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Understanding the Activity and Enantioselectivity of Acetyl-Protected Aminoethyl Quinoline Ligands in Palladium-Catalyzed β-C(sp3)–H Bond Arylation Reactions

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.9b06746· OSTI ID:1594499
 [1];  [2];  [3];  [3];  [2];  [3]
  1. Univ. of California, San Diego, La Jolla, CA (United States); UCSD
  2. The Scripps Research Inst., La Jolla, CA (United States)
  3. Univ. of California, San Diego, La Jolla, CA (United States)
+ Show Author Affiliations
Chiral acetyl-protected aminoalkyl quinoline (APAQ) ligands were recently discovered to afford highly active and enantiose-lective palladium catalysts for the arylation of methylene C(sp3)-H bonds, and herein, we investigate the origins of these heightened properties. Unprecedented amide-bridged APAQ-Pd dimers were predicted by DFT calculations and were con-firmed by single crystal X-ray diffraction studies. Comparison of structural features between APAQ-Pd complexes and an acetyl-protected aminoethyl pyridine APAPy-Pd complex strongly suggests that the high activity of the former originates from the presence of the quinoline ring which slows the formation of the off-cycle palladium dimer. Furthermore, steric topographic maps for a representative subset of monomeric, monoligated palladium complexes allowed us to draw a unique parallel between the 3-dimensional structures of these catalysts and their reported asymmetric induction in β-C(sp3)-H bond arylation reactions. Lastly, cooperative non-covalent interactions present between the APAQ ligand and the substrate were identified as a crucial factor for imparting selectivity between chemically equivalent methylenic C(sp3)-H bonds prior to con-certed metalation deprotonation activation.
Research Organization:
Univ. of California, San Diego, La Jolla, CA (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0009376
OSTI ID:
1594499
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 42 Vol. 141; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Arylation
Ligands
Oligomers
Palladium
Quinolines