1-O-benzyl-5-methyl-2-hexyne-1,4-diol | 532940-99-1

• 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-methyl-2-hexyne-1,4-diol
• 英文别名: 6-(benzyloxy)-2-methyl-4-hexyn-3-ol；6-benzyloxy-2-methyl-hex-4-yn-3-ol；2-Methyl-6-phenylmethoxyhex-4-yn-3-ol
• CAS: 532940-99-1
• 化学式: C₁₄H₁₈O₂
• 分子量: 218.296
• InChiKey: CCNGTRSDSIBCSG-UHFFFAOYSA-N

物化性质

• 沸点：
  349.8±22.0 °C(Predicted)
• 密度：
  1.043±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 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-methyl-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-methyl-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：

  苯甲醇 在 正丁基锂 、 sodium hydride 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 0.5h， 生成 1-O-benzyl-5-methyl-2-hexyne-1,4-diol
  参考文献：
  名称：

  铜催化炔丙基二氟化物的“三键迁移”加氢脱氟

  摘要：

  报道了铜催化的炔丙基二氟化物的加氢脱氟反应，其中两个 C-F 键还原转化为 C-H 键，并通过三键迁移一个亚甲基得到了一种新的炔烃产物。机理研究表明，该产物是通过逐步C-F键还原加氢获得的，并且提出了烯基一氟化物作为活性中间体之一。

  DOI：

  10.1016/j.tet.2022.132897

文献信息

• Iron carbonyl-mediated homologous Michael reactions of γ-alkoxy alkenones
  作者：Tianhao Zhou、James R. Green

  DOI：10.1016/0040-4039(93)88068-t

  日期：1993.7

  Iron tetracarbonyl complexes of γ-benzyloxy-α,β-unsaturated ketones react with several nucleophiles in the presence of Lewis acids to give γ-substitution products. The allyltetracarbonyliron cation intermediates generated allow retention of configuration of the double bond.

  γ-苄氧基-α，β-不饱和酮的四羰基铁配合物在路易斯酸存在下与几种亲核试剂反应生成γ取代产物。生成的烯丙基四羰基铁阳离子中间体可保留双键的构型。
• Diastereoselective Zinco-Cyclopropanation of Chiral Allylic Alcohols with <i>g</i><i>em</i>-Dizinc Carbenoids
  作者：Jean-François Fournier、Simon Mathieu、André B. Charette

  DOI：10.1021/ja054328+

  日期：2005.9.28

  allylic alcohols using gem-dizinc carbenoids is described. The reaction produces three contiguous stereogenic centers, and the resulting chiral cyclopropylzinc derivatives can be trapped with electrophiles with retention of configuration. Simple functional group manipulations lead to the efficient synthesis of orthogonally protected 1,2,3-substituted cyclopropane derivatives.

  描述了使用 gem-dizinc carbenoids 对手性烯丙醇进行高度非对映选择性锌环丙烷化反应。该反应产生三个连续的立体中心，所得的手性环丙基锌衍生物可以被亲电试剂捕获并保留构型。简单的官能团操作可有效合成正交保护的 1,2,3-取代环丙烷衍生物。
• 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.
• Copper catalyzed hydrodefluorination of propargylic gem-difluorides with “triple bonds migration”
  作者：Ting Wang、Zhirong Li、Jiayi Hu、Tao Wu

  DOI：10.1016/j.tet.2022.132897

  日期：2022.8

  A copper catalyzed hydrodefluorination of propargylic gem-difluorides was reported, in which two C–F bonds was reductive converted to C–H bonds and a new alkyne product was afforded with the triple bond migrating one methylene. Mechanistic studies show that the products are achieved by stepwise C–F bond reductive hydrogenation, and an allenyl monofluoride is proposed to be one of the active intermediates

  报道了铜催化的炔丙基二氟化物的加氢脱氟反应，其中两个 C-F 键还原转化为 C-H 键，并通过三键迁移一个亚甲基得到了一种新的炔烃产物。机理研究表明，该产物是通过逐步C-F键还原加氢获得的，并且提出了烯基一氟化物作为活性中间体之一。