Umpolung-Enabled Divergent Dearomative Carbonylations

Area of Science:

• Organic Chemistry
• Catalysis
• Synthetic Methodology

Background:

• Dearomative functionalizations transform flat aromatic compounds into complex 3D structures.
• Simple arenes are challenging substrates due to high aromatic stabilization energy.
• Existing methods for arene dearomatization are limited.

Purpose of the Study:

• To develop a novel dearomative strategy for simple arenes.
• To enable sequential addition of two nucleophiles to arene π-bonds.
• To achieve divergent dearomative carbonylation reactions.

Main Methods:

• Umpolung of chromium-arene complexes.
• Sequential addition of nucleophiles to benzene derivatives.
• Carbonylation reactions under CO-gas-free conditions.

Main Results:

• Modular synthesis of functionalized esters and amides.
• Toleration of diverse nucleophiles, alcohols, and amines.
• Tunable synthesis of 1,3- and 1,4-cyclohexadienes.
• Construction of carbon quaternary centers.

Conclusions:

• The developed dearomatization strategy offers versatile access to complex molecules.
• The method demonstrates significant synthetic utility through late-stage modifications.
• The findings open new avenues for synthesizing challenging and bioactive compounds.