Reaction of 1-adamantyl cation with carbon monoxide in the presence of adamantane and trifluoromethanesulfonic acid: a convenient route to 3,4-homoadamantanediol

✍ Scribed by Ken'Ichi Takeuchi; Fumio Akiyama; Tadakazu Miyazaki; Itsuko Kitagawa; Kunio Okamoto

• Publisher: Elsevier Science
• Year: 1987
• Tongue: French
• Weight: 947 KB
• Volume: 43
• Category: Article
• ISSN: 0040-4020
• DOI: 10.1016/s0040-4020(01)90004-3

✦ Synopsis

The carbonylat-ion of the l-adama~tyl cation with carbon monoxide In carbon tetrachlorfde at atmosoher$c oressure in the oresence of tr6f3uacondittcns.. Among various l-adakantyl cation pre&rsors teste& l~ad~~t~~ trjfluor~thanesulfo~ate (tr*ftatef and ~tbanesul~onate (mesylate) have gfven the best, comparable results, A% to the acid catalyst, floo~sulfon~~ acid is less effective than triflic acid, and 100% sulfuric acid and methanesulfonic acid are completely ineffective to praduce 2. It is recommended to use F4vt! mol each of triflic acid and ada~nta~~ per mol of l-adamantyl mesylatc or triflate. fh+s reaction proceeds via the addition of the l-adamantanecarbonyl cation ta 1-adamantanecarbaldehyde, a transient intermediate, followed by the Uagner-Fleerwein rearrangement. The hydroxy ester 2 is easily converted into 3,4-h~oadamantanedjol which is a promising startfng material for J,B-bifunctional h~aadamantane derivatives.