4,4-dimethyl-1-pentadecen-6-yn-5-one | 139313-54-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4,4-dimethyl-1-pentadecen-6-yn-5-one
• 英文别名: 4,4-Dimethylpentadec-1-en-6-yn-5-one
• CAS: 139313-54-5
• 化学式: C₁₇H₂₈O
• 分子量: 248.409
• InChiKey: TYGJBMAZCWFZFC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.6
• 重原子数：
  18
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 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：

  4,4-dimethyl-1-pentadecen-6-yn-5-one 在 (-)-diisopinocamphenylborane chloride 作用下， 以 neat (no solvent) 为溶剂， 反应 48.0h， 以71%的产率得到4,4-dimethyl-1-pentadecen-6-yn-5-ol
  参考文献：
  名称：

  Chiral synthesis via organoboranes. 34. Selective reductions. 47. Asymmetric reduction of hindered .alpha.,.beta.-acetylenic ketones with B-chlorodiisopinocampheylborane to propargylic alcohols of very high enantiomeric excess. Improved workup procedure for the isolation of product alcohols

  摘要：

  The Midland reagent, Alpine-Borane (2a), is excellent for the asymmetric reduction of many acetylenic ketones, but it fails with hindered derivatives. On the other hand, B-chlorodiisopinocampheylborane (DIP-Chloride, 4) reacts with hindered alpha,beta-acetylenic ketones to provide the corresponding propargylic alcohols in 96 to greater-than-or-equal-to 99% ee. The reaction is in accordance with the tentative mechanism proposed earlier. While 4-phenyl-3-butyn-2-one is reduced in only 21% ee, 4 reduces 4-methyl-1-phenyl-1-pentyn-3-one in 53% ee and 4,4-dimethyl-1-phenyl-1-pentyn-3-one in greater-than-or-equal-to 99% ee. The generality of this observation is demonstrated by reducing a series of hindered acetylenic ketones with increasing steric requirements and differing electronic environments. Thus, 2,2-dimethyl-4-tridecyn-3-one, 1-cyclopentyl-4,4-dimethyl-1-pentyn-3-one, and 3,3-dimethyl-5-tetradecyn-4-one are all reduced to the corresponding alcohols in greater-than-or-equal-to 99% ee and 97% ee, respectively. A modified and operationally simpler workup procedure for obtaining the alcohols in high isolated yields is described. Comparison of reagent 4 with 2a is also made, making clear the range of applicability of each reagent. This development makes it possible to reduce asymmetrically any acetylenic ketone by a judicious choice of either 2a or 4.

  DOI：

  10.1021/jo00034a034
• 作为产物：
  描述：

  2,2-二甲基-4-戊烯醛 在 重铬酸吡啶 、 正丁基锂 、 4 A molecular sieve 作用下， 以 二氯甲烷 为溶剂， 反应 16.5h， 生成 4,4-dimethyl-1-pentadecen-6-yn-5-one
  参考文献：
  名称：

  Chiral synthesis via organoboranes. 34. Selective reductions. 47. Asymmetric reduction of hindered .alpha.,.beta.-acetylenic ketones with B-chlorodiisopinocampheylborane to propargylic alcohols of very high enantiomeric excess. Improved workup procedure for the isolation of product alcohols

  摘要：

  The Midland reagent, Alpine-Borane (2a), is excellent for the asymmetric reduction of many acetylenic ketones, but it fails with hindered derivatives. On the other hand, B-chlorodiisopinocampheylborane (DIP-Chloride, 4) reacts with hindered alpha,beta-acetylenic ketones to provide the corresponding propargylic alcohols in 96 to greater-than-or-equal-to 99% ee. The reaction is in accordance with the tentative mechanism proposed earlier. While 4-phenyl-3-butyn-2-one is reduced in only 21% ee, 4 reduces 4-methyl-1-phenyl-1-pentyn-3-one in 53% ee and 4,4-dimethyl-1-phenyl-1-pentyn-3-one in greater-than-or-equal-to 99% ee. The generality of this observation is demonstrated by reducing a series of hindered acetylenic ketones with increasing steric requirements and differing electronic environments. Thus, 2,2-dimethyl-4-tridecyn-3-one, 1-cyclopentyl-4,4-dimethyl-1-pentyn-3-one, and 3,3-dimethyl-5-tetradecyn-4-one are all reduced to the corresponding alcohols in greater-than-or-equal-to 99% ee and 97% ee, respectively. A modified and operationally simpler workup procedure for obtaining the alcohols in high isolated yields is described. Comparison of reagent 4 with 2a is also made, making clear the range of applicability of each reagent. This development makes it possible to reduce asymmetrically any acetylenic ketone by a judicious choice of either 2a or 4.

  DOI：

  10.1021/jo00034a034

文献信息

• Chiral synthesis via organoboranes. 34. Selective reductions. 47. Asymmetric reduction of hindered .alpha.,.beta.-acetylenic ketones with B-chlorodiisopinocampheylborane to propargylic alcohols of very high enantiomeric excess. Improved workup procedure for the isolation of product alcohols
  作者：P. Veeraraghavan Ramachandran、Aleksandar V. Teodorovic、Milind V. Rangaishenvi、Herbert C. Brown

  DOI：10.1021/jo00034a034

  日期：1992.4

  The Midland reagent, Alpine-Borane (2a), is excellent for the asymmetric reduction of many acetylenic ketones, but it fails with hindered derivatives. On the other hand, B-chlorodiisopinocampheylborane (DIP-Chloride, 4) reacts with hindered alpha,beta-acetylenic ketones to provide the corresponding propargylic alcohols in 96 to greater-than-or-equal-to 99% ee. The reaction is in accordance with the tentative mechanism proposed earlier. While 4-phenyl-3-butyn-2-one is reduced in only 21% ee, 4 reduces 4-methyl-1-phenyl-1-pentyn-3-one in 53% ee and 4,4-dimethyl-1-phenyl-1-pentyn-3-one in greater-than-or-equal-to 99% ee. The generality of this observation is demonstrated by reducing a series of hindered acetylenic ketones with increasing steric requirements and differing electronic environments. Thus, 2,2-dimethyl-4-tridecyn-3-one, 1-cyclopentyl-4,4-dimethyl-1-pentyn-3-one, and 3,3-dimethyl-5-tetradecyn-4-one are all reduced to the corresponding alcohols in greater-than-or-equal-to 99% ee and 97% ee, respectively. A modified and operationally simpler workup procedure for obtaining the alcohols in high isolated yields is described. Comparison of reagent 4 with 2a is also made, making clear the range of applicability of each reagent. This development makes it possible to reduce asymmetrically any acetylenic ketone by a judicious choice of either 2a or 4.