ethyl 6-methylene-8-oxo-bicyclo<3.2.1>octane-1-carboxylate | 133550-69-3

• 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 6-methylene-8-oxo-bicyclo<3.2.1>octane-1-carboxylate
• 英文别名: Ethyl 6-methylidene-8-oxobicyclo[3.2.1]octane-1-carboxylate
• CAS: 133550-69-3
• 化学式: C₁₂H₁₆O₃
• 分子量: 208.257
• InChiKey: VXERSQFHSQHJOU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  ethyl 3-bromo-1-(2-bromo-2-propenyl)-2-oxocyclohexanecarboxylate 在 sodium tetrahydroborate 、 cerium(III) chloride 、 草酰氯 、 偶氮二异丁腈 、 三正丁基氢锡 、 二甲基亚砜 、 三乙胺 、 calcium carbonate 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 28.83h， 生成 ethyl 6-methylene-8-oxo-bicyclo<3.2.1>octane-1-carboxylate
  参考文献：
  名称：

  Vinyl radical cyclizations: synthesis of substituted bicyclooctanols

  摘要：

  The preparation and free-radical bicyclic ring closure of 4-(2-bromo-2-propen-1-yl)cyclohexene 7 is described. The bicyclo[3.2.1] and -[2.2.2] alcohols 9 and 10 arising, respectively, from 5-exo and 6-endo (or 6-exo) modes of cyclization of a vinyl radical were isolated in a 1:1 ratio. Factors affecting the regiochemical outcome were investigated.

  DOI：

  10.1021/jo00009a032

文献信息

• Mn(III)-Based Oxidative Free-Radical Cyclizations of Unsaturated Ketones
  作者：Bridget McCarthy Cole、Luning Han、Barry B. Snider

  DOI：10.1021/jo961199u

  日期：1996.1.1

  free-radical cyclization of unsaturated ketones is a versatile synthetic procedure with broad applicability. For example, oxidation of cyclopentanone 1a with 2 equiv of Mn(OAc)(3).2H(2)O and 1 equiv of Cu(OAc)(2).H(2)O in AcOH at 80 degrees C for 1.5 h affords 75% of bicyclo[3.2.1]oct-3-en-8-one 8a and 15% of bicyclo[3.2.1]oct-2-en-8-one 9a. Bridged bicyclic ketones that cannot enolize further are isolated

  Mn（III）基的不饱和酮的氧化自由基环化是一种通用的合成方法，具有广泛的适用性。例如，在80摄氏度的条件下，在AcOH中用2当量的Mn（OAc）（3）.2H（2）O和1当量的Cu（OAc）（2）.H（2）O氧化环戊酮1a 1.5小时得到75％的双环[3.2.1] oct-3-en-8-one 8a和15％的双环[3.2.1] oct-2-en-8-one 9a。分离出不能进一步烯醇化的桥联双环酮，收率很高。可以烯化的单环β，γ-不饱和酮被进一步氧化，得到γ-乙酰氧基烯酮。从2-烯丙基环己酮（56a）以52％的收率形成双环[3.3.1] non-2-en-9-one（57a）表明，动力学控制的烯醇化是α-酮自由基形成过程中的决定速率的步骤。各种各样的示例描述了范围，限制，
• Synthesis of (±)-Gymnomitrol. Mn(OAc)₃-Initiated Free-Radical Cyclization of Alkynyl Ketones
  作者：Steven V. O'Neil、Cheri A. Quickley、Barry B. Snider

  DOI：10.1021/jo9622338

  日期：1997.4.1

  Mn(OAc)(3)-initiated cyclization of alkynyl ketones in 9-19:1 EtOH/HOAc at 90 degrees C is a useful cyclization procedure in favorable cases. Cyclization of (trimethylsilyl)alkynyl ketone 4e provides 62% of silylalkenes 26 and 27 in the key reaction of a seven-step (16% overall yield) synthesis of gymnomitrol (1) from readily available ketone 23. 9alpha-Hydroxygymnomitryl acetate (2) and 9-oxogymnomitryl

  在有利的情况下，Mn（OAc）（3）在9-19：1 EtOH / HOAc中于90摄氏度下引发炔基酮的环化是一种有用的环化程序。（三甲基甲硅烷基）炔基酮4e的环化反应是由容易获得的酮23合成七步法（总产率为16％）合成裸子油醇（1）的关键反应中，甲硅烷基烯26和27的含量为62％。9α-羟基乙二醛乙酸甘油酯（2）从裸子油醇中制备乙酸和9-氧代庚酰氨基甲酰乙酸（3）。炔丙基环己酮39a-c的环化以40-60％的产率提供双环化合物40-42。
• Mn(III)-based oxidative free radical cyclization of unsaturated ketones.
  作者：Barry B. Snider、Bridget McCarthy Cole

  DOI：10.1021/jo00122a006

  日期：1995.9
• Vinyl radical cyclizations: synthesis of substituted bicyclooctanols
  作者：William F. Berkowitz、Phyllis J. Wilson

  DOI：10.1021/jo00009a032

  日期：1991.4

  The preparation and free-radical bicyclic ring closure of 4-(2-bromo-2-propen-1-yl)cyclohexene 7 is described. The bicyclo[3.2.1] and -[2.2.2] alcohols 9 and 10 arising, respectively, from 5-exo and 6-endo (or 6-exo) modes of cyclization of a vinyl radical were isolated in a 1:1 ratio. Factors affecting the regiochemical outcome were investigated.