Functionalized Allyl Aryl Ether Synthesis from Benzoic Acids Using a Dearomatization and Decarboxylative Allylation...

Area of Science:

• Organic Chemistry
• Synthetic Chemistry

Background:

• Benzoic acids are common starting materials in organic synthesis.
• Allyl aryl ethers are valuable intermediates in various chemical applications.
• Existing methods for synthesizing substituted allyl aryl ethers can be limited in scope or efficiency.

Purpose of the Study:

• To develop a novel synthetic strategy for preparing substituted allyl aryl ethers.
• To explore the utility of a dearomatization and decarboxylative allylation (DcA) reaction.
• To demonstrate the application of this method in synthesizing complex molecules like multisubstituted phenols and dihydroplicatin B derivatives.

Main Methods:

• A two-step process involving dearomatization of benzoic acids to form ketoesters.
• Palladium-catalyzed decarboxylative allylation (DcA) of the ketoesters.
• Integration of the DcA reaction with a Claisen rearrangement for phenol synthesis.

Main Results:

• Successfully synthesized a variety of functionalized allyl aryl ethers from benzoic acids.
• Demonstrated the formation of alkylated 2,5-cyclohexadienyl ketoesters as key intermediates.
• Achieved the synthesis of multisubstituted phenols and a dihydroplicatin B derivative.

Conclusions:

• The presented dearomatization and decarboxylative allylation (DcA) strategy offers an efficient route to substituted allyl aryl ethers.
• The method is versatile and can be extended to synthesize complex phenolic compounds.
• This work expands the synthetic toolbox for accessing valuable organic molecules.