Stork enamine alkylation
Stork enamine alkylation, also known as the Stork-Enamine reaction, involves the addition of an enamine to an alpha,beta-unsaturated carbonyl acceptor in a process similar to the Michael reaction [1]. The product is then hydrolyzed by an aqueous acid to produce a 1,5-dicarbonyl compound.
The process:
- formation of an enamine from a ketone
- addition of the enamine to and alpha, beta-unsaturated aldehyde or ketone
- hydrolysis of the enamine back to a ketone
The reaction is named after its inventor: Gilbert Stork.
In a special case of this reaction type it is also possible to alkylate ketones or aldehydes with alkyl halides as less reactive electrophiles [2]:
In this method a carbonyl compound is converted to an imine by alkylimino-de-oxo-bisubstitution with a primary amine. The imine is then reacted with an Grignard reagent to the corresponding magnesium salt to an intermediate capable of displacing a halide. Hydrolysis once again yields the alkylated ketone.
References
- ↑ McMurry, John (2003-03-21). Organic Chemistry (Hardcover)
|format=requires|url=(help) (6th edition ed.). Belmont, CA: Thomson-Brooks/Cole. ISBN 0-534-38999-6. - ↑ A New Method for the Alkylation of Ketones and Aldehydes: the C-Alkylation of the Magnesium Salts of N-Substituted Imines Gilbert Stork and Susan R. Dowd J. Am. Chem. Soc.; 1963; 85(14) pp 2178 - 2180; doi:10.1021/ja00897a040