2-Methyl-2-((E)-4-oxo-pent-2-enyl)-cyclopentane-1,3-dione | 690660-57-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-Methyl-2-((E)-4-oxo-pent-2-enyl)-cyclopentane-1,3-dione
• 英文别名: 2-methyl-2-[(E)-4-oxopent-2-enyl]cyclopentane-1,3-dione
• CAS: 690660-57-2
• 化学式: C₁₁H₁₄O₃
• 分子量: 194.23
• InChiKey: PWKCWWJMQIISNQ-ONEGZZNKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  51.2
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-Methyl-2-((E)-4-oxo-pent-2-enyl)-cyclopentane-1,3-dione 在 bis(1,5-cyclooctadiene)rhodium(I) trifluoromethanesulfonate 氢气 、 potassium carbonate 、 三苯基膦 作用下， 以 1,2-二氯乙烷 为溶剂， 25.0 ℃ 、101.32 kPa 条件下， 以88%的产率得到(3aS,4S,6aS)-4-Acetyl-3a-hydroxy-6a-methyl-hexahydro-pentalen-1-one
  参考文献：
  名称：

  Enolate Generation under Hydrogenation Conditions:  Catalytic Aldol Cycloreduction of Keto-Enones

  摘要：

  [GRAPHIC]Formal heterolytic activation of elemental hydrogen under Rh catalysis enables the reductive generation of enolates from enones under hydrogenation conditions. Enolates generated in this fashion participate in catalytic C-C bond formation via carbonyl addition to aldehyde and, as demonstrated in this account, ketone partners. Notably, the use of appendant dione partners enables diastereoselective formation of cycloaidol products possessing 3-stereogenic centers, including 2-contiguous quaternary centers.

  DOI：

  10.1021/ol0300219
• 作为产物：
  描述：

  2-烯丙基-2-甲基-1,3-环戊二酮 在 臭氧 作用下， 以 二氯甲烷 、 氯仿 为溶剂， 生成 2-Methyl-2-((E)-4-oxo-pent-2-enyl)-cyclopentane-1,3-dione
  参考文献：
  名称：

  Enolate Generation under Hydrogenation Conditions:  Catalytic Aldol Cycloreduction of Keto-Enones

  摘要：

  [GRAPHIC]Formal heterolytic activation of elemental hydrogen under Rh catalysis enables the reductive generation of enolates from enones under hydrogenation conditions. Enolates generated in this fashion participate in catalytic C-C bond formation via carbonyl addition to aldehyde and, as demonstrated in this account, ketone partners. Notably, the use of appendant dione partners enables diastereoselective formation of cycloaidol products possessing 3-stereogenic centers, including 2-contiguous quaternary centers.

  DOI：

  10.1021/ol0300219

文献信息

• Copper-Catalyzed Tandem Conjugate Addition−Electrophilic Trapping:  Ketones, Esters, and Nitriles as Terminal Electrophiles
  作者：Kyriacos Agapiou、David F. Cauble、Michael J. Krische

  DOI：10.1021/ja030603l

  日期：2004.4.1

  Exposure of enone substrates 1a-18a, which possess appendant ketone, ester, and nitrile moieties, to Et2Zn in the presence of catalytic Cu(OTf)2/P(OEt)3 provides the cyclized products in good to excellent yields and diastereoselectivities. These results represent the first use of ketones, esters, and nitriles as terminal electrophiles in Cu-catalyzed conjugate addition-electrophilic trapping.
• Access to Polyfunctionalized Diquinanes, Hydrindanes, and Decalines via TiCl₄ Promoted Michael–Aldol and Baylis–Hillman Reactions
  作者：Blandine Ressault、Alexis Jaunet、Philippe Geoffroy、Sébastien Goudedranche、Michel Miesch

  DOI：10.1021/ol203118t

  日期：2012.1.6

  The addition of 0.5 equiv of TiCl4 to (cyclo)alkanones tethered to alpha,beta-unsaturated ketones afforded polyfunctionalized diquinanes, hydrindanes, and decalines. These products, resulting from a Michael-aldol or a Baylis-Hillman reaction, can be obtained with high or total diastereoselectivity in moderate to high yields. These scaffolds represent interesting building blocks for the synthesis of complex natural products.
• Enolate Generation under Hydrogenation Conditions:  Catalytic Aldol Cycloreduction of Keto-Enones
  作者：Ryan R. Huddleston、Michael J. Krische

  DOI：10.1021/ol0300219

  日期：2003.4.1

  [GRAPHIC]Formal heterolytic activation of elemental hydrogen under Rh catalysis enables the reductive generation of enolates from enones under hydrogenation conditions. Enolates generated in this fashion participate in catalytic C-C bond formation via carbonyl addition to aldehyde and, as demonstrated in this account, ketone partners. Notably, the use of appendant dione partners enables diastereoselective formation of cycloaidol products possessing 3-stereogenic centers, including 2-contiguous quaternary centers.