1-O-benzyl-5,5-dimethyl-2-hexyne-1,4-diol

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1-O-benzyl-5,5-dimethyl-2-hexyne-1,4-diol
• 英文别名: 6-(benzyloxy)-2,2-dimethyl-4-hexyn-3-ol；2,2-Dimethyl-6-phenylmethoxyhex-4-yn-3-ol
• 化学式: C₁₅H₂₀O₂
• 分子量: 232.323
• InChiKey: IHDFBRQRMATCEU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-O-benzyl-5,5-dimethyl-2-hexyne-1,4-diol 在 4-二甲氨基吡啶 、 三乙胺 、 红铝 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 3.0h， 生成 (E)-6-(benzyloxy)-2,2-dimethyl-4-hexen-3-yl benzoate
  参考文献：
  名称：

  Stereoselective Synthesis of (2Z,4E)-2,4-Pentadien-1-ols via Sequential 1,4-Elimination Reaction and [1,2]-Wittig Rearrangement Starting from (E)-4-Alkoxy-2-butenyl Benzoates

  摘要：

  The sequential 1,4-elimination reaction of (E)-4-alkoxy-2-butenyl benzoates and [1,2]-Wittig rearrangement gave (2Z,4E)-2,4-pentadien-1-ols stereoselectively. Z-Selective formation of intermediary vinyl ethers, whose stereochemistry was well elucidated by the "syn-effect", was achieved by treatment of the 2-butenyl benzoates with KOH in the presence of Pd catalyst. The subsequent [1,2]-Wittg rearrangement by use of n-BuLi proceeded with retention of the stereochemistry of the intermediary vinyl ethers.

  DOI：

  10.1021/jo402272r
• 作为产物：
  描述：

  苄基丙炔基醚 、 特戊醛 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 3.83h， 以42%的产率得到1-O-benzyl-5,5-dimethyl-2-hexyne-1,4-diol
  参考文献：
  名称：

  Stereoselective Synthesis of (2Z,4E)-2,4-Pentadien-1-ols via Sequential 1,4-Elimination Reaction and [1,2]-Wittig Rearrangement Starting from (E)-4-Alkoxy-2-butenyl Benzoates

  摘要：

  The sequential 1,4-elimination reaction of (E)-4-alkoxy-2-butenyl benzoates and [1,2]-Wittig rearrangement gave (2Z,4E)-2,4-pentadien-1-ols stereoselectively. Z-Selective formation of intermediary vinyl ethers, whose stereochemistry was well elucidated by the "syn-effect", was achieved by treatment of the 2-butenyl benzoates with KOH in the presence of Pd catalyst. The subsequent [1,2]-Wittg rearrangement by use of n-BuLi proceeded with retention of the stereochemistry of the intermediary vinyl ethers.

  DOI：

  10.1021/jo402272r

文献信息

• Catalytic Alkynylation of Ketones and Aldehydes Using Quaternary Ammonium Hydroxide Base
  作者：Teruhiko Ishikawa、Tomohiro Mizuta、Kumiko Hagiwara、Toshiaki Aikawa、Takayuki Kudo、Seiki Saito

  DOI：10.1021/jo026592g

  日期：2003.5.1

  Catalytic alkynylation of diverse ketones and aldehydes using nonmetallic benzyltrimethylammonium hydroxide or a basic resin of the hydroxide type in DMSO is described. Aliphatic or alicyclic carbonyl partners gave satisfactory results, whereas aromatic ones afforded products with low yields. When aromatic aldehydes were reacted with phenylacetylene, enones such as chalcone derivatives were obtained in place of ynols. These organobase-catalyzed systems provide a practical nonmetallic protocol for C-C bond formation.
• Stereoselective Synthesis of (2<i>Z</i>,4<i>E</i>)-2,4-Pentadien-1-ols via Sequential 1,4-Elimination Reaction and [1,2]-Wittig Rearrangement Starting from (<i>E</i>)-4-Alkoxy-2-butenyl Benzoates
  作者：Takeo Nakano、Takahiro Soeta、Kohei Endo、Katsuhiko Inomata、Yutaka Ukaji

  DOI：10.1021/jo402272r

  日期：2013.12.20

  The sequential 1,4-elimination reaction of (E)-4-alkoxy-2-butenyl benzoates and [1,2]-Wittig rearrangement gave (2Z,4E)-2,4-pentadien-1-ols stereoselectively. Z-Selective formation of intermediary vinyl ethers, whose stereochemistry was well elucidated by the "syn-effect", was achieved by treatment of the 2-butenyl benzoates with KOH in the presence of Pd catalyst. The subsequent [1,2]-Wittg rearrangement by use of n-BuLi proceeded with retention of the stereochemistry of the intermediary vinyl ethers.