Corey–House synthesis

Corey–House synthesis, also known as the Corey–House–Posner–Whitesides reaction, is a series of chemical reactions utilized in organic chemistry for the synthesis of alkanes. It is named after the American chemists Elias James Corey, William S. House, William D. Posner, and George M. Whitesides who developed the method. This reaction is significant for its ability to form carbon-carbon (C-C) bonds, enabling the construction of complex molecular structures from simpler precursors.

Overview

The Corey–House synthesis involves the reaction of an alkyl halide with lithium to form an alkyl lithium reagent, which is then reacted with a copper(I) halide to produce a lithium dialkylcuprate. This organocopper compound is then reacted with a second alkyl halide, leading to the formation of a new alkane with a carbon-carbon bond joining the two alkyl groups. The general reaction scheme can be summarized as follows:

1. R-X + 2 Li → R-Li + LiX 2. R-Li + CuX → R_2CuLi + LiX 3. R_2CuLi + R'-X → R-R' + CuX + LiX

where R and R' represent alkyl or aryl groups and X represents a halogen.

Mechanism

The mechanism of the Corey–House synthesis involves several key steps. The first step is the formation of an alkyl lithium compound from an alkyl halide and lithium metal. This is followed by the transmetalation step, where the alkyl group is transferred to copper(I) halide to form a lithium dialkylcuprate. The final step is the nucleophilic substitution of a second alkyl halide by the dialkylcuprate, forming the desired alkane.

Applications

The Corey–House synthesis is widely used in organic synthesis for the construction of complex molecules. It is particularly valuable for its ability to form carbon-carbon bonds in a controlled manner, allowing for the synthesis of a wide range of alkanes that are difficult to obtain by other methods. This reaction has found applications in the synthesis of natural products, pharmaceuticals, and other biologically active compounds.

Limitations

Despite its utility, the Corey–House synthesis has some limitations. The reaction conditions can be sensitive to the nature of the substrates, and certain functional groups may interfere with the reaction. Additionally, the use of organolithium and organocopper reagents requires careful handling due to their reactivity and potential toxicity.

See Also

• Organometallic chemistry
• Nucleophilic substitution
• Transmetalation
• Alkyl halide
• Lithium
• Copper(I) halide

References

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  Diagram of the Corey–House synthesis reaction mechanism.

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  Illustration of the Kochi-Schlosser coupling reaction.

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  Photograph of a U.S. Marine Corps training exercise.