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Published November 6, 2020 | Supplemental Material
Journal Article Open

Insights into the Role of Transient Chiral Mediators and Pyridone Ligands in Asymmetric Pd-Catalyzed C–H Functionalization

Abstract

Mechanistic investigations uncover a novel role for 2-pyridone ligands and interrogate the origin of enantioselectivity in the (+)-norbornene-mediated Pd-catalyzed meta-C(aryl)–H functionalization of diarylmethylamines. Observations from kinetic analysis in concert with in situ ¹⁹F NMR monitoring allow us to propose that the pyridone ligand plays a role in enhancing the rate- and enantio-determining insertion of an arylpalladium species into a chiral norbornene derivative. The unprecedented features of 2-pyridone ligands in asymmetric 1,2 migratory insertion, and norbornene as a transient chiral mediator in relay chemistry, provide new insights into this ligand scaffold for future developments in stereoselective transition-metal-catalyzed C–H functionalization.

Additional Information

© 2020 American Chemical Society. Received: July 31, 2020; Published: September 29, 2020. This work was supported by the National Science Foundation under Chemical Innovation Center for Selective C–H Functionalization (CHE-1700982) and by the Center for Rapid Online Analysis of Reactions (ROAR) at Imperial College London [EPSRC, EP/R008825/1]. Dr. Jason Chen, Brittany Sanchez, and Emily Sturgell of the Scripps Automated Synthesis Center are acknowledged for valuable guidance and support on analytical methods. Prof. Mimi Hii, Dr. Benjamin Deadman, and Dr. Paola Ferrini are acknowledged for helpful discussion and support on analytical methods. The authors declare no competing financial interest.

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