3-Methyl-3-(1-methylethenyl)cyclopentanone | 133447-97-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-Methyl-3-(1-methylethenyl)cyclopentanone
• 英文别名: 3-methyl-3-(prop-1-en-2-yl)cyclopentanone；3-methyl-3-(prop-2-en-1-yl)cyclopentanone；3-Methyl-3-prop-1-en-2-ylcyclopentan-1-one
• CAS: 133447-97-9
• 化学式: C₉H₁₄O
• 分子量: 138.21
• InChiKey: SIHVPCPVEGXFEH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  溴化环丙基三苯鏻 、 3-Methyl-3-(1-methylethenyl)cyclopentanone 在 sodium hydride 、 三(3,6-二氧杂庚基)胺 作用下， 以 四氢呋喃 为溶剂， 反应 23.0h， 以0.096g的产率得到3-cyclopropylidene-1-methyl-1-(prop-1-en-2-yl)cyclopentane
  参考文献：
  名称：

  Gold(I)-Catalyzed Formation of Bicyclo[4.2.0]oct-1-enes

  摘要：

  Gold(I) catalysts effectively promote the Cope rearrangement of acyclic 1,S-dienes bearing a terminal cyclopropylidene. When this methodology is applied to cyclic substrates an unexpected transformation occurs, resulting in the formation of a tricyclic compound incorporating a bicyclo[4.2.0]oct-1-ene core, a portion of which is found in a number of natural products. Density functional theory calculations (M06 and M06-2X) reveal insight into the mechanism and thermodynamics of this unique transformation.

  DOI：

  10.1021/jo400139g
• 作为产物：
  描述：

  3-溴丙腈 、 2,3-二甲基-1,3-丁二烯 在 盐酸 、 magnesium 作用下， 生成 3-Methyl-3-(1-methylethenyl)cyclopentanone
  参考文献：
  名称：

  Chemistry of substituted (2-butene-1,4-diyl)magnesium: a facile approach to complex carbocycles, functionalized ketones and alcohols, and silicon-containing heterocycles

  摘要：

  Highly reactive magnesium reacts with a wide variety of substituted 1,3-dienes to give the corresponding substituted (2-butene-1,4-diyl)magnesium complexes. Reactions of symmetrical (2-butene-1,4-diyl)magnesium with alpha,omega-alkylene dihalides form three-, four-, five-, and six-membered carbocycles. Significantly, the cyclizations are always stereospecific and completely regioselective. Depending on the initial 1,3-diene and specific electrophiles, uncyclized products can be obtained. Stepwise reactions of (2,3-dimethyl-2-butene-1,4-diyl)magnesium with two different electrophiles afford polyfunctionalized ketones with the generation of a quaternary center. Formal 1,2-additions can be effected in this manner. Substituted five- and six-membered cyclic ketones can also be synthesized in one step by this approach. Treatment of unsymmetrical (2-butene-1,4-diyl)magnesium complexes with triorganosilyl chlorides followed by cyclohexanone results in additions across a terminal double bond with high regioselectivity. Silicon-containing heterocycles or spiro compounds can be readily synthesized by using the bis-Grignard reagents.

  DOI：

  10.1021/jo00009a034

文献信息

• Formation of Quaternary Stereogenic Centers by Copper-Catalyzed Asymmetric Conjugate Addition Reactions of Alkenylaluminums to Trisubstituted Enones
  作者：Daniel Müller、Alexandre Alexakis

  DOI：10.1002/chem.201302856

  日期：2013.11.4

  undergo asymmetric copper‐catalyzed conjugate addition (ACA) to β‐substituted enones allowing the formation of stereogenic all‐carbon quaternary centers. Phosphinamine–copper complexes proved to be particularly active and selective compared with phosphoramidite ligands. After extensive optimization, high enantioselectivities (up to 96 % ee) were obtained for the addition of alkenylalanes to β‐substituted

  烯基铝经过不对称的铜催化共轭加成（ACA）至β取代的烯酮，从而形成立体立体的全碳四元中心。与亚磷酰胺配体相比，膦胺-铜络合物被证明具有特别的活性和选择性。经过广泛的优化后，将烯基丙氨酸添加到β-取代的烯酮中获得了很高的对映选择性（高达ee的96％  ）。为了产生芳基和烷基取代的烯基亲核试剂，探索了两种生成必需的烯基铝的策略。此外，首次将烷基取代的次膦胺（SimplePhos）配体鉴定为Cu催化的ACA的高效配体。
• Creation of Highly Congested Quaternary Centers via Cu-catalyzed Conjugate Addition of Alkenyl Alanates to β-Substituted Cyclic Enones
  作者：Daniel Müller、Alexandre Alexakis

  DOI：10.1021/ol400378v

  日期：2013.4.5

  prepared alkenylalanates proved to be excellent nucleophiles for the creation of highly congested quaternary centers via copper-catalyzed conjugate addition. In addition, functionalized cis-decaline systems can now be prepared in a simple two-step sequence involving Cu-catalyzed conjugate addition with functionalized alkenylalanates.

  易于制备的链烯基丙二酸被证明是极好的亲核试剂，可通过铜催化的共轭加成产生高度拥挤的季中心。另外，现在可以以简单的两步顺序制备功能化的顺式癸胺系统，该步骤涉及铜催化的加有功能化链烯基丙二酸酯的共轭物的加成。
• Chemistry of substituted (2-butene-1,4-diyl)magnesium: a facile approach to complex carbocycles, functionalized ketones and alcohols, and silicon-containing heterocycles
  作者：Reuben D. Rieke、Heping Xiong

  DOI：10.1021/jo00009a034

  日期：1991.4

  Highly reactive magnesium reacts with a wide variety of substituted 1,3-dienes to give the corresponding substituted (2-butene-1,4-diyl)magnesium complexes. Reactions of symmetrical (2-butene-1,4-diyl)magnesium with alpha,omega-alkylene dihalides form three-, four-, five-, and six-membered carbocycles. Significantly, the cyclizations are always stereospecific and completely regioselective. Depending on the initial 1,3-diene and specific electrophiles, uncyclized products can be obtained. Stepwise reactions of (2,3-dimethyl-2-butene-1,4-diyl)magnesium with two different electrophiles afford polyfunctionalized ketones with the generation of a quaternary center. Formal 1,2-additions can be effected in this manner. Substituted five- and six-membered cyclic ketones can also be synthesized in one step by this approach. Treatment of unsymmetrical (2-butene-1,4-diyl)magnesium complexes with triorganosilyl chlorides followed by cyclohexanone results in additions across a terminal double bond with high regioselectivity. Silicon-containing heterocycles or spiro compounds can be readily synthesized by using the bis-Grignard reagents.
• Gold(I)-Catalyzed Formation of Bicyclo[4.2.0]oct-1-enes
  作者：Ryan J. Felix、Osvaldo Gutierrez、Dean J. Tantillo、Michel R. Gagné

  DOI：10.1021/jo400139g

  日期：2013.6.7

  Gold(I) catalysts effectively promote the Cope rearrangement of acyclic 1,S-dienes bearing a terminal cyclopropylidene. When this methodology is applied to cyclic substrates an unexpected transformation occurs, resulting in the formation of a tricyclic compound incorporating a bicyclo[4.2.0]oct-1-ene core, a portion of which is found in a number of natural products. Density functional theory calculations (M06 and M06-2X) reveal insight into the mechanism and thermodynamics of this unique transformation.