1,1'-diacetyl-3-methyl-4-methylenecyclopentane | 74142-69-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,1'-diacetyl-3-methyl-4-methylenecyclopentane
• 英文别名: 1-(1-Acetyl-3-methyl-4-methylidenecyclopentyl)ethanone
• CAS: 74142-69-1
• 化学式: C₁₁H₁₆O₂
• 分子量: 180.247
• InChiKey: GSFAVHSTGGTZLT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,1'-diacetyl-3-methyl-4-methylenecyclopentane 、 醋酸钯 生成 1-(1-Acetyl-3,4-dimethyl-cyclopent-2-enyl)-ethanone
  参考文献：
  名称：

  GRIGG R.; MITCHELL T. R. B.; RAMASUBBU A., J. CHEM. SOC. CHEM. COMMUN., 1980, NO 1, 27-28

  摘要：

  DOI：
• 作为产物：
  描述：

  3,3-二烯丙基-2,4-戊二酮 在 Wilkinson's catalyst 盐酸 作用下， 以 氯仿 为溶剂， 反应 12.0h， 以87%的产率得到1,1'-diacetyl-3-methyl-4-methylenecyclopentane
  参考文献：
  名称：

  铑催化的取代亚甲基环戊烷的合成

  摘要：

  在沸腾的氯仿中，通过威尔金森催化剂[RhCl（PPh 3）3 ]，将4,4-二取代的1,6-二烯以高收率环化为亚甲基环戊烷。

  DOI：

  10.1039/c39800000027

文献信息

• Ruthenium-Catalyzed One-Pot Double Allylation/Cycloisomerization of 1,3-Dicarbonyl Compounds Leading toexo-Methylenecyclopentanes
  作者：Yoshihiko Yamamoto、Yu-ichiro Nakagai、Kenji Itoh

  DOI：10.1002/chem.200305340

  日期：2004.1.5

  tion of 1,3-diketones and methyl acetoacetate gave exo-methylenecyclopentanes in moderate to good yields with high isomer selectivity. The double allylation step effectively proceeded in the presence of a Ru(II) precatalyst, [Cp*RuCl(cod)], in 1,2-dichloroethane at 90 degrees C. The subsequent cycloisomerization was carried out upon addition of triethylsilane as a hydride source without purification

  钌催化的1，3-二酮和乙酰乙酸甲酯的一锅双烯丙基化/环异构化反应以中等到良好的收率得到了高亚甲基环戊烷的异构体选择性。双重烯丙基化步骤在Ru（II）预催化剂[Cp * RuCl（cod）]存在下于1,2-二氯乙烷中于90摄氏度下有效地进行。随后的环异构化反应是在加入三乙基硅烷作为氢化物后进行的。源，无需纯化1,6-二烯中间体。通过（1）NMR光谱对反应进行的详细检查显示，三乙基甲硅烷基甲基醚对于将在双烯丙基化步骤中形成的钌（IV）烯丙基络合物转化成环异构化所需的钌（II）物种起着重要作用。
• Rhodium-catalysed synthesis of substituted methylene cyclopentanes
  作者：Ronald Grigg、Thomas R. B. Mitchell、Ashok Ramasubbu

  DOI：10.1039/c39800000027

  日期：——

  4,4-Disubstituted 1,6-dienes are cyclised in good yield by Wilkinson's catalyst [RhCl(PPh3)3], in boiling chloroform, to methylene cyclopentanes.

  在沸腾的氯仿中，通过威尔金森催化剂[RhCl（PPh 3）3 ]，将4,4-二取代的1,6-二烯以高收率环化为亚甲基环戊烷。
• Cycloisomerization Promoted by the Combination of a Ruthenium–Carbene Catalyst and Trimethylsilyl Vinyl Ether, and its Application in The Synthesis of Heterocyclic Compounds: 3-Methylene-2,3-dihydroindoles and 3-Methylene-2,3-dihydrobenzofurans
  作者：Yukiyoshi Terada、Mitsuhiro Arisawa、Atsushi Nishida

  DOI：10.1002/anie.200454157

  日期：2004.8.6
• Ruthenium(II)-Catalyzed Isomer-Selective Cyclization of 1,6-Dienes Leading to <i>e</i><i>xo</i>-Methylenecyclopentanes:  Unprecedented Cycloisomerization Mechanism Involving Ruthenacyclopentane(hydrido) Intermediate
  作者：Yoshihiko Yamamoto、Yu-ichiro Nakagai、Naoki Ohkoshi、Kenji Itoh

  DOI：10.1021/ja010134s

  日期：2001.7.1

  In the presence of a catalytic amount of ruthenium(II) complexes, [RuCl2(cod)](n), RuCl2(cod)(MeCN)(2), [RuCl2(nbd)](n). [RuCl2(CO)(3)](2), and Cp*Ru(cod)Cl, 1,6-dienes were effectively converted into the corresponding exo-methylenecyclopentanes in good to excellent yields with good isomer purity in i-PrOH at 90 degreesC. The alcoholic solvent was essential for the present catalytic cyclization, and the efficiency increased in the following order: t-BuOH << EtOH less than or equal to i-PrOH. In contrast, a Ru(0) complex. (C6Me6)Ru(cod), catalyzed the cycloisomerization only in 1,2-dichloroethane. The unusual isomer-selectivity occurred when a 1,7-octadiene was subjected to cyclization to give a similar exo-methylenecyclopentane isomer as the major product. The identical isomer selectivity was observed for the cyclization of unsymmetrical 1,6-dienes having one terminal- and one internal-alkene termini. On the basis of the results from the studies using the known ruthenium hydrides and deuterium-labeling substrates, the novel mechanism via the Ru(II) <--> Ru(IV) system involving a ruthenacyclopentane(hydrido) intermediate was proposed, which better explains the particular regiochemistry of the present cyclization than other previous mechanisms.
• Grigg, Ronald; Malone, John F.; Mitchell, Thomas R. B., Journal of the Chemical Society. Perkin transactions I, 1984, # 8, p. 1745 - 1754
  作者：Grigg, Ronald、Malone, John F.、Mitchell, Thomas R. B.、Ramasubbu, Asnok、Scott, Ronald M.

  DOI：——

  日期：——