4,4-Dimethyl-5-oxa-7-octen-2-one | 90646-74-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4,4-Dimethyl-5-oxa-7-octen-2-one
• 英文别名: 4-allyloxy-4-methylpentan-2-one；4-methyl-4-(2-propen-1-yloxy)-2-pentanone；4-Methyl-4-prop-2-enoxypentan-2-one
• CAS: 90646-74-5
• 化学式: C₉H₁₆O₂
• 分子量: 156.225
• InChiKey: FRLPXYGMPFTIMX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  11
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4,4-Dimethyl-5-oxa-7-octen-2-one 、 二苯基二硒醚 在 samarium diiodide 作用下， 生成 (4R*,5R*)-2,2,4-Trimethyl-5-<(phenylseleno)methyl>tetrahydropyran-4-ol
  参考文献：
  名称：

  Stereochemical Investigations of Samarium(II) Iodide-Promoted 5-Exo and 6-Exo Ketyl-Olefin Radical Cyclization Reactions

  摘要：

  Samarium(II) iodide (SmI2)-promoted ketyl cyclizations of several substituted, unsaturated ketones, providing various cyclopentyl and cyclohexyl systems, have been investigated. The resulting experiments provide stereochemical insight into these reactions and in addition outline the synthetic potential of these 5-exe and 6-exo radical cyclization processes.

  DOI：

  10.1021/jo00109a018
• 作为产物：
  描述：

  4-甲基-3戊烯-2-酮 、 烯丙醇 在 P(i-BuNCH₂CH₂)3N 作用下， 反应 3.0h， 以88%的产率得到4,4-Dimethyl-5-oxa-7-octen-2-one
  参考文献：
  名称：

  Synthesis of new proazaphosphatranes and their application in organic synthesis

  摘要：

  We report herein the synthesis of the new proazaphosphatrane strong bases P(RNCH2CH2)(3)N (R=Me3CCH2, Me2CHCH2) and P(HNCH2CH2)(2)NCH2CH2N-i-Pr (1g). The new azaphosphatranes [HP(RNCH2CH2)(3)N]Cl (R=Me3CCH2, Me2CHCH2)have P-N-ax distances of 2.047 and 1.958 Angstrom, respectively. We also report the synthesis of the tetramine precursor proazaphosphatrane 1g [namely, (H2NCH2CH2)(2)NCH2CH2NH-i-Pr] in 41% yield and the use of a complexation-extraction technique to separate it from a mixture containing the di- and tri-isopropyl substituted analogs. Using a P-31 NMR technique, we report the pK(a) value for 1gH(+) (34.49). The catalytic properties of three bases P(RNCH2CH2)(3)N (R=i-Pr, Piv, i-Bu) are compared in the synthesis of several beta -hydroxy nitriles, beta -nitroalkanols, alpha,beta -unsaturated esters and for the Michael addition of allyl alcohol to alpha,beta -unsaturate ketones. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(00)01016-4

文献信息

• P(RNCH₂CH₂)₃N:  Efficient 1,4-Addition Catalysts
  作者：Philip B. Kisanga、Palanichamy Ilankumaran、Brandon M. Fetterly、John G. Verkade

  DOI：10.1021/jo010228k

  日期：2002.5.1

  The 1,4-addition of primary alcohols, higher nitroalkanes, and a Schiff's base of an alpha-amino ester to alpha,beta-unsaturated substrates produces the corresponding products in moderate to excellent yields when carried out at -63 to 70 degreesC in the presence of catalytic amounts of the nonionic strong bases P(RNCH2CH2)(3)N (R = Me, i-Pr, i-Bu) in isobutyronitrile. Diastereoselectivity for the anti form of the product is high in the case of the Schiff's base in the absence of lithium ion. These catalysts are easily removed from the product by either column filtration through silica gel or via aqueous workup.
• Molecular Design of Organic Superbases, Azacalix[3](2,6)pyridines: Catalysts for 1,2- and 1,4-Additions
  作者：Natsuko Uchida、Junpei Kuwabara、Ayako Taketoshi、Takaki Kanbara

  DOI：10.1021/jo3017428

  日期：2012.12.7

  The molecular design, characteristics, and catalytic activity of macrocyclic amino compounds, azacalix[3](2,6)pyridine derivatives, were studied. The introduction of an electron-donating group on the pyridine moiety and bridging amino phenyl group enabled the enhancement of the basicity of azacalix[3](2,6)pyridine up to pK(BH+) = 29.5 in CD3CN. These derivatives were shown to be efficient catalysts for 1,4-addition reactions of nitroalkanes or primary alcohols to alpha,beta-unsaturated carbonyl compounds and 1,2-addition reactions of nitroalkanes to aromatic aldehydes.
• Stereochemical Investigations of Samarium(II) Iodide-Promoted 5-Exo and 6-Exo Ketyl-Olefin Radical Cyclization Reactions
  作者：Gary A. Molander、Jeffrey A. McKie

  DOI：10.1021/jo00109a018

  日期：1995.2

  Samarium(II) iodide (SmI2)-promoted ketyl cyclizations of several substituted, unsaturated ketones, providing various cyclopentyl and cyclohexyl systems, have been investigated. The resulting experiments provide stereochemical insight into these reactions and in addition outline the synthetic potential of these 5-exe and 6-exo radical cyclization processes.
• Synthesis of new proazaphosphatranes and their application in organic synthesis
  作者：Philip B. Kisanga、John G. Verkade

  DOI：10.1016/s0040-4020(00)01016-4

  日期：2001.1

  We report herein the synthesis of the new proazaphosphatrane strong bases P(RNCH2CH2)(3)N (R=Me3CCH2, Me2CHCH2) and P(HNCH2CH2)(2)NCH2CH2N-i-Pr (1g). The new azaphosphatranes [HP(RNCH2CH2)(3)N]Cl (R=Me3CCH2, Me2CHCH2)have P-N-ax distances of 2.047 and 1.958 Angstrom, respectively. We also report the synthesis of the tetramine precursor proazaphosphatrane 1g [namely, (H2NCH2CH2)(2)NCH2CH2NH-i-Pr] in 41% yield and the use of a complexation-extraction technique to separate it from a mixture containing the di- and tri-isopropyl substituted analogs. Using a P-31 NMR technique, we report the pK(a) value for 1gH(+) (34.49). The catalytic properties of three bases P(RNCH2CH2)(3)N (R=i-Pr, Piv, i-Bu) are compared in the synthesis of several beta -hydroxy nitriles, beta -nitroalkanols, alpha,beta -unsaturated esters and for the Michael addition of allyl alcohol to alpha,beta -unsaturate ketones. (C) 2001 Elsevier Science Ltd. All rights reserved.