2-methylenecycloundecanone | 24848-08-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-methylenecycloundecanone
• 英文别名: 2-Methylen-cycloundecanon-(1)；2-Methylenecycloundecanone；2-methylidenecycloundecan-1-one
• CAS: 24848-08-6
• 化学式: C₁₂H₂₀O
• 分子量: 180.29
• InChiKey: LJPIYMLCMDJZEZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  1.0
• 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：

  三甲基氯硅烷 、 2-methylenecycloundecanone 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 以37%的产率得到Trimethyl-((Z)-11-methylene-cycloundec-1-enyloxy)-silane
  参考文献：
  名称：

  A Ring-Expansion Approach to Roseophilin

  摘要：

  Preparation of a cyclopentenone-fused pyrrolophane, which serves as a model for the tricyclic core of roseophilin (1), is described. The synthetic scheme features a palladium-catalyzed annulation and oxidative cleavage sequence to provide a macrocyclic ketoester (17). Modified Paal-Knorr pyrrole synthesis and Friedel-Crafts acylation complete the pyrrolophane model system (20).

  DOI：

  10.1021/ol051730k

文献信息

• Asymmetric Hydrogenation of Olefins with Aprotic Oxygen Functionalities Catalyzed by BINAP-Ru(II) Complexes
  作者：Tetsuo Ohta、Tsutomu Miyake、Nobuo Seido、Hidenori Kumobayashi、Hidemasa Takaya

  DOI：10.1021/jo00107a014

  日期：1995.1

  Cyclic alpha,beta-unsaturated ketones, alkylidene lactones, and alkenyl ethers have been hydrogenated in high enantiomeric excesses by use of BINAP-Ru(II) complexes (BINAP = 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl) as catalysts. 2-Alkylidenecyclopentanones were hydrogenated in the presence of [RuCl(BINAP)(benzene)]Cl, Ru2Cl4(BINAP)2(NEt(3)), or Ru(OCO CH3 )(2)(BINAP) in up to 98% ee, while in the case of 2-benzylidene- and 2-(3-phenylpropylidene)cyclopentanones, enantiomeric excesses of the hydrogenation were below 50% under the same conditions. The sense of asymmetric induction as well as the enantioselectivity (95% ee) obtained in the hydrogenation of (E)-2-propylidene-gamma-butyrolactone were the same as those of the (Z)-isomer. Lactones, 2- and 4-alkylidene-gamma-butyrolactones, were converted to the corresponding saturated gamma-butyrolactones in 95% ee. Hydrogenation of diketene with the catalytic system derived from RuCl[(S)-BINAP](benzene)}Cl and triethylamine or complex Ru2Cl4[(S)-BINAP](2)(NEt(3)) established a new synthetic route to (R)-4-methyl-2-oxetanone, a promising monomer of biodegradable polymers, in up to 97% selectivity and 92% ee. Alkenyl ethers, 2-methylenetetrahydrofuran, and 2-methyl-3,4-dihydrofuran have also been hydrogenated to give 2-methyltetrahydrofuran in 91 and 87% ee, respectively.
• A Ring-Expansion Approach to Roseophilin
  作者：Samuel G. Salamone、Gregory B. Dudley

  DOI：10.1021/ol051730k

  日期：2005.9.1

  Preparation of a cyclopentenone-fused pyrrolophane, which serves as a model for the tricyclic core of roseophilin (1), is described. The synthetic scheme features a palladium-catalyzed annulation and oxidative cleavage sequence to provide a macrocyclic ketoester (17). Modified Paal-Knorr pyrrole synthesis and Friedel-Crafts acylation complete the pyrrolophane model system (20).