Led by Justin Du Bois
The ability to exact control over product selectivity in molecules possessing multiple, disparate C–H bonds is arguably the defining challenge for C–H functionalization research. Over the past several years, CCHF researchers have had a leading role in establishing intrinsic patterns of C–H bond reactivity and in demonstrating the influence of substrate structure and functional group substitution on reaction outcomes.
Differential rates of C–H functionalization are evident in all molecules, but such dissimilarities are typically small and often insufficient to bias reactions towards a single product outcome. Accordingly, the ultimate objective in C–H functionalization research is to control product selectivity (i.e., chemo-, regio-, stereo-) through judicious reagent and catalyst selection. Within the collaborative environment of CCHF, the need for such solutions has become even more acute, as substrates designed by Center members en route to natural products and active pharmaceutical ingredients are ever-more complex.
A primary goal of CCHF is to produce a ‘guidebook’ for identifying catalyst, reagent(s), and reaction conditions that would enable specific control over site- and stereoselectivity in all types of C–H functionalization reactions, thus empowering chemists who wish to employ such technologies for streamlining chemical synthesis and/or for the rapid structural diversification of chemical entities. To realize this ambitious challenge, the Center is leveraging the talents of multiple research labs that span analytical, mechanistic, biochemical, inorganic, synthetic, materials, and theoretical chemistry along with chemical engineering.
01/2019
Synthesis and Catalytic Properties of Dirhodium Paddlewheel Complexes with Tethered, Axially Coordinating Thioether Ligands
RESEARCH
01/2019
New chromium, molybdenum, and cobalt complexes of the chelating esp ligand
RESEARCH
12/2018
Desymmetrization of cyclohexanes by site- and stereoselective C–H functionalization
RESEARCH
09/2018
Intermolecular Allylic C−H Etherification of Internal Olefins
RESEARCH
09/2018
Comparison of Reactivity and Enantioselectivity between Chiral Bimetallic Catalysts: Bismuth–Rhodium- and Dirhodium-Catalyzed Carbene Chemistry
RESEARCH
08/2018
Design of catalysts for site-selective and enantioselective functionalization of non-activated primary C–H bonds
RESEARCH
01/2018
Evolving artificial metalloenzymes via random mutagenesis
RESEARCH
01/2018
Site-Selective Carbene-Induced C–H Functionalization Catalyzed by Dirhodium Tetrakis(triaryl cyclopropanecarboxylate) Complexes
RESEARCH
11/2017
Site-selective and stereoselective functionalization of non-activated tertiary C–H bonds
RESEARCH
11/2017
Rhodium Complexes of 2,6-Bis(dialkylphosphinomethyl)pyridines: Improved C–H Activation, Expanded Reaction Scope, and Catalytic Direct Arylation
RESEARCH
09/2017
Entrances, Traps, and Rate-Controlling Factors for Nickel-Catalyzed C−H Functionalization
RESEARCH
09/2017
Selective C(sp3)–H Monoarylation Catalyzed by a Covalently Cross-Linked Reverse Micelle-Supported Palladium Catalyst
RESEARCH
06/2017
Ruthenium-Catalyzed C–H Hydroxylation in Aqueous Acid Enables Selective Functionalization of Amine Derivatives
RESEARCH
06/2017
Mono-N-protected amino acid ligands stabilize dimeric palladium(II) complexes of importance to C–H functionalization
