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Photocatalysis Enables Chemodivergent Radical Polar Crossover: Ritter-Type Amidation vs Heck-Type Olefin
Mattia Lepori1, Cassie Pratley1, Indrasish Dey1
1Fakultät für Chemie und Pharmazie, Universität Regensburg, Universitatsstraße 31, Regensburg, 93053, Germany.
Chemistry (Weinheim an Der Bergstrasse, Germany)
|March 18, 2025
Summary
This study introduces a novel photoredox-catalyzed method for alkene difunctionalization, enabling the efficient synthesis of complex molecules via Ritter-type carboamidation and Heck-type carbofunctionalization reactions.
Area of Science:
- Organic Chemistry
- Catalysis
- Synthetic Methodology
Background:
- Three-component alkene difunctionalization reactions are crucial for rapidly building molecular complexity.
- Simultaneous introduction of two distinct functional groups into the C═C bond is highly desirable.
Purpose of the Study:
- To develop a photoredox-catalyzed Ritter-type carboamidation of styrenes using non-stabilized primary radicals.
- To achieve chemoselective Heck-type products by altering olefin acceptors.
- To explore photocatalytic chemodivergent radical polar crossover for synthesizing trisubstituted alkenes.
Main Methods:
- Photoredox catalysis
- Utilizing carboxylic acid-derived redox-active esters for radical generation
- Employing electronically diverse styrenes and 1,1-diarylolefins as substrates
- Mechanistic studies and Density Functional Theory (DFT) calculations
Main Results:
- Successful Ritter-type carboamidation of styrenes with primary radicals.
- Chemoselective synthesis of Heck-type products by switching olefin acceptors.
- Synthesis of various trisubstituted alkenes via chemodivergent radical polar crossover.
- Demonstrated scalability of both Ritter-type and Heck-type reactions up to 4 mmol scale in batch and flow.
Conclusions:
- The developed methodology offers a versatile platform for alkene difunctionalization.
- Product switchability between Ritter-type and Heck-type pathways is achieved and understood.
- The reactions are scalable and demonstrate significant synthetic utility.
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