5-cyclohexyl-2,2-dimethyl-4-penten-3-one | 727381-76-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5-cyclohexyl-2,2-dimethyl-4-penten-3-one
• 英文别名: (E)-1-cyclohexyl-4,4-dimethylpent-1-en-3-one
• CAS: 727381-76-2
• 化学式: C₁₃H₂₂O
• 分子量: 194.317
• InChiKey: YFTHUKKZEYCXOI-MDZDMXLPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  5-cyclohexyl-2,2-dimethyl-4-penten-3-one 在 sodium hypochlorite 、 chiral quaternary ammonium bromide 作用下， 以 甲苯 为溶剂， 反应 48.0h， 以80%的产率得到trans-epoxy-5-cyclohexyl-2,2-dimethylpentan-3-one
  参考文献：
  名称：

  设计具有双重功能的新型手性相转移催化剂，用于 α,β-不饱和酮的高对映选择性环氧化

  摘要：

  一种具有二芳基甲醇官能团作为底物识别位点的新型手性溴化铵 1-Br 已被设计为一种有前途的双功能催化剂，用于在温和的相转移条件下对 α,β-不饱和酮进行高度对映选择性环氧化。例如，将查耳酮、1-Br (3 mol%) 和 13% NaOCl 在甲苯中的混合物在 0°C 下剧烈搅拌 24 小时，可定量生成 96% ee 的环氧查耳酮。各种 α,β-不饱和酮也可以通过严格的立体化学控制进行环氧化，清楚地证明了本系统的有效性和实用性。此外，1-PF6 的成功单晶 X 射线衍射分析揭示了其独特的三维分子结构，并为假设过渡态提供了有用的信息。

  DOI：

  10.1021/ja048600b
• 作为产物：
  描述：

  1-cyclohexyl-1-hydroxy-4,4-dimethylpentan-3-one 在 双[Α,Α-双(三氟甲基)苯甲醇合]二苯硫 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以99%的产率得到5-cyclohexyl-2,2-dimethyl-4-penten-3-one
  参考文献：
  名称：

  SmI₂-Promoted Reformatsky-Type Coupling Reactions in Exceptionally Hindered Contexts

  摘要：

  Highly substituted, very hindered enones were synthesized using a two-step procedure that utilizes a diiodosamarium-promoted Reformatsky-type coupling and dehydration using Martin sulfurane. Both alpha-chloro- and alpha-bromoketones were coupled with a variety of carbonyl nucleophiles to form the intermediate beta-hydroxyketones, occurring with excellent diastereoselectivity, favoring the syn isomer (R-1 = Me). This technique complements other methods,and enables the preparation of enones outside of the scope of current olefination methodology.

  DOI：

  10.1021/ol800099a

文献信息

• Highly Effective Vinylogous Mukaiyama−Michael Reaction Catalyzed by Silyl Methide Species Generated from 1,1,3,3-Tetrakis(trifluoromethanesulfonyl)propane
  作者：Arata Takahashi、Hikaru Yanai、Min Zhang、Takaaki Sonoda、Masaaki Mishima、Takeo Taguchi

  DOI：10.1021/jo902641g

  日期：2010.2.19

  Silyl methide species in situ generated from 1,1,3,3-tetrakis(trifluoromethanesulfonyl)propane (Tf2CHCH2CHTf2) performed as an excellent acid catalyst for the vinylogous Mukaiyama-Michael reaction of alpha,beta-unsaturated ketones with 2-silyloxyfurans. Notably, the required loading of Tf2CHCH2CHTf2 to obtain the 1,4-adducts in reasonable yield was significantly low (from 0.05 to 1.0 mol %). This carbon acid-mediated VMM reaction provides a powerful synthetic methodology to construct highly substituted gamma-butenolide structure.
• SmI₂-Promoted Reformatsky-Type Coupling Reactions in Exceptionally Hindered Contexts
  作者：Brian A. Sparling、Ryan M. Moslin、Timothy F. Jamison

  DOI：10.1021/ol800099a

  日期：2008.3.1

  Highly substituted, very hindered enones were synthesized using a two-step procedure that utilizes a diiodosamarium-promoted Reformatsky-type coupling and dehydration using Martin sulfurane. Both alpha-chloro- and alpha-bromoketones were coupled with a variety of carbonyl nucleophiles to form the intermediate beta-hydroxyketones, occurring with excellent diastereoselectivity, favoring the syn isomer (R-1 = Me). This technique complements other methods,and enables the preparation of enones outside of the scope of current olefination methodology.
• Design of New Chiral Phase-Transfer Catalysts with Dual Functions for Highly Enantioselective Epoxidation of α,β-Unsaturated Ketones
  作者：Takashi Ooi、Daisuke Ohara、Masazumi Tamura、Keiji Maruoka

  DOI：10.1021/ja048600b

  日期：2004.6.1

  has been designed as a promising, dual-functioning catalyst for the highly enantioselective epoxidation of α,β-unsaturated ketones under mild phase-transfer conditions. For instance, vigorous stirring of a mixture of chalcone, 1-Br (3 mol %), and 13% NaOCl in toluene at 0 °C for 24 h gave rise to epoxy chalcone quantitatively with 96% ee. A variety of α,β-unsaturated ketones can also be epoxidized with

  一种具有二芳基甲醇官能团作为底物识别位点的新型手性溴化铵 1-Br 已被设计为一种有前途的双功能催化剂，用于在温和的相转移条件下对 α,β-不饱和酮进行高度对映选择性环氧化。例如，将查耳酮、1-Br (3 mol%) 和 13% NaOCl 在甲苯中的混合物在 0°C 下剧烈搅拌 24 小时，可定量生成 96% ee 的环氧查耳酮。各种 α,β-不饱和酮也可以通过严格的立体化学控制进行环氧化，清楚地证明了本系统的有效性和实用性。此外，1-PF6 的成功单晶 X 射线衍射分析揭示了其独特的三维分子结构，并为假设过渡态提供了有用的信息。