2,2-dimethyl-3-(2-propenyl)cyclohexanone | 144225-48-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,2-dimethyl-3-(2-propenyl)cyclohexanone
• 英文别名: 2,2-Dimethyl-5-prop-2-enylcyclohexan-1-one
• CAS: 144225-48-9
• 化学式: C₁₁H₁₈O
• 分子量: 166.263
• InChiKey: IPZYQSDNEDGSEB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 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：

  2,2-dimethyl-3-(2-propenyl)cyclohexanone 在 氢溴酸 作用下， 以 正己烷 为溶剂， 生成 5-(3-Bromo-propyl)-2,2-dimethyl-cyclohexanone
  参考文献：
  名称：

  A facile synthesis of bicyclo[m.n.1]alkan-1-ols. Evidence for organosamarium intermediates in the samarium(II) iodide promoted intramolecular Barbier-type reaction

  摘要：

  Samarium(II) iodide (SmI2) has been successfully employed as a reductive coupling agent for the intramolecular Barbier-type synthesis of bicyclo[m.n.1]alkan-1-ols. Thus, a variety of 3-(omega-iodoalkyl)cycloalkanones, upon treatment with SmI2 and a catalytic quantity of iron complex in tetrahydrofuran (THF), provide the title compounds in excellent yields. The reaction is quite general for the construction of diverse bicyclic ring systems, including the highly strained bicyclo[2.1.1]hexan-1-ol. In addition to exploring the synthetic utility of this reaction, studies have been performed which provide insight on the mechanistic details of the SmI2-promoted intramolecular Barbier-type synthesis. Compelling evidence for the intermediacy of organosamarium species has thus been gathered.

  DOI：

  10.1021/jo00013a008
• 作为产物：
  描述：

  allylsilane 、 6,6-二甲基-2-环己烯-1-酮 在 四氯化钛 作用下， 以82%的产率得到2,2-dimethyl-3-(2-propenyl)cyclohexanone
  参考文献：
  名称：

  C-2 dimethyl seco-mevinic acids. Synthesis of monocyclic HMG-CoA reductase inhibitors from (R)-(-)-carvone.

  摘要：

  An efficient preparation of novel monocyclic HMG-CoA reductase inhibitors from (R)-(-)-carvone is reported. Utilizing this chiral carbon pool, the C-2 dimethyl seco-mevinic acid 3a was prepared in 17 steps and 5.2 % overall yield. The key chiral intermediate aldehyde 10a was prepared via a short and efficient synthetic sequence (six steps, 27% yield) from (R)-(-)-carvone. The appropriate chirality of the diol acid side chain was secured by employing the chiral acetate synthon ''(S)-HYTRA'' and by performing a stereoselective 1,3-syn reduction on the beta-hydroxy ketone 19. Structural requirements at the C-2 position are rather stringent, and deletion of or addition of an extra methyl group are both unacceptable modifications for this novel class of monocyclic HMG-CoA reductase inhibitors.

  DOI：

  10.1021/jo00052a031

文献信息

• Allylbarium Reagents: Unprecedented Regio- and Stereoselective Allylation Reactions of Carbonyl Compounds
  作者：Akira Yanagisawa、Shigeki Habaue、Katsutaka Yasue、Hisashi Yamamoto

  DOI：10.1021/ja00093a010

  日期：1994.7

  The first direct preparation of allylbarium reagents by reaction of insitu generated reactive barium with various allylic chlorides and their new and unexpected selective allylation reactions with carbonyl compounds are disclosed. Highly reactive barium was readily prepared by the reduction of barium iodide with 2 equiv of lithium biphenylide in dry THF at room temperature. A variety of carbonyl compounds reacted with barium reagents generated from (E)- or (Z)-allylic chlorides in THF at -78 degrees C. All reactions resulted in high yields with remarkable alpha-selectivities not only with aldehydes but also with ketones. The double bond geometry of the starting allylic chloride was completely retained in each case. Stereochemically homogeneous (E)- and (Z)beta,gamma-unsaturated carboxylic acids were easily prepared in good yields by highly alpha-selective carboxylation of allylic barium reagents with carbon dioxide. A selective Michael addition reaction with alpha,beta-unsaturated cycloalkanone was also achieved using an allylbarium reagent. Treatment of 2-cyclopentenone (1 equiv) with allylbarium chloride (2 equiv) in THF at -78 degrees C for 20 min afforded 3-allylcyclopentanone in 94% yield with a 1,4/1,2 ratio of >99/1. Furthermore, the in situ generated barium enolate was efficiently trapped with various kinds of electrophiles (Me(2)C=CHCH2Br, (C5H11CHO)-C-n, and CH3COCl).
• A facile synthesis of bicyclo[m.n.1]alkan-1-ols. Evidence for organosamarium intermediates in the samarium(II) iodide promoted intramolecular Barbier-type reaction
  作者：Gary A. Molander、Jeffrey A. McKie

  DOI：10.1021/jo00013a008

  日期：1991.6

  Samarium(II) iodide (SmI2) has been successfully employed as a reductive coupling agent for the intramolecular Barbier-type synthesis of bicyclo[m.n.1]alkan-1-ols. Thus, a variety of 3-(omega-iodoalkyl)cycloalkanones, upon treatment with SmI2 and a catalytic quantity of iron complex in tetrahydrofuran (THF), provide the title compounds in excellent yields. The reaction is quite general for the construction of diverse bicyclic ring systems, including the highly strained bicyclo[2.1.1]hexan-1-ol. In addition to exploring the synthetic utility of this reaction, studies have been performed which provide insight on the mechanistic details of the SmI2-promoted intramolecular Barbier-type synthesis. Compelling evidence for the intermediacy of organosamarium species has thus been gathered.
• C-2 dimethyl seco-mevinic acids. Synthesis of monocyclic HMG-CoA reductase inhibitors from (R)-(-)-carvone.
  作者：Dinesh V. Patel、Robert J. Schmidt、Eric M. Gordon

  DOI：10.1021/jo00052a031

  日期：1992.12

  An efficient preparation of novel monocyclic HMG-CoA reductase inhibitors from (R)-(-)-carvone is reported. Utilizing this chiral carbon pool, the C-2 dimethyl seco-mevinic acid 3a was prepared in 17 steps and 5.2 % overall yield. The key chiral intermediate aldehyde 10a was prepared via a short and efficient synthetic sequence (six steps, 27% yield) from (R)-(-)-carvone. The appropriate chirality of the diol acid side chain was secured by employing the chiral acetate synthon ''(S)-HYTRA'' and by performing a stereoselective 1,3-syn reduction on the beta-hydroxy ketone 19. Structural requirements at the C-2 position are rather stringent, and deletion of or addition of an extra methyl group are both unacceptable modifications for this novel class of monocyclic HMG-CoA reductase inhibitors.