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I came across the following reaction, whose mechanism is said to involve a 1,2-alkyl migration with a double inversion in configuration. The reagents used were nitrous acid (generated in situ) followed by acidic hydrolysis.

I got a hint that the first step involves the reaction of nitrous acid with the NH group. But, I cannot understand how the reaction works. Could anyone explain the mechanism?

User AndyWilson
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1 Answer

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Final answer:

The reaction in question involves a nucleophilic substitution mechanism with organic compounds, possibly leading to a 1,2-alkyl migration with double inversion. It begins with the reaction of nitrous acid forming a diazonium intermediate, which then undergoes nucleophilic attack and group migration. Acid serves as a catalyst, speeding up hydrolysis and substitution steps.

Step-by-step explanation:

The process you are asking about is a reaction mechanism that involves nucleophilic substitution with a 1,2-alkyl migration and double inversion of configuration. This mechanism starts with the reaction of nitrous acid with an amino group (NH), which typically leads to the formation of a diazonium intermediate.

This intermediate can undergo various reactions, including nucleophilic attack and subsequent migration of alkyl groups, resulting in the change of configuration if a chiral center is involved.

The typical nucleophilic substitution mechanism for primary alkyl halides involves a nucleophile attacking the carbon of the alkyl halide, with inversion of stereochemistry at that carbon. In the context of the reaction with nitrous acid and acidic hydrolysis, the hydroxyl group originating from hydrolysis can act as nucleophile attacking the diazonium ion. Acid in these types of reactions often serves as a catalyst, helping to speed up certain steps in the mechanism.

Nucleophilic acyl substitution reactions proceed through the nucleophilic addition of a nucleophile to an acyl group containing substrate, followed by elimination. The reaction rate can be enhanced by using a base to deprotonate the nucleophile, making it more reactive.

User Andeart
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