Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Enhancing Substrate–Metal Catalyst Affinity via Hydrogen Bonding: Pd(II)-Catalyzed β-C(sp3)–H Bromination of Free Carboxylic Acids

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.3c04223· OSTI ID:2339620
 [1];  [2];  [3];  [4];  [3];  [2];  [2];  [2];  [2];  [4];  [4];  [3];  [2]
  1. The Scripps Research Institute, La Jolla, CA (United States); University of California San Diego
  2. The Scripps Research Institute, La Jolla, CA (United States)
  3. University of California Los Angeles, CA (United States)
  4. University of California, San Diego, La Jolla, CA (United States)
+ Show Author Affiliations
Achieving sufficient substrate-metal catalyst affinity is a fundamental challenge for developing synthetically useful C–H activation reactions of weakly coordinating native substrates. While hydrogen bonding has been harnessed to bias site selectivity in existing C(sp2)–H activation reactions, the potential for designing catalysts with hydrogen bond donors (HBDs) to enhance catalyst substrate affinity, and thereby facilitate otherwise unreactive C(sp3)–H activation, remains to be demonstrated. Herein, we report the discovery of a ligand scaffold containing a remote amide motif that can form a favorable meta-macrocyclic hydrogen bonding interaction with the aliphatic acid substrate. The utility of this ligand scaffold is demonstrated through the development of an unprecedented C(sp3)–H bromination of α-tertiary and α-quaternary free carboxylic acids, which proceeds in exceedingly high mono-selectivity. Furthermore, the geometric relationship of the NHAc hydrogen bond donor and the coordinating quinoline ligand is crucial for forming the meta-macrocyclophane-like hydrogen bonding interaction, providing a guideline for the future design of catalysts employing secondary interactions.
Research Organization:
University of California, San Diego, La Jolla, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0009376
OSTI ID:
2339620
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 30 Vol. 145; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (48)

