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Ambident Nucleophiles - Examples, Reactions and Conditions

Learning Objective: To study the ambident nucleophiles and how and from which end they attack the substrates to undergo chemical reactions.

Skill Level - Intermediate

Prerequisites: 

 

Chapter: Fundamentals of Organic Reactions

Sub-topic: Nucleophiles

 

Author's Note: Once we expose ourselves to nucleophiles and their role in reactions, it becomes easier to understand another subset, ambident nucleophiles. Why?

Displacement reactions commonly use cyanide or nitrite for functional group interconversions. Nucleophile reagents like these have two ends that can attack the substrate, leading to the formation of two products, one desired and the other not so much. So, knowing what to use and when and how to tweak reactions to get the desired outcome becomes highly important. Therefore, I have included ambident nucleophiles in this chapter on nucleophiles. I have shown what they are, how they react, and what conditions are required for their preferential attack. 

Mnemonics are also included to aid memory.

Ambident Nucleophiles

In some nucleophiles, the donating pair of electrons is present in two or more atoms of the same molecule. This provides the nucleophile two ways to approach the substrate's electron-deficient or electrophilic site (here, R δ+).

 

Such nucleophiles with two or more sites to donate electrons and initiate a chemical reaction are called ambident nucleophiles.

Some examples of ambident nucleophiles are- cyanide (CN-), nitrite (ONO-), Phenoxide ions (C6H5-O-), diketones (R-CO-CHR-CO-R), etc.

Ambident nucleophilicity could be as a result of....

 

The nature of the substrate in ambident nucleophile

The ambident nucleophile has two ends, one more electronegative than the other. In a displacement reaction with the ambident nucleophile, the side that will attack the substrate will depend on ....

 

Influence of the Positive Counter Ions in Ambident Nucleophile

The metal ions like Ag, Hg, Cu, Na, K, Li, etc. are the usual positive counterion of the ambident nucleophiles- for example, ....

 

Effect of Solvent on the Ambident Nucleophile

The more electronegative end of the ambident nucleophile is free when the solvent molecule doesn’t surround it....

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The key takeaway here is that the attack by the electronegative end of the ambident nucleophile is not the only criterion determining the SN1 or SN2 route. The other factors like the ....

Subscribe to read about the ambident nucleophiles and how to use them in reactions for functional group interconversions.

 

Fundamentals of Organic Reactions
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Drawing Organic Structures

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Functional Groups in Organic Chemistry

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Reactive Intermediates

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