RESEARCH
06/2017
Synthesis of D/A-Substituted Diazo Compounds in Flow and Their Application in Enantioselective Dirhodium-Catalyzed Cyclopropanation and C–H Functionalization
RESEARCH
04/2017
Pd-Catalyzed Aerobic Oxidative Biaryl Coupling: Non-Redox Cocatalysis by Cu(OTf)2 and Discovery of Fe(OTf)3 as a Highly Effective Cocatalyst
RESEARCH
02/2017
Selective C–H bond functionalization using repurposed or artificial metalloenzymes
RESEARCH
11/2016
Toward a mild dehydroformylation using base-metal catalysis
RESEARCH
012/2016
Copper-Catalyzed Oxidative Cyclization of Carboxylic Acids
RESEARCH
11/2016
Copper-Catalyzed Bromination of C(sp3)−H Bonds Distal to Functional Groups
RESEARCH
11/2016
Sodium Hydroxide Catalyzed Dehydrocoupling of Alcohols with Hydrosilanes
RESEARCH
10/2016
Catalyst-Controlled and Tunable, Chemoselective Silver-Catalyzed Intermolecular Nitrene Transfer: Experimental and Computational Studies
RESEARCH
09/2016
Ligand-accelerated enantioselective methylene C(sp3)–H bond activation
RESEARCH
07/2016
Biochemical and Structural Characterization of MycCI, a Versatile P450 Biocatalyst from the Mycinamicin Biosynthetic Pathway
RESEARCH
06/2016
The Uranyl Cation as a Visible-Light Photocatalyst for C(sp3)−H Fluorination
RESEARCH
05/2016
The Development of Multidimensional Analysis Tools for Asymmetric Catalysis and Beyond
RESEARCH
05/2016
Site Selective and Stereoselective Functionalization of Unactivated C–H Bonds
RESEARCH
05/2016
The first bismuth(II)–rhodium(II) oxypyridinate paddlewheel complexes: Synthesis and structural characterization
RESEARCH
02/2016
Directed evolution of RebH for catalyst-controlled halogenation of indole C–H bonds
RESEARCH
02/2016
Iridium(III)-bis(imidazolinyl)phenyl catalysts for enantioselective C–H functionalization with ethyl diazoacetate
RESEARCH
01/2016
Rh2(II,III) Catalysts with Chelating Carboxylate and Carboxamidate Supports: Electronic Structure and Nitrene Transfer Reactivity
RESEARCH
01/2016
Oxygen Activation by Co(II) and a Redox Non-Innocent Ligand: Spectroscopic Characterization of a Radical–Co(II)–Superoxide Complex with Divergent Catalytic Reactivity
RESEARCH
12/2015
Hapalindole/Ambiguine Biogenesis Is Mediated by a Cope Rearrangement, C–C Bond-Forming Cascade
RESEARCH
12/2015
Factors Controlling Stability and Reactivity of Dimeric Pd(II) Complexes in C–H Functionalization Catalysis
RESEARCH
12/2015
Acceptorless dehydrogenation of small molecules through cooperative base metal catalysis
RESEARCH
11/2015
Expanding the family of heterobimetallic Bi–Rh paddlewheel carboxylate complexes via equatorial carboxylate exchange
RESEARCH
12/2015
Comparative Study of the Limitations and Challenges in Atom-Transfer C–H Oxidations
RESEARCH
08/2015
Cu(II)-Mediated C(sp2)–H Hydroxylation
RESEARCH
07/2015
Evolution of Efficient Modular Polyketide Synthases by Homologous Recombination
RESEARCH
07/2015
Cobalt catalyzed sp3 C–H amination utilizing aryl azides
RESEARCH
07/2015
Engineering a dirhodium artificial metalloenzyme for selective olefin cyclopropanation
RESEARCH
06/2015
Enzymatic hydroxylation of an unactivated methylene C–H bond guided by molecular dynamics simulations
RESEARCH
06/2015
Decarbonylative cross-coupling of esters by Ni-catalysis
RESEARCH
06/2015
