Syntheses of 1,2-distributed adamantanes

✍ Scribed by Ashraf N. Abdel-Sayed; Ludwig Bauer

• Book ID: 104205259
• Publisher: Elsevier Science
• Year: 1988
• Tongue: French
• Weight: 919 KB
• Volume: 44
• Category: Article
• ISSN: 0040-4020
• DOI: 10.1016/s0040-4020(01)90330-8

✦ Synopsis

Electrophilically-catalyzed reactions of Q-exe-and Q-endo-epoxymethyleneprotoadamantane (1) and of 4-protoadamantanone (21 provided a variety of 1,tdisubstituted adamantanes. Reactions of I with Lewis acids such as aluminum chloride, bromide and iodide at -78 'C afforded t-chloro-, 2-bromo-, and 2-iodo-I-(hydroxymethyl)adamantanes in excellent yields. An interesting fluoride ion transfer took place when 1 was reacted with boron trifluoride to form 2-fluoro-1-(hydroxymethyl)adamantane. The reaction of 1 with benzene in the presence of aluminum bromide produced I-(hydroxymethyl)_2phenyladamantane in 70% yield. From the acid-catalyzed addition and rearrangement of 2 with hydrohalic acids there were obtained excellent yields of 2-ha&l-adamantanols and 1,2-dihaloadamantanes. 2-Halo-l-adamantanols served as starting materials for the synthesis of twelve additional 1,2--