Palladium‐Catalyzed Asymmetric Iodination of Unactivated CH Bonds under Mild Conditions journal March 2005
Tuning a P450 Enzyme for Methane Oxidation journal March 2011
Synergistic Palladium‐Catalyzed C(sp3)H Activation/C(sp3)O Bond Formation: A Direct, Step‐Economical Route to Benzolactones journal October 2011
Enantiotopos‐Selective CH Oxygenation Catalyzed by a Supramolecular Ruthenium Complex journal November 2014
Ligand‐Enabled PdII‐Catalyzed Iterative γ‐C(sp3)−H Arylation of Free Aliphatic Acid journal August 2019
Direct β‐ and γ‐C(sp3)−H Alkynylation of Free Carboxylic Acids** journal October 2020
Enzymatic Late‐Stage Modifications: Better Late Than Never journal March 2021
β‐ andγ‐C(sp3)−H Heteroarylation of Free Carboxylic Acids: A Modular Synthetic Platform for Diverse Quaternary Carbon Centers journal January 2023
Distal meta-alkenylation of formal amines enabled by catalytic use of hydrogen-bonding anionic ligands journal April 2023
Charge-controlled Pd catalysis enables the meta-C–H activation and olefination of arenes journal April 2023
From Pd(OAc) 2 to Chiral Catalysts: The Discovery and Development of Bifunctional Mono-N-Protected Amino Acid Ligands for Diverse C–H Functionalization Reactions journal March 2020
Transition Metal Catalysis Controlled by Hydrogen Bonding in the Second Coordination Sphere journal May 2022
Use of Bromine and Bromo-Organic Compounds in Organic Synthesis journal May 2016
Palladium-Catalyzed Transformations of Alkyl C–H Bonds journal December 2016
Bidentate Directing Groups: An Efficient Tool in C–H Bond Functionalization Chemistry for the Expedient Construction of C–C Bonds journal January 2020
“Magic Chloro”: Profound Effects of the Chlorine Atom in Drug Discovery journal April 2023
Discovery of Asciminib (ABL001), an Allosteric Inhibitor of the Tyrosine Kinase Activity of BCR-ABL1 journal August 2018
Direct β-C(sp3)–H Acetoxylation of Aliphatic Carboxylic Acids journal August 2019
Palladium-Catalyzed meta-Selective C–H Functionalization by Noncovalent H-Bonding Interaction journal August 2021
C–H Activation: Toward Sustainability and Applications journal February 2021
Bidentate, Monoanionic Auxiliary-Directed Functionalization of Carbon–Hydrogen Bonds journal March 2015
Pivotal Role of Water in the Mechanism of P450BM-3 † journal November 2001
Nature's Inventory of Halogenation Catalysts:  Oxidative Strategies Predominate journal June 2006
Palladium-Catalyzed Ligand-Directed C−H Functionalization Reactions journal February 2010
Palladium-Catalyzed Methylation and Arylation of sp2 and sp3 C−H Bonds in Simple Carboxylic Acids journal March 2007
Synthesis of β-, γ-, and δ-Lactams via Pd(II)-Catalyzed C−H Activation Reactions journal October 2008
Ligand-Enabled Monoselective β-C(sp3)–H Acyloxylation of Free Carboxylic Acids Using a Practical Oxidant journal March 2020
Achieving Site-Selectivity for C–H Activation Processes Based on Distance and Geometry: A Carpenter’s Approach journal May 2020
Late-Stage β-C(sp3)–H Deuteration of Carboxylic Acids journal July 2021
Ligand-Enabled Pd(II)-Catalyzed β-Methylene C(sp3)–H Arylation of Free Aliphatic Acids journal November 2022
Ligand-Enabled Pd(II)-Catalyzed Bromination and Iodination of C(sp 3 )–H Bonds journal April 2017
Noncovalent Interactions in Ir-Catalyzed C–H Activation: L-Shaped Ligand for Para-Selective Borylation of Aromatic Esters journal June 2017
Ligand-Enabled β-C(sp3)–H Olefination of Free Carboxylic Acids journal July 2018
Sulfoximine Assisted Pd(II)-Catalyzed Bromination and Chlorination of Primary β-C(sp3)–H Bond journal September 2014
Exploiting non-covalent π interactions for catalyst design journal March 2017
A meta-selective C–H borylation directed by a secondary interaction between ligand and substrate journal August 2015
Pd-catalysed ligand-enabled carboxylate-directed highly regioselective arylation of aliphatic acids journal April 2017
The structure of the cytochrome p450BM-3 haem domain complexed with the fatty acid substrate, palmitoleic acid journal February 1997
Lactonization as a general route to β-C(sp3)–H functionalization journal December 2019
Mono- and binuclear cyclometallated palladium(ii) complexes containing bridging (N,O-) and terminal (N-) imidate ligands: Air stable, thermally robust and recyclable catalysts for cross-coupling processes journal January 2004
P450 BM3 (CYP102A1): connecting the dots journal January 2012
Auxiliary-assisted palladium-catalyzed halogenation of unactivated C(sp3)–H bonds at room temperature journal January 2016
Harnessing non-covalent interactions to exert control over regioselectivity and site-selectivity in catalytic reactions journal January 2017
Pd-catalyzed cross-coupling reactions of alkyl halides journal January 2011
Attractive noncovalent interactions in asymmetric catalysis: Links between enzymes and small molecule catalysts journal October 2010
Molecular Recognition in the Selective Oxygenation of Saturated C-H Bonds by a Dimanganese Catalyst journal June 2006
Enantioselective remote C–H activation directed by a chiral cation journal March 2020
Ligand-controlled divergent dehydrogenative reactions of carboxylic acids via C–H activation journal December 2021

Similar Records

Understanding the Activity and Enantioselectivity of Acetyl-Protected Aminoethyl Quinoline Ligands in Palladium-Catalyzed β-C(sp3)–H Bond Arylation Reactions
Journal Article · Sat Sep 28 20:00:00 EDT 2019 · Journal of the American Chemical Society · OSTI ID:1594499
Hydrodenitrogenation of benzo(f)quinoline and benzo(h)quinoline over a sulfided NiO-MoO sub 3 /. gamma. -Al sub 2 O sub 3 catalyst
Journal Article · Mon Aug 01 00:00:00 EDT 1988 · Journal of Catalysis; (USA) · OSTI ID:6583735
Modulating solvation interactions of deep eutectic solvents formed by ammonium salts and carboxylic acids through varying the molar ratio of hydrogen bond donor and acceptor
Journal Article · Wed Feb 17 19:00:00 EST 2021 · Journal of Chromatography · OSTI ID:1773342

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Halogenation
Ligands
Macrocycles
Noncovalent interactions
Organic acids