Carbocation Rearrangements: The Pinacol, Wagner–Meerwein, Demjanov, and Tiffeneau–Demjanov Rearrangements

This Name Reaction Biography presents various carbocation rearrangements by five European chemists.

The first carbocation rearrangement to be observed and characterized was the pinacol rearrangement, discovered by German chemist Rudolph Fittig and optimized by Aleksandr Mikhailovich Butlerov who was responsible for first proposing the correct structure of both pinacol and its acid rearrangement product. By far the most commonly encountered carbocation rearrangements are Wagner–Meerwein rearrangements. The first such rearrangement characterized was reported by Yegor Yegorovich Vagner, better known by the German form of his name, Georg Wagner.
In 1903, Nikolai Yavkovlevich Dem’yanov and his student, Mikhail Alekseevich Lushnikov, published the first paper describing the rearrangement of the cyclobutylcarbinyl system to the cyclopentyl system by the treatment of (cyclobutylmethyl)amine with nitrous acid. In 1937, Marc Émile Pierre Adolphe Tiffeneau published a paper in which he described the rearrangement of 1­(aminomethyl)cyclohexanol to cycloheptanone by treatment with nitrous acid, now known as the Tiffeneau–Demjanov rearrangement.

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