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. 2010 May 21;75(10):3515-7.
doi: 10.1021/jo100456z.

Sulfonylation-induced N- to O-acetyl migration in 2-acetamidoethanol derivatives

Takao Yamaguchi  1 , Dusan Hesek, Mijoon Lee, Allen G Oliver, Shahriar Mobashery
Affiliations

Sulfonylation-induced N- to O-acetyl migration in 2-acetamidoethanol derivatives

Takao Yamaguchi et al. J Org Chem. .

Abstract

The first example of sulfonylation-induced N- to O-acetyl migration of 2-acetamidoethanol derivatives is described. This type of reaction could happen with any 2-acetamidoethanol derivatives under typical sulfonylation conditions (TsCl or MsCl, pyridine) and might be a common side reaction of significance. Furthermore, the results reveal that 2-acetamidoethanol derivatives with a sterically encumbered hydroxyl group result in the migration products in high yields. The mechanism of the migration reaction is discussed.

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Figures

FIGURE 1
FIGURE 1
1H NMR spectra of the compounds (A) 1a in DMSO-d6, (B) 2a in CDCl3 and (C) 3a in CDCl3. Compound 1a was not soluble in CDCl3.
SCHEME 1
SCHEME 1
Tosylation of N-acetylglucosamine derivative 1a
SCHEME 2
SCHEME 2
The acetyl migration reactions of 2-acetamidoethanol derivatives
SCHEME 3
SCHEME 3
Mechanistic possibilities of N- to O-acetyl migration of 1a
SCHEME 4
SCHEME 4
Tosylation of the compound 14
SCHEME 5
SCHEME 5
The proposed mechanistic outcome for transformations of 1b
SCHEME 6
SCHEME 6
Mesylation of the compound 1d
See this image and copyright information in PMC

References

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    1. The same type of acyl migration to Scheme 2a is known: D’hooghe M, Vervisch K, Van Nieuwenhove A, De Kimpe N. Tetrahedron Lett. 2007;48:1771–1774.Feng Z, Mohapatra S, Klimko PG, Hellberg MR, May JA, Kelly C, Williams G, McLaughlin MA, Sharif NA. Bioorg Med Chem Lett. 2007;17:2998–3002.Gornostaev LM, Sokolova MS. Russ J Org Chem. 2006;42:1473–1476.Avenoza A, Busto JH, Canal N, Peregrina JM. J Org Chem. 2005;70:330–333.

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