Oxymercuration reaction

Oxymercuration-demercuration is a two-step organic reaction that converts an alkene into a neutral alcohol by the addition of water, in the presence of mercuric acetate and a reducing agent. This reaction is an essential method in organic chemistry for the hydration of alkenes without the addition of acidic conditions, which can lead to rearrangements and other side reactions. The process is particularly useful for the synthesis of alcohols in a regioselective manner.

Mechanism

The oxymercuration-demercuration reaction proceeds via a three-step mechanism:

1. Oxymercuration: The alkene reacts with mercuric acetate (acetic acid and mercury) in an aqueous solution, forming a mercurinium ion intermediate. This step is facilitated by the electrophilic nature of mercury, which forms a bond with the less substituted carbon of the alkene, leading to the formation of a cyclic mercurinium ion.
2. Nucleophilic attack: Water, acting as a nucleophile, attacks the more substituted carbon atom of the mercurinium ion. This step is regioselective, favoring the formation of the more stable carbocation intermediate.
3. Demercuration: The addition of a reducing agent, such as sodium borohydride (NaBH₄), leads to the removal of the mercury group and the formation of the alcohol product. This step restores the carbon skeleton to a neutral state without the incorporation of mercury into the final product.

Advantages

The oxymercuration-demercuration reaction offers several advantages over direct acid-catalyzed hydration of alkenes:

• Regioselectivity: The reaction typically follows Markovnikov's rule, where the hydroxyl group attaches to the more substituted carbon atom, allowing for predictable product formation.
• Mild Conditions: The reaction avoids the use of strong acids, minimizing the risk of carbocation rearrangements and other side reactions.
• Functional Group Tolerance: The conditions are generally mild enough to be compatible with a variety of functional groups, making the reaction applicable to complex molecule synthesis.

Applications

Oxymercuration-demercuration is widely used in the synthesis of complex organic molecules, including natural products and pharmaceuticals. Its ability to selectively introduce a hydroxyl group into the molecular framework of alkenes makes it a valuable tool in the arsenal of organic chemists.

Limitations

Despite its advantages, the oxymercuration-demercuration reaction has limitations:

• Toxicity: Mercury compounds are toxic and require careful handling and disposal.
• Cost: Mercury reagents can be expensive and may not be suitable for large-scale applications.

See Also

• Hydration reaction
• Markovnikov's rule
• Organic synthesis
• Regioselectivity

References

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  Oxymercuration-reduction reaction mechanism

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  Oxymercuration reaction mechanism

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  Stereocontrol in oxymercuration

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  Regiocontrol in oxymercuration

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  Oxymercuration reaction

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  Oxymercuration of vinyl ethers

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  Mechanism of oxymercuration of vinyl ethers