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

Hill, David E. and Yu, Jin-Quan and Blackmond, Donna G. (2020) Insights into the Role of Transient Chiral Mediators and Pyridone Ligands in Asymmetric Pd-Catalyzed C–H Functionalization. Journal of Organic Chemistry . ISSN 0022-3263. (In Press) https://resolver.caltech.edu/CaltechAUTHORS:20200930-133707825

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Abstract

Mechanistic investigations uncover a novel role for 2-pyridone ligands and interrogate the origin of enantiose-lectivity 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 me-diator in relay chemistry, provide new insights into this ligand scaffold for future developments in stereoselective transition-metal catalyzed C–H functionalization.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acs.joc.0c01798DOIArticle
ORCID:
AuthorORCID
Hill, David E.0000-0002-7326-2509
Yu, Jin-Quan0000-0003-3560-5774
Blackmond, Donna G.0000-0001-9829-8375
Additional Information:© 2020 American Chemical Society. Publication Date: September 29, 2020. This is work was supported by the National Science Foundation under the Center for Chemical Innovation Center for Selective C−H Functionalization (CHE-1700982) and by the Centre for Rapid Online Analysis of Reactions (ROAR) at Imperial College London [EPSRC, EP/R008825/1]. Dr. Jason Chen, Brittaney Sanchez, and Emily Strugell 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.
Funders:
Funding AgencyGrant Number
NSFCHE-1700982
Imperial College LondonUNSPECIFIED
Engineering and Physical Sciences Research Council (EPSRC)EP/R008825/1
Record Number:CaltechAUTHORS:20200930-133707825
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20200930-133707825
Official Citation:Insights into the Role of Transient Chiral Mediators and Pyridone Ligands in Asymmetric Pd-Catalyzed C–H Functionalization. David E. Hill, Jin-Quan Yu, and Donna G Blackmond. The Journal of Organic Chemistry. Just Accepted Manuscript; DOI: 10.1021/acs.joc.0c01798
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:105692
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:30 Sep 2020 20:48
Last Modified:30 Sep 2020 20:48

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