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Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions
Published on: March 20, 2014
Proximal and Remote Twofold Stereogenicity Enabled by Rhodium-Catalyzed and Phosphine-Directed Murai Reaction.
Junwei Li1, Qiao Li1, Zeqin Zhao1
1Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education and School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an 710062, China.
Journal of the American Chemical Society
|June 23, 2026
Summary
This study introduces a novel rhodium-catalyzed Murai reaction integrating asymmetric catalysis and olefin chain-walking. The method achieves high regio- and stereoselectivity in aromatic C-H bond functionalization, creating valuable chiral compounds.
Area of Science:
- Organic Chemistry
- Catalysis
- Asymmetric Synthesis
Background:
- The Murai reaction inserts arene C-H bonds into alkenes, typically yielding 1,2-selectivity.
- Olefin chain-walking allows remote functionalization but often requires external hydride sources.
- Integrating asymmetric catalysis with olefin chain-walking for enhanced regio- and stereoselectivity remains a significant challenge.
Purpose of the Study:
- To develop a rhodium-catalyzed Murai reaction that combines asymmetric catalysis with olefin chain-walking.
- To expand the scope of arene C-H functionalization by controlling regio- and stereoselectivity.
- To synthesize value-added aromatic compounds with proximal and distal axial and central chirality.
Main Methods:
- Rhodium-catalyzed Murai reaction utilizing arenes with an ortho-diarylphosphino directing group.
- Employing amide-functionalized terminal alkenes, including long-chained and α-substituted acrylamides.
- Optimization of additives and a chiral phosphoramidite ligand to control catalytic activity and selectivity.
Main Results:
- Hydroarylation of long-chained olefin-amides resulted in branched products with Markovnikov selectivity and proximal chirality.
- 1,2-Hydroarylation of α-substituted acrylamides yielded products with anti-Markovnikov selectivity and distal chirality.
- The reaction proceeded with high enantioselectivity, excellent diastereoselectivity (>20:1 d.r.), and 100% atom economy.
- The synthesized products demonstrated utility as chiral ligands in asymmetric C-C coupling reactions.
Conclusions:
- A novel catalytic system for asymmetric Murai reaction coupled with olefin chain-walking has been established.
- This method provides access to chiral aromatic compounds with controlled regio- and stereochemistry.
- The developed chiral products show potential as ligands in further asymmetric transformations.
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