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. [cite journal
title = Ueber einige Derivate des Traubenzuckers und der Galactose (p )
author = Wilhelm Koenigs and Edward Knorr
journal = Berichte der deutschen chemischen Gesellschaft
volume = 34
issue = 1
pages = 957–981
year = 1901
url =
doi = 10.1002/cber.190103401162 ] Shortly afterwards Fischer and Armstrong reported very similar findings. [cite journal
title = Ueber die isomeren Acetohalogen-Derivate des Traubenzuckers und die Synthese der Glucoside
author = Hermann Emil Fischer, Armstrong, E.F.
journal = Berichte der deutschen chemischen Gesellschaft
volume = 34
issue = 2
pages = 2885–2900
year = 1901
url =
doi = 10.1002/cber.190103402251 Fischer, E. and Armstrong, E.F. (1901) "Ber. Dtsch. Chem. Ges.", 34, 2885]

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 generally provide good anchimeric assistance, whereas ethers (eg 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. [Helferich, B. and Zirner, J. (1962) "Chem. Ber.", 95, 2604] [Hanessian, S. and Banoub, J. (1980) "Methods Carbohydr. Chem.", 8, 247]

Other glycosidation methods are Fischer glycosidation and the Helferich method.

References