The Boekelheide reaction is a rearrangement of α-picoline-N-oxides to hydroxymethylpyridines. It is named after Virgil Boekelheide who first reported it in 1954.[1] Originally the reaction was carried out using acetic anhydride, which typically required a period at reflux (~140 °C). The reaction can be performed using trifluoroacetic anhydride (TFAA), which often allows for a room temperature reaction.[2]
The mechanism of the Boekelheide reaction begins by an acyl transfer from the trifluoroacetic anhydride to the N-oxide oxygen. The α-methyl carbon is then deprotonated by the trifluoroacetate anion. This sets the molecule up for a [3.3]-sigmatropic rearrangement which furnishes the trifluoroacetylated methylpyridine. Hydrolysis of the trifluoroacetate releases the hydroxymethylpyridine.
Mechanism of the Boekelheide reaction
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ReferencesEdit
^Boekelheide, V.; Linn, W. J. (March 1954). "Rearrangements of N-Oxides. A Novel Synthesis of Pyridyl Carbinols and Aldehydes". Journal of the American Chemical Society. 76 (5): 1286–1291. doi:10.1021/ja01634a026.
^Fontenas, C.; Bejan, E.; Haddou, H. Aït; Balavoine, G. G. A. (23 September 2006). "The Boekelheide Reaction: Trifluoroacetic Anhydride as a Convenient Acylating Agent". Synthetic Communications. 25 (5): 629–633. doi:10.1080/00397919508011399.
August 29, 2023
boekelheide, reaction, rearrangement, picoline, oxides, hydroxymethylpyridines, named, after, virgil, boekelheide, first, reported, 1954, originally, reaction, carried, using, acetic, anhydride, which, typically, required, period, reflux, reaction, performed, . The Boekelheide reaction is a rearrangement of a picoline N oxides to hydroxymethylpyridines It is named after Virgil Boekelheide who first reported it in 1954 1 Originally the reaction was carried out using acetic anhydride which typically required a period at reflux 140 C The reaction can be performed using trifluoroacetic anhydride TFAA which often allows for a room temperature reaction 2 Boekelheide reactionNamed after Virgil Carl BoekelheideReaction type Rearrangement reaction Overall reaction of the Boekelheide reactionMechanism EditThe mechanism of the Boekelheide reaction begins by an acyl transfer from the trifluoroacetic anhydride to the N oxide oxygen The a methyl carbon is then deprotonated by the trifluoroacetate anion This sets the molecule up for a 3 3 sigmatropic rearrangement which furnishes the trifluoroacetylated methylpyridine Hydrolysis of the trifluoroacetate releases the hydroxymethylpyridine Mechanism of the Boekelheide reaction Wikimedia Commons has media related to Boekelheide reaction References Edit Boekelheide V Linn W J March 1954 Rearrangements of N Oxides A Novel Synthesis of Pyridyl Carbinols and Aldehydes Journal of the American Chemical Society 76 5 1286 1291 doi 10 1021 ja01634a026 Fontenas C Bejan E Haddou H Ait Balavoine G G A 23 September 2006 The Boekelheide Reaction Trifluoroacetic Anhydride as a Convenient Acylating Agent Synthetic Communications 25 5 629 633 doi 10 1080 00397919508011399 Retrieved from https en wikipedia org w index php title Boekelheide reaction amp oldid 1121932666, wikipedia, wiki, book, books, library,
