(1S,4R,5R)-4,6,6-trimethyl-4-vinylbicyclo[3.1.1]heptan-2-one | 134655-24-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (1S,4R,5R)-4,6,6-trimethyl-4-vinylbicyclo[3.1.1]heptan-2-one
• 英文别名: (1S,4R,5R)-4-ethenyl-4,6,6-trimethylbicyclo[3.1.1]heptan-2-one
• CAS: 134655-24-6
• 化学式: C₁₂H₁₈O
• 分子量: 178.274
• InChiKey: UKOUVTROMKPGBE-UISBYWKRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (1S,4R,5R)-4,6,6-trimethyl-4-vinylbicyclo[3.1.1]heptan-2-one 在 氢溴酸 作用下， 以 正己烷 为溶剂， 以84%的产率得到(1S,2R,5S)-2-(2-Bromoethyl)-4-oxopinane
  参考文献：
  名称：

  A facile synthesis of bicyclo[m.n.1]alkan-1-ols. Evidence for organosamarium intermediates in the samarium(II) iodide promoted intramolecular Barbier-type reaction

  摘要：

  Samarium(II) iodide (SmI2) has been successfully employed as a reductive coupling agent for the intramolecular Barbier-type synthesis of bicyclo[m.n.1]alkan-1-ols. Thus, a variety of 3-(omega-iodoalkyl)cycloalkanones, upon treatment with SmI2 and a catalytic quantity of iron complex in tetrahydrofuran (THF), provide the title compounds in excellent yields. The reaction is quite general for the construction of diverse bicyclic ring systems, including the highly strained bicyclo[2.1.1]hexan-1-ol. In addition to exploring the synthetic utility of this reaction, studies have been performed which provide insight on the mechanistic details of the SmI2-promoted intramolecular Barbier-type synthesis. Compelling evidence for the intermediacy of organosamarium species has thus been gathered.

  DOI：

  10.1021/jo00013a008
• 作为产物：
  描述：

  马鞭草烯醇 在 盐酸 、 四甲基乙二胺 作用下， 反应 0.83h， 生成 (1S,4R,5R)-4,6,6-trimethyl-4-vinylbicyclo[3.1.1]heptan-2-one
  参考文献：
  名称：

  A facile synthesis of bicyclo[m.n.1]alkan-1-ols. Evidence for organosamarium intermediates in the samarium(II) iodide promoted intramolecular Barbier-type reaction

  摘要：

  Samarium(II) iodide (SmI2) has been successfully employed as a reductive coupling agent for the intramolecular Barbier-type synthesis of bicyclo[m.n.1]alkan-1-ols. Thus, a variety of 3-(omega-iodoalkyl)cycloalkanones, upon treatment with SmI2 and a catalytic quantity of iron complex in tetrahydrofuran (THF), provide the title compounds in excellent yields. The reaction is quite general for the construction of diverse bicyclic ring systems, including the highly strained bicyclo[2.1.1]hexan-1-ol. In addition to exploring the synthetic utility of this reaction, studies have been performed which provide insight on the mechanistic details of the SmI2-promoted intramolecular Barbier-type synthesis. Compelling evidence for the intermediacy of organosamarium species has thus been gathered.

  DOI：

  10.1021/jo00013a008

文献信息

• New entry to the synthesis of clerodane diterpenes. The first enantioselective syntheses of 7-oxo-kolavenic acid and methyl solidagonate
  作者：Michiharu Kato、Hiroshi Kosugi、Tsuyoshi Ichiyanagi、Hisahiro Hagiwara、Ariko Kodaira、Takashi Kusakari、Takao Suzuki、Minako Ando、Jasmine Lee、Peter Drechsel、Bernhard Vogler

  DOI：10.1016/s0040-4020(01)00821-3

  日期：2001.9

  three kinds of key intermediates, conjugate enones 9 and 10 for the syntheses of neo-trans-clerodanes and 11 for those of neo-cis-clerodanes. Starting with the compound 10, the first enantioselective syntheses of (−)-(5R,8S,9S,10R)-7-oxo-cleroda-3,13E-dien-15-oic acid (7-oxo-kolavenic acid) (1) and solidagonic acid (2) as its methyl ester (48) were achieved.

