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Di-Palladium Complexes are Active Catalysts for Mono-N-Protected Amino Acid Accelerated Enantioselective C-H Functionalization

preprint
revised on 10.02.2019 and posted on 11.02.2019 by Joseph Gair, Brandon E. Haines, Alexander S. Filatov, Djamaladdin G. Musaev, Jared C. Lewis
The role of mono-protected amino acid (MPAA) ligands in accelerating enantioselective cyclopalladation and palladium catalyzed C-H func-tionalization was investigated using kinetic, spectroscopic, and computational methods. Single crystal X-ray diffraction and NMR spectroscopy demonstrate that MPAA ligands bind catalytically competent di-palladium complexes as bridging carboxylates. The catalytic relevance of the observed di-palladium species was evaluated by kinetic analysis. The kinetic method of continuous variation demonstrated that a complex contain-ing a single MPAA-bridged di-palladium core (Pd2(MPAA)1) is an active catalyst for the reactions studied. The experimental studies are con-sistent with density functional theory calculations that indicate enantioinduction can be achieved by a single MPAA ligand bridging a di-palladium catalyst through secondary sphere hydrogen-bonding interactions that lower the barrier to C-H activation of the major enantiomer.

Funding

CHE-1205646

DGE-1144082

History

Email Address of Submitting Author

jcl3@iu.edu

Institution

Indiana University

Country

USA

ORCID For Submitting Author

0000-0003-2800-8330

Declaration of Conflict of Interest

no conflict of interest

Version Notes

Added PDF copy of SI

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