4-oxo-2-phenyl-cyclooct-1-enecarboxylic acid ethyl ester

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: 4-oxo-2-phenyl-cyclooct-1-enecarboxylic acid ethyl ester
• 英文别名: ethyl (Z)-4-oxo-2-phenyl-1-cyclooctenecarboxylate；ethyl (1Z)-4-oxo-2-phenylcyclooct-1-ene-1-carboxylate；ethyl (1Z)-4-oxo-2-phenylcyclooctene-1-carboxylate
• 化学式: C₁₇H₂₀O₃
• 分子量: 272.344
• InChiKey: IJHHOPIHFKPONH-NXVVXOECSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.41
• 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：

  4-oxo-2-phenyl-cyclooct-1-enecarboxylic acid ethyl ester 在 对甲苯磺酸 作用下， 以 间二甲苯 为溶剂， 反应 48.0h， 以53%的产率得到(1S*,5R*)-4-phenylbicyclo[3.3.1]non-3-ene-2,9-dione
  参考文献：
  名称：

  Acid-Catalyzed Synthesis of Bicyclo[3.n.1]alkenediones

  摘要：

  An acid-catalyzed Dieckmann-type reaction has been developed to access functionalized bicyclo[3.2.1]alkenediones. This methodology has been successfully extended to more substituted and larger ring homologues, providing a new and efficient route to the core of numerous attractive natural products and their analogues.

  DOI：

  10.1021/ol102909t
• 作为产物：
  描述：

  苯丙炔酸甲酯 在 盐酸 、 水 、 sodium hydride 、 lithium chloride 作用下， 以 四氢呋喃 、 二甲基亚砜 、 mineral oil 为溶剂， 反应 23.67h， 生成 4-oxo-2-phenyl-cyclooct-1-enecarboxylic acid ethyl ester
  参考文献：
  名称：

  Acid-Catalyzed Synthesis of Bicyclo[3.n.1]alkenediones

  摘要：

  An acid-catalyzed Dieckmann-type reaction has been developed to access functionalized bicyclo[3.2.1]alkenediones. This methodology has been successfully extended to more substituted and larger ring homologues, providing a new and efficient route to the core of numerous attractive natural products and their analogues.

  DOI：

  10.1021/ol102909t

文献信息

• Efficient Catalytic Insertion of Acetylenes into a Carbon−Carbon Single Bond of Nonstrained Cyclic Compounds under Mild Conditions
  作者：Yoichiro Kuninobu、Atsushi Kawata、Kazuhiko Takai

  DOI：10.1021/ja064022i

  日期：2006.9.1

  medium-sized cyclic compound in excellent yield. By using isocyanide as an additive, the catalytic activity of the rhenium complex changes dramatically, and the insertion of acetylenes into a carbon-carbon single bond occurs under mild conditions. A plausible mechanism is that the reaction proceeds via the formation of a rhenacyclopentene intermediate, ring opening by a retro-aldol reaction, isomerization

  铼配合物 [ReBr(CO)3(thf)]2 催化 1,3-二羰基环状化合物与乙炔的反应，以优异的产率得到中等大小的环状化合物。通过使用异氰化物作为添加剂，铼配合物的催化活性发生显着变化，乙炔插入碳碳单键的过程在温和条件下发生。一个合理的机制是反应通过形成环戊烯中间体、通过逆羟醛反应开环、异构化和还原消除来进行。
• Rhenium- and Manganese-Catalyzed Insertion of Alkynes into a Carbon-Carbon Single Bond of Cyclic and Acyclic 1,3-Dicarbonyl Compounds
  作者：Yoichiro Kuninobu、Atsushi Kawata、Mitsumi Nishi、Salprima Yudha S.、Jingjin Chen、Kazuhiko Takai

  DOI：10.1002/asia.200900137

  日期：2009.9.1

  presence of a catalytic amount of a rhenium or manganese complex gives ring‐expanded and carbon‐chain extension products, respectively. In these reactions, alkynes insert into a non‐strained carbon–carbon single bond of 1,3‐dicarbonyl compounds. The ring‐expansion reaction is also promoted by the addition of 4‐Å molecular sieves instead of a catalytic amount of an isocyanide.

  在催化量的or或锰配合物存在下，用环状和无环的1,3-二羰基化合物处理炔烃，分别得到扩环和扩碳产物。在这些反应中，炔烃插入1,3-二羰基化合物的非应变碳-碳单键中。通过添加4Å分子筛代替催化量的异氰化物也可以促进环扩环反应。