Led by Jamal Musaev
One of the central thrusts of this multi-faceted research project is to build up the mechanistic understanding of C-H functionalization in an aim to develop:
- Next-generation, selective, and more efficient catalysts including earth-abundant transition metals.
- Predictive models for determining site selectivity in complex target synthesis.
Predictive models for C–H modification are challenged and refined in the context of the late-stage C-H functionalization, novel disconnections in complex target synthesis, and design of new approaches for novel materials preparation and drug discovery. Thus, fundamental (computational and mechanistic) studies are the cornerstone of the proposed multi-faceted research project and designed to guide and impact selective C-H functionalization strategies through new and more efficient catalyst design and direct elucidation of both the successes and limiting factors of current C-H functionalization methodologies in preparation of novel materials, natural products, fine chemistry and effective drugs.
In order to gain a comprehensive mechanistic understanding of the factors that control chemo-, regio-, and stereoselectivity in C–H functionalization, during the reporting period, investigators have launched several cutting-edge collaborative (experimental and theoretical) projects. These multi-disciplinary research efforts offer the most compelling and most needed fundament knowledge for the design of new and more efficient catalysts for the C-H bond functionalization to improve the application of this revolutionary synthetic strategy for materials preparation, as well as natural product, fine chemistry and effective drug synthesis.
10/2018
On the Mechanism of Permanganate Promoted Dihydroxylation of Complex Diketopiper-azines: Critical Roles of Counter-Cation and Ion-Pairing
RESEARCH
08/2018
Design of catalysts for site-selective and enantioselective functionalization of non-activated primary C–H bonds
RESEARCH
05/2018
Numerical Nuclear Second Derivatives on a Computing Grid: Enabling and Accelerating Frequency Calculations on Complex Molecular Systems
RESEARCH
04/2018
Unveiling the Role of Base and Additive in the Ullmann-Type of Arene-Aryl C–C Coupling Reaction
RESEARCH
10/2017
Quantitative Modeling of Bis(pyridine)silver(I) Permanganate Oxidation of Hydantoin Derivatives: Guidelines for Predicting the Site of Oxidation in Complex Substrates
RESEARCH
11/2017
Inverting Steric Effects: Using “Attractive” Noncovalent Interactions To Direct Silver-Catalyzed Nitrene Transfer
RESEARCH
03/2018
Are Phosphines Viable Ligands for Pd-Catalyzed Aerobic Oxidation Reactions? Contrasting Insights from a Survey of Six Reactions
RESEARCH
02/2018
Unprecedented Dearomatized Spirocyclopropane in a Sequential Rh(III)-catalyzed C-H Activation and Rearrangement Reaction
RESEARCH
01/2018
A General Protocol for Addressing Speciation of the Active Catalyst Applied to Ligand-Accelerated Enantioselective C(sp3)–H Bond Arylation
RESEARCH
11/2017
Quantifying Structural Effects of Amino Acid Ligands in Pd(II)-Catalyzed Enantioselective C–H Functionalization Reactions
RESEARCH
12/2017
Multiple roles of silver salts in palladium-catalyzed C–H activations
RESEARCH
12/2017
Dynamic Ligand Exchange as a Mechanistic Probe in Pd-Catalyzed Enantioselective C–H Functionalization Reactions Using Monoprotected Amino Acid Ligands
RESEARCH
01/2018
Key mechanistic insights into the intramolecular C-H bond amination and double bond aziridination in sulfamate esters catalyzed by dirhodium tetracarboxylate complexes
RESEARCH
11/2017