Highly Active Nickel Catalysts for C–H Functionalization Identified through Analysis of Off-Cycle Intermediates
RESEARCH
06/2015
Iodoarene-Catalyzed Stereospecific Intramolecular sp3 C–H Amination
RESEARCH
06/2015
Ir-Catalyzed enantioselective group transfer reactions
RESEARCH
04/2015
Composite Polymer/Oxide Hollow Fiber Contactors: Versatile and Scalable Flow Reactors
RESEARCH
02/2015
Cu(II)-Catalyzed Coupling of Aromatic C–H Bonds with Malonates
RESEARCH
01/2015
Rh(III)-catalyzed C–H olefination of N-pentafluoroaryl benzamides
RESEARCH
01/2015
Silylation of C–H bonds in aromatic heterocycles by an Earth-abundant metal catalyst
RESEARCH
09/2014
Iron(II) Complexes Supported by Sulfonamido Tripodal Ligands
RESEARCH
10/2014
Polymer- and Silica-Supported Iron BPMEN-Inspired Catalysts for C–H Functionalization
RESEARCH
08/2014
Exceedingly Fast Copper(II)-Promoted ortho C–H Trifluoromethylation of Arenes using TMSCF3
RESEARCH
08/2014
Cu(II)-Mediated Ortho C–H Alkynylation of (Hetero)Arenes with Terminal Alkynes
RESEARCH
07/2014
Speciation and decomposition pathways of ruthenium catalysts used for selective C–H hydroxylation
RESEARCH
07/2014
Pd(II)-Catalyzed meta-C–H Olefination, Arylation, and Acetoxylation of Indolines Using a U-Shaped Template
RESEARCH
06/2014
Role of Sterically Demanding Chiral Dirhodium Catalysts in Site-Selective C–H Functionalization of Activated Primary C–H Bonds
RESEARCH
04/2014
Carboxylate-Assisted C(sp3)–H Activation in Olefin Metathesis-Relevant Ruthenium Complexes
RESEARCH
07/2014
Manganese terpyridine artificial metalloenzymes for benzylic oxygenation and olefin epoxidation
RESEARCH
04/2014
Recyclable Silica-Supported Iridium Bipyridine Catalyst for Aromatic C–H Borylation
RESEARCH
12/2013
Role of N-Acyl Amino Acid Ligands in Pd(II)-Catalyzed Remote C–H Activation of Tethered Arenes
RESEARCH
12/2013
Organocatalytic C–H hydroxylation with Oxone enabled by an aqueous fluoroalcohol solvent system
RESEARCH
12/2013
A General Method for Artificial Metalloenzyme Formation through Strain-Promoted Azide–Alkyne Cycloaddition
RESEARCH
11/2013
Silica-Immobilized Chiral Dirhodium(II) Catalyst for Enantioselective Carbenoid Reactions
RESEARCH
10/2013
Artificial Metalloenzymes and Metallopeptide Catalysts for Organic Synthesis
RESEARCH
09/2013
Dichotomous Hydrogen Atom Transfer vs Proton-Coupled Electron Transfer
RESEARCH
09/2013
Direct Spectroscopic Characterization of a Transitory Dirhodium Donor-Acceptor Carbene Complex
RESEARCH
04/2013
Iridium(III)-bis(oxazolinyl)phenyl catalysts for enantioselective C–H functionalization
RESEARCH
09/2012
Capturing fleeting intermediates in a catalytic C–H amination reaction cycle
RESEARCH
06/2012
Insight into Mechanistic Features of Ruthenium(II)-Pybox Catalyzed C-H Amination
RESEARCH
11/2011
Synthesis of Ruthenium(II)-2,6-Bisiminopyridyl Complexes for C-H Amination of Sulfamate Esters
RESEARCH
11/2011
D2-Symmetric Dirhodium Catalyst Derived from a 1,2,2-triarylcyclopropane carboxylate Ligand: Design, Synthesis and Application
RESEARCH
10/2011
A Diruthenium Catalyst for Selective, Intramolecular Allylic C-H Amination
RESEARCH
01/2011
Bystanding F+ Oxidants Enable Selective Reductive Elimination from High-Valent Metal Centers in Catalysis
RESEARCH
01/2010
Solvent-free catalytic enantioselective C–C bond forming reactions with very high catalyst turnover numbers
RESEARCH