2-methyl-2-(1-propyn-3-yl)cyclohexane-1,3-dione | 32561-55-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-methyl-2-(1-propyn-3-yl)cyclohexane-1,3-dione
• 英文别名: 2-methyl-2-propargyl-1,3-cyclohexanedione；2-methyl-2-(prop-2-yn-1-yl)cyclohexane-1,3-dione；1,3-Cyclohexanedione, 2-methyl-2-(2-propynyl)-；2-methyl-2-prop-2-ynylcyclohexane-1,3-dione
• CAS: 32561-55-0
• 化学式: C₁₀H₁₂O₂
• 分子量: 164.204
• InChiKey: AQLBDNIXPWFZLZ-UHFFFAOYSA-N

物化性质

• 沸点：
  275.0±20.0 °C(Predicted)
• 密度：
  1.054±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 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：

  2-methyl-2-(1-propyn-3-yl)cyclohexane-1,3-dione 生成 (2SR,3SR)-3-hydroxy-2-methyl-2-(2-propynyl)cyclohexanone
  参考文献：
  名称：

  BROOKS, D. W.;MAZDIYASNI, H.;GROTHAUS, P. G., J. ORG. CHEM., 52,(1987) N 15, 3223-3232

  摘要：

  DOI：
• 作为产物：
  描述：

  3-(2,2-dimethylhydrazino)cyclohex-2-en-1-one 在 盐酸 、 正丁基锂 、 potassium hydride 、 碘甲烷 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 为溶剂， 反应 0.08h， 生成 2-methyl-2-(1-propyn-3-yl)cyclohexane-1,3-dione
  参考文献：
  名称：

  Regioselective Alkylations of Cyclic 1,3-Diketonesvia Metalated Dimethylhydrazones

  摘要：

  Cyclic 1,3- diketones 1 are transformed into their 2,2-dimethylhydrazones 2, which can be alkylated regioselectively at different positions after mono-, di-, tri-, and tetrametalation. Monometalated C-2 unsubstituted hydrazones afford C-2 and N-alkylation, monometalated C-2 substituted hydrazones afford only C-2 alkylation. The regioselectivity of the alkylation of the polymetalated hydrazones follows Hauser's rule according to the sequence: NH- > C-4 Ha > C-5 > C-4 Hb. Hydrolysis of the product hydrazones 3-5 afforded mono-and polyalkylated 1,3- diketones 7 in good yields.

  DOI：

  10.1002/prac.19973390199

文献信息

• An NMR tool for cyclodextrin selection in enantiomeric resolution by high-performance liquid chromatography
  作者：Antonio Laverde、Gelson J. A. da Conceição、Sonia C. N. Queiroz、Fred Y. Fujiwara、Anita J. Marsaioli

  DOI：10.1002/mrc.1043

  日期：2002.7

  Complexation-induced chemical shifts and diffusion coefficients (HR-DOSY) of enantiomers with native and derivatized cyclodextrins were used for calculations of the apparent binding constants of three cyclohexanone inclusion complexes. Correlations between these data and high-performance liquid chromatography were established, revealing that this approach can be applied as an alternative method to predict enantiomeric discrimination. Copyright © 2002 John Wiley & Sons, Ltd.

  原生和衍生环糊精与手性分子的络合诱导化学位移和扩散系数（HR-DOSY）被用于计算三种环己酮包合物表观结合常数。通过这些数据与高效液相色谱之间的关联，揭示了该方法可作为预测手性识别的替代手段。版权© 2002 John Wiley & Sons, Ltd.
• Ruthenium(II)-Catalyzed Hydration of Terminal Alkynes in PEG-400
  作者：Prathama Mainkar、Srivari Chandrasekhar、Venkataraju Chippala、Rambabu Chegondi

  DOI：10.1055/s-0035-1561864

  日期：——

  The ruthenium(II)-catalyzed hydration of terminal alkynes in PEG-400 to yield methyl ketones through Markovnikov addition of water across alkyne is reported.

  报道了在 PEG-400 中钌 (II) 催化的末端炔烃的水合作用，通过在炔烃上加入马尔可夫尼科夫水生成甲基酮。
• Enantioselective Nickel-Catalyzed <i>anti</i>-Carbometallative Cyclizations of Alkynyl Electrophiles Enabled by Reversible Alkenylnickel <i>E</i>/<i>Z</i> Isomerization
  作者：Christopher Clarke、Celia A. Incerti-Pradillos、Hon Wai Lam

  DOI：10.1021/jacs.6b04206

  日期：2016.7.6

  Nickel-catalyzed additions of arylboronic acids to alkynes, followed by enantioselective cyclizations of the alkenylnickel species onto tethered ketones or enones, are reported. These reactions are reliant upon the formal anti-carbonickelation of the alkyne, which is postulated to occur by the reversible E/Z isomerization of an alkenylnickel species.

  据报道，镍催化芳基硼酸加成到炔烃上，然后将烯基镍物质对映选择性环化到束缚酮或烯酮上。这些反应依赖于炔烃的形式反碳化反应，推测这是通过烯基镍物质的可逆 E/Z 异构化发生的。
• Iridium‐Catalyzed Arylative Cyclization of Alkynones by 1,4‐Iridium Migration
  作者：Benjamin M. Partridge、Jorge Solana González、Hon Wai Lam

  DOI：10.1002/anie.201403271

  日期：2014.6.16

  1,4‐Metal migrations enable the remote functionalization of CH bonds, and have been utilized in a wide variety of valuable synthetic methods. The vast majority of existing examples involve the 1,4‐migration of palladium or rhodium. Herein, the stereoselective synthesis of complex polycycles by the iridium‐catalyzed arylative cyclization of alkynones with arylboronic acids is described. To our knowledge

  1,4-金属迁移能够实现C - H键的远程功能化，并已被用于多种有价值的合成方法中。绝大多数现有例子涉及钯或铑的 1,4-迁移。本文描述了通过铱催化炔酮与芳基硼酸的芳基化环化来立体选择性合成复杂多环。据我们所知，这些反应涉及首次报道的 1,4-铱迁移实例。
• Enantio- and Diastereoselective Synthesis of Functionalized Carbocycles by Cu-Catalyzed Borylative Cyclization of Alkynes with Ketones
  作者：Joseph M. Zanghi、Shuang Liu、Simon J. Meek

  DOI：10.1021/acs.orglett.9b01769

  日期：2019.7.5

  and diastereoselective tandem hydroboration/borylative cyclization of alkynes with ketones for the synthesis of carbocycles is reported. The reaction proceeds via desymmetrization and generates four contiguous stereocenters, including an all-carbon quaternary center. The method provides rapid access to [6,5]- and [5,5]-bicycles and cyclopentane products. Catalyst-controlled diastereoselectivity by selection

  据报道，炔烃与酮的单锅铜催化对映和非对映选择性串联硼氢化/硼化环化反应可用于合成碳环。反应通过去对称化进行，并产生四个连续的立体中心，包括全碳四元中心。该方法提供了对[6,5]-和[5,5]-自行车和环戊烷产物的快速访问。注意到通过选择双膦配体的催化剂控制的非对映选择性。通过提供有价值的烯基和烯丙基有机硼的位点和化学选择性转化证明了产品的实用性。