Remote 1,5-Difunctionalization of Alkenes via a Sulfinyl-Smiles Rearrangement and Vinylcyclopropane Ring-Opening...

Area of Science:

• Organic Chemistry
• Catalysis
• Asymmetric Synthesis

Background:

• Enantioselective remote difunctionalization of alkenes via radical pathways is challenging due to poor stereocontrol.
• Existing methods often struggle with site selectivity and stereochemical outcomes in open-shell processes.

Purpose of the Study:

• To develop a novel photoredox-catalyzed method for asymmetric remote 1,5-difunctionalization of alkenes.
• To achieve precise site selectivity and high enantioselectivity in radical cascade reactions.

Main Methods:

• Utilized photoredox catalysis combined with the strain-release ring opening of vinylcyclopropanes.
• Incorporated a stereocontrolled sulfinyl-Smiles rearrangement for radical cascade.
• Bypassed kinetically disfavored hydrogen atom transfer pathways.

Main Results:

• Achieved efficient and enantioselective remote 1,5-difunctionalization of alkenes.
• Demonstrated accommodation of both sulfur- and carbon-centered radicals.
• Provided access to enantioenriched α-aryl γ,δ-unsaturated amides and derivatives.

Conclusions:

• The developed method offers a powerful strategy for asymmetric synthesis of complex molecules.
• Enables mild and efficient access to valuable chiral building blocks with high stereocontrol.