2-Brom-2-carbomethoxycyclopentanon | 36596-60-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-Brom-2-carbomethoxycyclopentanon
• 英文别名: Methyl 1-bromo-2-oxocyclopentane-1-carboxylate；methyl 1-bromo-2-oxocyclopentane-1-carboxylate
• CAS: 36596-60-8
• 化学式: C₇H₉BrO₃
• 分子量: 221.051
• InChiKey: XWKPBKQXCILMQG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 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-Brom-2-carbomethoxycyclopentanon 在 sodium azide 、 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 二甲基亚砜 、 苯 为溶剂， 生成 6-氧代-哌啶-2-羧酸甲酯
  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-甲氧羰基环戊酮 在 N-溴代丁二酰亚胺(NBS) 作用下， 以 四氯化碳 为溶剂， 生成 2-Brom-2-carbomethoxycyclopentanon
  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

文献信息

• Lipophilic indole mediated chemoselective α-monobromination of 1,3-dicarbonyl compounds
  作者：Jonathan Wong、Zhihai Ke、Ying-Yeung Yeung

  DOI：10.1016/j.tetlet.2020.151772

  日期：2020.4

  A mild and efficient mono-selective bromination of 1,3-dicarbonyl compounds has been developed using lipophilic indole catalysts. Inexpensive and commercially available N-bromosuccinimide (NBS) was used as the brominating reagent. The selectivity was further enhanced when using stoichiometric amount of 3-bromoindole species. Mechanistic studies reveal that the indole catalyst has dual functions in

  已经使用亲脂性吲哚催化剂开发了温和而有效的1,3-二羰基化合物的单选择溴化反应。廉价且可商购的N-溴琥珀酰亚胺（NBS）用作溴化试剂。当使用化学计量的3-溴吲哚类时，选择性进一步提高。机理研究表明，吲哚催化剂在单溴化过程中具有双重功能。
• 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.