2-Ethyl-2-propargyl-cyclopentan-1,3-dion | 71450-35-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-Ethyl-2-propargyl-cyclopentan-1,3-dion
• 英文别名: 2-ethyl-2-(prop-2-ynyl)cyclopentane-1,3-dione；2-Ethyl-2-prop-2-ynylcyclopentane-1,3-dione
• CAS: 71450-35-6
• 化学式: C₁₀H₁₂O₂
• 分子量: 164.204
• InChiKey: FMXIBPPMSQLPSA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  12
• 可旋转键数：
  2
• 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-Ethyl-2-propargyl-cyclopentan-1,3-dion 在 mercury(II) sulfate sodium hydroxide 、 硫酸 、 水 作用下， 以 甲醇 、 乙醚 、 水 、 正戊烷 为溶剂， 反应 32.0h， 生成 dicyclohexylammonium (+/-)-2-(3-ethyl-2-methyl-5-oxocyclopentenyl)acetate
  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：

  1,3-环戊二酮 在 二氢吡啶 、 碳酸氢钠 、 L-脯氨酸 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 17.0h， 生成 2-Ethyl-2-propargyl-cyclopentan-1,3-dion
  参考文献：
  名称：

  Synthesis of highly strained bicyclic[3.n.1]alkenes by a metal-catalyzed Conia-ene reaction

  摘要：

  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。

  DOI：

  10.1039/c5cc05926g

文献信息

• Synergistic Catalysis: Metal/Proton-Catalyzed Cyclization of Alkynones Toward Bicyclo[3.<i>n</i>.1]alkanones
  作者：Shifa Zhu、Qiaohui Zhang、Kai Chen、Huanfeng Jiang

  DOI：10.1002/anie.201504964

  日期：2015.8.3

  highly efficient and practical synergistically metal/proton‐catalyzed Conia–ene reaction for the synthesis of bicyclo[3.n.1]alkanones has been developed. This synergistic catalysis was successfully utilized in modifying natural compounds such as methyl dihydrojasmonate, α,β‐thujone, and 5α‐cholestan‐3‐one. Furthermore, the bridged carbonyl group of bicyclo[3.2.1]alkanones could be easily attacked by nucleophiles

  已开发出一种高效且实用的协同金属/质子催化的Conia-ene反应合成双环[3.n.1]烷酮。这种协同催化作用已成功用于修饰天然化合物，例如二氢茉莉酮酸甲酯，α，β-thujone和5α-cholestan-3-one。此外，亲核试剂很容易攻击双环[3.2.1]链烷酮的桥连羰基，从而以优异的收率得到开环的环庚烯酮产物或双环[4.2.1]酰胺。这些反应提供了从简单的起始原料或天然存在的化合物快速进入各种环状结构的途径。
• Carbonyl-assisted reverse regioselective cascade annulation of 2-acetylenic ketones triggered by Ru-catalyzed C–H activation
  作者：Krishna Kumar Gollapelli、Shivakrishna Kallepu、Nagendra Govindappa、Jagadeesh Babu Nanubolu、Rambabu Chegondi

  DOI：10.1039/c6sc01456a

  日期：——

  The first reverse regioselective intermolecular annulation of aryl substituted 2-acetylenic ketones with O-substituted N-hydroxybenzamides or acrylamides followed by tandem cyclization via ruthenium-catalyzed C–H activation, is reported.

  报道了芳基取代的2-乙炔基酮与取代的N-羟基苯甲酰胺或丙烯酰胺进行反向区域选择性分子间环化反应，随后通过钌催化的C-H活化串联环化。
• Mn(<scp>i</scp>)-Catalyzed nucleophilic addition/ring expansion <i>via</i> C–H activation and C–C cleavage
  作者：Bingxian Liu、Yin Yuan、Panjie Hu、Guangfan Zheng、Dachang Bai、Junbiao Chang、Xingwei Li

  DOI：10.1039/c9cc05973c

  日期：——

  Mn(I)-Catalyzed synthesis of seven- or eight-membered carbocycles is disclosed via C–H activation of heteroarenes and coupling with alkyne-functionalized 1,3-cyclopentadiones or 1,3-cyclohexadiones. This n to n + 2 (n = 5, 6) ring expansion reaction proceeded via a C–H alkenylation/carbonyl addition/retro-Aldol cascade. Structurally diverse mid-sized carbocycles were constructed via cleavage of both

  锰（Ⅰ）催化的七元或八元碳环的合成是通过杂芳烃的CH活化并与炔基官能化的1，3-环戊二酮或1，3-环己二酮偶联而公开的。此n至n + 2（n = 5，6）的扩环反应是通过C–H烯基化/羰基加成/复古-Aldol级联反应进行的。在一次操作中，通过裂解C–H和C–C键可构造结构多样的中型碳环。
• 2,2-disubstituierte cyclopentan-1,3-dione—2
  作者：Hans Schick、Hartmut Schwarz、Angelika Finger、Sigfrid Schwarz

  DOI：10.1016/0040-4020(82)85114-4

  日期：1982.1

  preferentially yield products of C-alkylation. Dipolar aprotic solvents favour O-alkylation; water favours C-alkylation. On the basis of these results procedures for the prepartion of 2-allyl-2-methyl-, 2-allyl-2-ethyl-, 2-methyl-2-propargyl- and 2 - benzyl - 2 - mehtyl - cyclopentane - 1,3 - dione have been developed. The alkylation of 2 - methyl - cyclopentane - 1,3 - dione with methyl bromoacetate was also

  2-甲基-环戊烷-1,3-二酮的碱金属盐与烷基卤化物的烷基化的区域选择性在很大程度上取决于烷基化试剂的结构和反应中所用溶剂的类型。除甲基碘外，未取代的饱和伯烷基卤化物优先产生O-烷基化的产物。带有SP 2的烷基卤化物在β-位上的-或sp-杂化碳原子优先产生C-烷基化的产物。偶极非质子溶剂促进O-烷基化；水有利于C-烷基化。根据这些结果，制备2-烯丙基-2-甲基-，2-烯丙基-2-乙基-，2-甲基-2-炔丙基-和2-苄基-2-甲基-甲基-环戊烷的制备方法， 3-二酮已经开发出来。还对2-甲基-环戊烷-1,3-二酮与溴乙酸甲酯的烷基化进行了深入研究。
• Cobalt(III)-Catalyzed C–H Activation/Annulation Cascade Reaction of N-Chlorobenzamides with 2-Acetylenic Ketones at Room Temperature
  作者：Yong Wu、Zhouping Wu、Qinwen Zheng、Guanghui Lv、Ruizhi Lai、Yao Hu、Li Hai

  DOI：10.1055/a-1794-1314

  日期：2022.7

  N-chlorobenz­amides with 2-acetylenic ketones at room temperature is reported. This reaction sets N–Cl bond of N-chlorobenzamide as an internal oxidant, displaying broad functional group tolerance and excellent reverse selectivity of alkyne insertion under mild and safe conditions. The cascade reaction offers a straightforward and mild protocol to construct isoquinolones in high yields at room temperature

  报道了在室温下Co(III) 催化的N-氯苯甲酰胺与 2-炔酮的温和级联环化。该反应将 N-氯苯甲酰胺的N -Cl 键设置为内氧化剂，在温和安全的条件下表现出广泛的官能团耐受性和出色的炔烃插入反向选择性。级联反应提供了一种简单而温和的方案，可在室温下以高产率构建异喹诺酮类药物。