2-methyl-2-propargyl-1,3-cyclopentanedione | 68197-04-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-methyl-2-propargyl-1,3-cyclopentanedione
• 英文别名: 2-methyl-2-(prop-2-yn-1-yl)cyclopentane-1,3-dione；2-Methyl-2-prop-2-ynylcyclopentane-1,3-dione
• CAS: 68197-04-6
• 化学式: C₉H₁₀O₂
• 分子量: 150.177
• InChiKey: LQCXAPHLYVLUKY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.56
• 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-propargyl-1,3-cyclopentanedione 在 sodium hydroxide 、 水 作用下， 反应 8.0h， 以79%的产率得到(+/-)-5-methyl-4-oxooct-7-ynoic acid
  参考文献：
  名称：

  Conversion of 2-Alkyl-2-(2-oxopropyl)cyclopentane-1,3-diones into 2,3,5- and 2,3,4-Trisubstituted Cyclopent-2-enones by Intramolecular Aldolizations to 2,3-Diacylcyclopropanolates Followed by Remarkable Skeletal Rearrangements¹

  摘要：

  2-Alkyl-2-(prop-2-ynyl)cyclopentane-1,3-diones 2, conveniently prepared from 2-alkylcyclopentane-1,3-diones 1 and prop-2-ynyl bromide, afford the triketones 3 by Hg2+-catalyzed hydration of the acetylenic triple bond. Treatment of these triketones with aqueous sodium hydroxide gives rise to the 2,3,5-trisubstituted cyclopent-2-enones 5, which are accompanied by the isomeric 2,3,4-trisubstituted cyclopent-2-enones 7 as byproducts. The formation of these isomers can be avoided, when the 2,2-disubstituted cyclopentane-1,3-diones 2 are first converted by ring cleavage into the 5-alkyl-4-oxooct-7-ynaic acids 4 and then by subsequent hydration into the 5-alkyl-4,7-dioxoalkanoic acids 6. An intramolecular aldolization of the latter forms exclusively the cyclopentenones 5. A mechanism explaining the simultaneous formation of 5 and 7 from 3 is based on the formation of the 2,3-diacylcyclopropanolates 11 and 16 by intramolecular aldolization and subsequent ring opening to the 2-acetylcyclohexane-1,4-diones 13 and 18. A further ring opening to the 4,7-dioxoalkanoates 15 and 20 followed by intramolecular aldol condensation then gives rise to the isomeric trisubstituted cyclopent-2-enones 5 and 7.

  DOI：

  10.1021/jo960189q
• 作为产物：
  描述：

  2-甲基-1,3-环戊二酮 在 盐酸 、 正丁基锂 、 对甲苯磺酸 、 碘甲烷 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 、 苯 为溶剂， 反应 0.08h， 生成 2-methyl-2-propargyl-1,3-cyclopentanedione
  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

• A General and Highly Selective Palladium‐Catalyzed Hydroamidation of 1,3‐Diynes
  作者：Jiawang Liu、Carolin Schneider、Ji Yang、Zhihong Wei、Haijun Jiao、Robert Franke、Ralf Jackstell、Matthias Beller

  DOI：10.1002/anie.202010768

  日期：2021.1.4

  3‐diynes is described. Key for the success of this novel transformation is the utilization of an advanced palladium catalyst system with the specific ligand Neolephos. The synthetic value of this general approach to synthetically useful α‐alkynyl‐α, β‐unsaturated amides is showcased by diversification of several structurally complex molecules and marketed drugs. Control experiments and density‐functional

  描述了（不）对称 1,3-二炔的化学选择性、区域选择性和立体选择性单氢酰胺化。这种新型转化成功的关键是采用具有特定配体 Neolephos 的先进钯催化剂系统。这种合成有用的 α-炔基-α, β-不饱和酰胺的通用方法的合成价值通过几种结构复杂的分子和上市药物的多样化得到了展示。控制实验和密度泛函理论 (M06L-SMD) 计算也表明底物在控制不对称 1,3-二炔的区域选择性中发挥着关键作用。
• Synthesis of highly strained bicyclic[3.n.1]alkenes by a metal-catalyzed Conia-ene reaction
  作者：Shivakrishna Kallepu、Krishna Kumar Gollapelli、Jagadeesh Babu Nanubolu、Rambabu Chegondi

  DOI：10.1039/c5cc05926g

  日期：——

  A high yielding metal-catalysed Conia-ene reaction of 2-acetylenic ketones for the synthesis of bicyclo[3.n.1]alkenes has been developed.

  一种高产率的金属催化Conia-ene反应用于合成双环[3.n.1]烯烃的2-乙炔基酮已经被开发出来。
• 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。
• Ni-Catalyzed Reductive Antiarylative Cyclization of Alkynones
  作者：Zhijun Zhou、Wenfeng Liu、Wangqing Kong

  DOI：10.1021/acs.orglett.0c02534

  日期：2020.9.4

  A new catalyst system for the antiarylative cyclization of alkynones and aryl halides through a reductive cross-coupling strategy is developed. The transformation proceeds smoothly in the absence of organometallic reagents and features high functional group tolerance. This method provides an effective platform to access a wide variety of synthetically useful endocyclic tetrasubstituted allylic alcohols

  开发了一种新的催化剂体系，用于通过还原性交叉偶联策略实现炔烃和芳基卤化物的抗芳基环化。在没有有机金属试剂的情况下，转化过程顺利进行，并且具有很高的官能团耐受性。该方法提供了有效的平台，以立体选择性的方式获得各种合成上有用的内环四取代的烯丙基醇。
• 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。