Group 14 Elements Hetero-Difunctionalizations via Nickel-Catalyzed Electroreductive Cross-Coupling

Area of Science:

• Organic Chemistry
• Catalysis
• Electrochemistry

Background:

• Difunctionalization of unsaturated bonds is key for molecular complexity.
• Hetero-difunctionalization of unsaturated bonds is less explored due to selectivity challenges.
• Introducing two similar atoms from the same group across unsaturated bonds is particularly difficult.

Purpose of the Study:

• To develop a novel catalytic method for hetero-difunctionalization of 1,3-enynes.
• To achieve selective introduction of group 14 elements across unsaturated bonds.
• To establish a mild, selective, and general protocol for silyl-, germanyl-, and stannyl-alkylation.

Main Methods:

• Nickel-catalyzed three-component reductive coupling.
• Electrochemical synthesis.
• Utilizing 1,3-enynes, group 14 element precursors (chlorosilanes, chlorogermans, chlorostannanes), and alkyl bromides.

Main Results:

• Successful silyl-, germanyl-, and stannyl-alkylation of 1,3-enynes.
• Demonstrated generality with various substrates including aryl/alkyl-substituted enynes and different types of alkyl bromides.
• Achieved mild and selective reaction conditions.

Conclusions:

• The developed electroreductive coupling is a powerful new method for group 14 element hetero-difunctionalization.
• This protocol offers a versatile approach to synthesize complex molecules containing silicon, germanium, or tin.
• The method overcomes previous limitations in chemo-, regio-, and stereoselectivity for such transformations.