  使用易于从（+）-nopinone（3）获得的（1 S，5 S）-（-）-马洛酮（8b）作为手性来源，我们建立了制备三种关键中间体的通用方法，合成新反式-环烷烷的共轭烯酮9和10，新-顺式-环丙烷烷的共轭烯酮为11。从化合物10开始，（-）-（5 R，8 S，9 S，10 R）-7-oxo-cleroda-3,13 E的第一对映选择性合成获得了作为其甲酯（48）的-dien-15-Oic酸（7-氧代-Kolavenic酸）（1）和多角体酸（2）。
• Efficient synthesis of (1S,5S)-4-alkyl-6,6-dimethylbicyclo[3.1.1]hept-3-en-2-ones from (1R,5S)-(+)-nopinone and preparation of some chiral building blocks suitable for the asymmetric synthesis
  作者：Masataka Watanabe、Bahlul Z. Awen、Michiharu Kato

  DOI：10.1021/jo00067a026

  日期：1993.7

  A general and convenient transformation of (1R,5S)-(+)-nopinone (1) into (1S,5S)-4-alkyl-6,6-dimethylbicyclo[3.1.1]hept-3-en-2-ones, i.e., (-)-verbenone (6a) as the simplest compound and its C(4)-alkyl homologs 6b-f, via (+)-apoverbenone (7) is developed and applied, starting with 6a,e, to the syntheses of (4R,5R)-1-acetoxy-4-isopropenyl-5-methyl-5-vinyl-1-cyclohexene (12a) and (4R,5S)- and (4R,5R)-1-acetoxy-5-(3-butenyl)-4-isopropenyl-5-methyl-1-cyclohexene (12b and 12c), in connection with a search for chiral building blocks suitable for the asymmetric synthesis. Preparation of 12a indicates the formal synthesis of the elemanoid sesquiterpenes (-)-beta-elemenone and (-)-eleman-8beta,12-olide.
• Stereocontrolled synthesis of the key intermediate for the enantioselective synthesis of clerodane natural products
  作者：Michiharu Kato、Hiroshi Kosugi、Ariko Kodaira、Hisahiro Hagiwara、Bernhard Vogler

  DOI：10.1016/s0040-4039(97)01614-6

  日期：1997.9

  Stereocontrolled synthesis of (+)-trans-decalone 7 (R = CH=CH2) from (-)-verbenone (5), readily obtainable from (+)-nopinone (2), is described. The compound 7 possesses four correctly arranged chiral centers, C(5)-C(10)-C(9)-C(8), necessary for the enantioselective synthesis of neo-trans-clerodanes. (C) 1997 Elsevier Science Ltd.
• A facile synthesis of bicyclo[m.n.1]alkan-1-ols. Evidence for organosamarium intermediates in the samarium(II) iodide promoted intramolecular Barbier-type reaction
  作者：Gary A. Molander、Jeffrey A. McKie

  DOI：10.1021/jo00013a008

  日期：1991.6

  Samarium(II) iodide (SmI2) has been successfully employed as a reductive coupling agent for the intramolecular Barbier-type synthesis of bicyclo[m.n.1]alkan-1-ols. Thus, a variety of 3-(omega-iodoalkyl)cycloalkanones, upon treatment with SmI2 and a catalytic quantity of iron complex in tetrahydrofuran (THF), provide the title compounds in excellent yields. The reaction is quite general for the construction of diverse bicyclic ring systems, including the highly strained bicyclo[2.1.1]hexan-1-ol. In addition to exploring the synthetic utility of this reaction, studies have been performed which provide insight on the mechanistic details of the SmI2-promoted intramolecular Barbier-type synthesis. Compelling evidence for the intermediacy of organosamarium species has thus been gathered.