₁H₁₇BrO₃
• 分子量: 277.158
• InChiKey: JPPRNEDYZUYNHU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.61
• 重原子数：
  15.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  43.37
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  1-Bromo-2-oxo-cyclooctanecarboxylic acid ethyl ester 在 sodium azide 作用下， 以 二甲基亚砜 为溶剂， 生成 1-Azido-2-oxo-cyclooctanecarboxylic acid ethyl ester
  参考文献：
  名称：

  Radical Chain Reactions of α-Azido-β-keto Esters with Tributyltin Hydride. A Novel Entry to Amides and Lactams through Regiospecific Nitrogen Insertion

  摘要：

  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.

  DOI：

  10.1021/jo990837g
• 作为产物：
  描述：

  2-氧-1-环辛烷羧酸 在 N-溴代丁二酰亚胺(NBS) 作用下， 以 四氯化碳 为溶剂， 生成 1-Bromo-2-oxo-cyclooctanecarboxylic acid ethyl ester
  参考文献：
  名称：

  Radical Chain Reactions of α-Azido-β-keto Esters with Tributyltin Hydride. A Novel Entry to Amides and Lactams through Regiospecific Nitrogen Insertion

  摘要：

  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.

  DOI：

  10.1021/jo990837g