Acid DerivativesAldehydes and Ketones

Nitriles to Esters

There are a few ways to convert nitriles to esters. Let’s start with the Pinner reaction, which, although not commonly highlighted in textbooks, is a direct and efficient method for this transformation.

 

Pinner Reaction for Converting Nitriles to Esters

The reaction starts with protonation of the nitrogen, thus making the carbon of the nitrile more electrophilic. This facilitates the nucleophilic addition of alcohols, which leads to the formation of an imidic salt intermediate. From here, the reaction proceeds through a standard imine hydrolysis, similar to what we saw in the chapter on aldehydes and ketones. Water attacks the imine carbon, leading to its breakdown and forming the final ester product.

 

 

Let’s also mention a couple of interesting approaches for converting nitriles to esters.

 

Nitriles to Esters via Carboxylic Acids


We know that nitriles can be hydrolyzed under acidic or basic conditions to carboxylic acids:

 

 

Once we have the carboxylic acid, we can either subject it to a Fischer esterification or convert it into a carboxylate salt and use it for an SN2 substitution with an appropriate alkyl halide.

 

 

Nitriles to Esters with Ketones

You might remember that nitriles react with Grignard and organolithium reagents to form ketones. Once we have the ketone, we can use the Baeyer-Villiger oxidation to convert it into an ester:

 

 

Check the linked article for more details on the mechanisms of all the reactions mentioned in this post, which is dedicated to summarizing strategies for converting nitriles to esters.

 

Organic Chemistry Reaction Maps

Never struggle again to figure out how to convert an alkyl halide to an alcohol, an alkene to an alkyne, a nitrile to a ketone, a ketone to an aldehyde, and more! The comprehensive powerfull Reaction Maps of organic functional group transformations are here!

 

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