A short-cut from 1-acetyl adamantane to 2-(1-adamantyl)pyrroles
- 作者：Boris A. Trofimov ; Elena Yu. Schmidt ; Nadezhda V. Zorina ; Elena Yu. Senotrusova ; Nadezhda I. Protsuk ; Igor A. Ushakov ; Al’ ; bina I. Mikhaleva ; Rachel Mé ; allet-Renault ; Gilles Clavier
- 关键词：Pyrrole ; Adamantane ; Oxime ; Acetylene ; O-Vinyloxime ; 2-(1-Adamantyl)pyrrole
- 刊名：Tetrahedron Letters
- 出版年：2008
- 期刊代码：109_00404039
- 类别：ch
- 出版时间：7 July 2008
- 卷：49
- 期：28
- 页码：4362-4365
- 文件大小：182 K
摘要
The oxime of 1-acetyl adamantane <strong>2strong> is added to acetylene (KOH/DMSO, 70 °C, initial acetylene pressure 13 atm, 30 min) to afford the corresponding O-vinyl oxime <strong>5strong> in 80%yield. The latter upon heating (DMSO, 120 °C, 1 h) gives 2-(1-adamantyl)pyrrole <strong>3strong>, 1-acetyl adamantane <strong>1strong>, and adamantane (6:3:1 mass ratio), the yield of the pyrrole <strong>3strong> being 83%(based on 1-acetyl adamantane <strong>1strong> consumed). Under harsher conditions (NaOH/DMSO, 130 °C, atmospheric pressure of acetylene, 4 h) oxime <strong>2strong> reacts with acetylene to furnish pyrrole <strong>3strong>, 1-acetyl adamantane <strong>1strong>, 1-vinyl adamantane <strong>9strong>, and adamantane (6:7:3:1 mass ratio), with the isolated yield of pyrrole <strong>3strong> reaching 34%. Under pressure (NaOH/DMSO, 120 °C, initial acetylene pressure 14 atm, 1 h) the same reaction leads to 2-(1-adamantyl)-1-vinylpyrrole <strong>4strong> and ketone <strong>1strong> in 48%(based on consumed ketone <strong>1strong>) and 24%yields, respectively. The pyrrole <strong>4strong> is easily deprotected to the corresponding 1H-pyrrole <strong>3strong> in 77%yield by treatment (aqueous MeCN) with Hg(OAc)<sub>2sub> and NaBH<sub>4sub>.