Site-selective bromination of sp3 C–H bonds
RESEARCH
08/2017
Mechanistic analysis of a copper-catalyzed C–H oxidative cyclization of carboxylic acids
RESEARCH
11/2017
Synthesis of Diverse 11- and 12-Membered Macrolactones from a Common Linear Substrate Using a Single Biocatalyst
RESEARCH
10/2017
Bimodal Evans–Polanyi Relationships in Dioxirane Oxidations of sp3 C–H Bonds
RESEARCH
09/2017
Entrances, Traps, and Rate-Controlling Factors for Nickel-Catalyzed C−H Functionalization
RESEARCH
09/2017
Pomeranz–Fritsch Synthesis of Isoquinoline: Gas-Phase Collisional Activation Opens Additional Reaction Pathways
RESEARCH
09/2017
Mechanistic Basis for Efficient, Site-Selective, Aerobic Catalytic Turnover in Pd-Catalyzed C–H Imidoylation of Heterocycle-Containing Molecules
RESEARCH
05/2017
Enantioselectivity Model for Pd-Catalyzed C–H Functionalization Mediated by the Mono-N-protected Amino Acid (MPAA) Family of Ligands
RESEARCH
06/2017
The Origins of Dramatic Differences in Five-Membered vs Six-Membered Chelation of Pd(II) on Efficiency of C(sp3)–H Bond Activation
RESEARCH
06/2017
Mono-N-protected amino acid ligands stabilize dimeric palladium(II) complexes of importance to C–H functionalization
RESEARCH
06/2017
A Role for Pd(IV) in Catalytic Enantioselective C–H Functionalization with Monoprotected Amino Acid Ligands under Mild Conditions
RESEARCH
05/2017
Mechanism, Regio-, and Diastereoselectivity of Rh(III)-Catalyzed Cyclization Reactions of N-Arylnitrones with Alkynes: A Density Functional Theory Study
RESEARCH
06/2017
Ionic and Neutral Mechanisms for C–H Bond Silylation of Aromatic Heterocycles Catalyzed by Potassium tert-Butoxide
RESEARCH
06/2017
Potassium tert-Butoxide-Catalyzed Dehydrogenative C–H Silylation of Heteroaromatics: A Combined Experimental and Computational Mechanistic Study
RESEARCH
04/2017
Catalyst-Controlled Nitrene Transfer by Tuning Metal:Ligand Ratios: Insight into the Mechanisms of Chemoselectivity
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
Metal-Free C–H Functionalization of Alkanes by Aryldiazoacetates
RESEARCH
01/2017
Understanding Flavin-Dependent Halogenase Reactivity via Substrate Activity Profiling
RESEARCH
12/2016
Mesoscale Ordering and Charge-Transport of Crystalline Spiro-OMeTAD Organic Semiconductors
RESEARCH
11/2016
Rh(II)-Catalyzed β-C(sp2)-H Alkylation of Enol Ethers, Enamides and Enecarbamates with α-Diazo Dicarbonyl Compounds
RESEARCH
10/2016
Cu-Catalyzed aromatic C–H imidation with N-fluorobenzenesulfonimide: mechanistic details and predictive models
RESEARCH
05/2016
Computational Exploration of RhIII/RhV and RhIII/RhI Catalysis in Rhodium(III)-Catalyzed C–H Activation Reactions of N-Phenoxyacetamides with Alkynes
RESEARCH
10/2016
Catalyst-Controlled and Tunable, Chemoselective Silver-Catalyzed Intermolecular Nitrene Transfer: Experimental and Computational Studies
RESEARCH
09/2016
Flexible Reaction Pocket on Bulky Diphosphine–Ir Complex Controls Regioselectivity in para-Selective C–H Borylation of Arenes
RESEARCH
09/2016
Ligand-accelerated enantioselective methylene C(sp3)–H bond activation
RESEARCH
05/2016
The Development of Multidimensional Analysis Tools for Asymmetric Catalysis and Beyond
RESEARCH
03/2016
Molecular Dynamics of Dimethyldioxirane C–H Oxidation
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
12/2015
Factors Controlling Stability and Reactivity of Dimeric Pd(II) Complexes in C–H Functionalization Catalysis
RESEARCH
12/2015
Comparative Study of the Limitations and Challenges in Atom-Transfer C–H Oxidations
RESEARCH
09/2015
Mono-Oxidation of Bidentate Bis-phosphines in Catalyst Activation: Kinetic and Mechanistic Studies of a Pd/Xantphos-Catalyzed C–H Functionalization
