2-propyl-2-(prop-2-ynyl)cyclopentane-1,3-dione | 180690-31-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-propyl-2-(prop-2-ynyl)cyclopentane-1,3-dione
• 英文别名: 2-n-propyl-2-propargyl-1,3-cyclopentanedione；2-Propyl-2-prop-2-ynylcyclopentane-1,3-dione
• CAS: 180690-31-7
• 化学式: C₁₁H₁₄O₂
• 分子量: 178.231
• InChiKey: FOHSBNNJFCHOBW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  13
• 可旋转键数：
  3
• 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：

  2-propyl-2-(prop-2-ynyl)cyclopentane-1,3-dione 在 sodium hydroxide 、 水 作用下， 反应 8.0h， 以62%的产率得到(+/-)-4-oxo-5-propyloct-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-propylcyclopentane-1,3-dione 、 3-溴丙炔 在 potassium hydroxide 作用下， 以 水 、 甲苯 为溶剂， 反应 25.0h， 以65%的产率得到2-propyl-2-(prop-2-ynyl)cyclopentane-1,3-dione
  参考文献：
  名称：

  铜催化的酮与酮催化的硼化环化反应，对映体和非对映体选择性合成功能化的碳环。

  摘要：

  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。

  DOI：

  10.1021/acs.orglett.9b01769

文献信息

• 10.1021/acs.orglett.4c01997
  作者：Patil, Vaibhav B.、Raghu Ramudu、Chegondi, Rambabu

  DOI：10.1021/acs.orglett.4c01997

  日期：——

  Fused isocoumarins are frequently found in several natural products and pharmaceuticals. Herein, a cascade annulation of 2-alkynylbenzoate-tethered cyclic 1,3-diones via sequential trans-oxypalladation, carbonyl insertion, 1,3-Pd shift, and β-hydride elimination is reported. This method provides efficient access to highly diastereoselective tetracyclic cyclopentene-fused isocoumarins containing two

  稠合异香豆素常见于多种天然产物和药物中。在此，报道了通过连续的反式氧基钯化、羰基插入、1,3-Pd 移位和 β-氢化物消除，2-炔基苯甲酸酯系链的环状 1,3-二酮的级联环化。该方法提供了有效获得含有两个连续四元立体中心的高度非对映选择性四环环戊烯稠合异香豆素。基于机制研究（包括氘标记实验）提出了一种合理的反应机制。使用手性 Bpy 配体进行对映选择性合成的研究取得了令人鼓舞的初步结果。
• 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。
• 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
  作者：Hans Schick、Birgit Roatsch、Siegfried Schramm、Hans-Detlev Gilsing、Matthias Ramm、Egon Gründemann

  DOI：10.1021/jo960189q

  日期：1996.1.1

  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.