Deprotonative Single-Electron Oxidation as a General and Controllably Selective Platform for Benzylic C-H...

Area of Science:

• Organic Chemistry
• Radical Chemistry

Background:

• Benzyl radical generation is crucial for C-H functionalization.
• Existing methods often lack selectivity or functional group tolerance.

Purpose of the Study:

• To develop a new strategy for benzyl radical generation.
• To achieve improved selectivity and functional group tolerance in C-H functionalization.

Main Methods:

• Consecutive deprotonation using an HMDS base and single-electron oxidation.
• Capture of the benzyl carbanionic intermediate with TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl).

Main Results:

• The method enables selective radical coupling, avoiding dimerization.
• High functional group tolerance and site-selectivity control were achieved.
• Applicable to alkylarenes with high oxidation potentials and sensitive functional groups.

Conclusions:

• This protocol offers a versatile approach for benzyl-OTMP unit installation.
• Tunable site-selectivity can be achieved by adjusting base strength.
• Enhances benzylic C-H diversification for complex molecule synthesis.