Koenigs–Knorr reaction

The Koenigs–Knorr reaction in organic chemistry is the substitution reaction of a glycosyl halide with an alcohol to give a glycoside. It is one of the oldest and simplest glycosylation reactions. It is named after Wilhelm Koenigs (1851–1906), student of von Bayer and fellow student with Hermann Emil Fischer, and Edward Knorr, student of Koenigs.

In its original form, Koenigs and Knorr treated acetobromoglucose with alcohols in the presence of silver carbonate.[1] Shortly afterwards Fischer and Armstrong reported very similar findings.[2]

In the above example, the stereochemical outcome is determined by the presence of the neighboring group at C2 that lends anchimeric assistance, resulting in the formation of a 1,2-trans stereochemical arrangement. Esters (e.g. acetyl, benzoyl, pivalyl) generally provide good anchimeric assistance, whereas ethers (e.g. benzyl, methyl etc.) do not, leading to mixtures of stereoisomers.

Generally, the Koenigs–Knorr reaction refers to the use of glycosyl chlorides, bromides and more recently iodides as glycosyl donors.

The Koenigs–Knorr reaction can be performed with alternative promoters such as various heavy metal salts including mercuric bromide/mercuric oxide, mercuric cyanide and silver triflate.[3][4] When mercury salts are used, the reaction is normally called the Helferich method.

Other glycosidation methods are Fischer glycosidation, use of glycosyl acetates, thioglycosides, glycosyl trichloroacetimidates, glycosyl fluorides or n-pentenyl glycosides as glycosyl donors, or intramolecular aglycon delivery.

The mechanism for this reaction proceeds through release of a silver halide and is displayed on the German page in full detail.

References

  1. ↑ Wilhelm Koenigs and Edward Knorr (1901). "Ueber einige Derivate des Traubenzuckers und der Galactose (p )". Berichte der deutschen chemischen Gesellschaft 34 (1): 957–981. doi:10.1002/cber.190103401162.
  2. ↑ Hermann Emil Fischer, Armstrong, E.F. (1901). "Ueber die isomeren Acetohalogen-Derivate des Traubenzuckers und die Synthese der Glucoside". Berichte der deutschen chemischen Gesellschaft 34 (2): 2885–2900. doi:10.1002/cber.190103402251.Fischer, E. and Armstrong, E.F. (1901) Ber. Dtsch. Chem. Ges., 34, 2885
  3. ↑ Helferich, B. and Zirner, J. (1962) Chem. Ber., 95, 2604
  4. ↑ Hanessian, S. and Banoub, J. (1980) Methods Carbohydr. Chem., 8, 247
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