RESEARCH
10/2015
Syntheses of Isoquinoline and Substituted Quinolines in Charged Microdroplets
RESEARCH
07/2015
Acceleration of reaction in charged microdroplets
RESEARCH
07/2015
Pyridine N-Oxide vs Pyridine Substrates for Rh(III)-Catalyzed Oxidative C–H Bond Functionalization
RESEARCH
07/2015
Mechanistic Details of Pd(II)-Catalyzed C–H Iodination with Molecular I2: Oxidative Addition vs Electrophilic Cleavage
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
An IM-MS/DFT Study on Pd-Catalyzed C–H Activation
RESEARCH
06/2015
Iodoarene-Catalyzed Stereospecific Intramolecular sp3 C–H Amination
RESEARCH
05/2015
Mechanism and Stereoselectivity of Directed C(sp3)–H Activation and Arylation Catalyzed by Pd(II) with Pyridine Ligand and Trifluoroacetate
RESEARCH
05/2015
Fundamental Aspects of the Metal-Catalyzed C–H Bond Functionalization by Diazocarbenes
RESEARCH
03/2015
Using IR vibrations to quantitatively describe and predict site-selectivity in multivariate Rh-catalyzed C–H functionalization
RESEARCH
12/2014
Factors Impacting the Mechanism of the Mono-N-Protected Amino Acid Ligand-Assisted C–H Activation
RESEARCH
12/2014
Analysis of an asymmetric palladium-catalyzed conjugate addition
RESEARCH
09/2014
Iron(II) Complexes Supported by Sulfonamido Tripodal Ligands
RESEARCH
09/2014
Key Mechanistic Features of Ni-Catalyzed C–H/C–O Biaryl Coupling of Azoles and Naphthalen-2-yl Pivalates
RESEARCH
07/2014
Comparative Investigations of Cp*-Based Group 9 Metal-Catalyzed Direct C–H Amination of Benzamides
RESEARCH
07/2014
Speciation and decomposition pathways of ruthenium catalysts used for selective C–H hydroxylation
RESEARCH
04/2014
Carboxylate-Assisted C(sp3)–H Activation in Olefin Metathesis-Relevant Ruthenium Complexes
RESEARCH
03/2014
Analyzing Site Selectivity in Rh2(esp)2-Catalyzed Intermolecular C–H Amination Reactions
RESEARCH
03/2014
Versatile reactivity of Pd-catalysts: features of the mono-N-protected AA ligand and cesium-X base in Pd-catalyzed C–H functionalization
RESEARCH
02/2014
Distortion/Interaction Analysis Reveals the Origins of Selectivities in Iridium-Catalyzed C–H Borylation of Substituted Arenes and 5-Membered Heterocycles
RESEARCH
12/2013
Role of N-Acyl Amino Acid Ligands in Pd(II)-Catalyzed Remote C–H Activation of Tethered Arenes
RESEARCH
12/2013
Pd-Catalyzed meta-Selective C–H Activation with a Nitrile-Containing Template: Computational Study on Mechanism and Origins of Selectivity
RESEARCH
09/2013
Direct Spectroscopic Characterization of a Transitory Dirhodium Donor-Acceptor Carbene Complex
RESEARCH
09/2013
Understanding the Reactivity of Pd(0)/PR3-Catalyzed Intermolecular C(sp3)-H Bond Arylation
RESEARCH
07/2013
Can bis(imino)pyridine iron, (PDI)FeL1L2, complexes catalyze C–H bond functionalization?
RESEARCH
05/2013
Chemoselective Pd-catalyzed Oxidation of Polyols: Synthetic Scope and Mechanistic Studies
RESEARCH
04/2013
Rhodium-catalyzed enantioselective cyclopropanation of electron-deficient alkenes
RESEARCH
04/2013
Iridium(III)-bis(oxazolinyl)phenyl catalysts for enantioselective C–H functionalization
RESEARCH
11/2012
Cafestol to Tricalysiolide B and Oxidized Analogues: Biosynthetic and Derivatization Studies Using Non-heme Iron Catalyst Fe(PDP)
RESEARCH
09/2012
Capturing fleeting intermediates in a catalytic C–H amination reaction cycle
RESEARCH
08/2012
Mechanistic Insights into the Aerobic Copper(I)-Catalyzed Cross-Coupling
RESEARCH
07/2012
Understanding Reactivity and Stereoselectivity in Palladium-Catalyzed Diastereoselective sp3 C–H Bond Activation
RESEARCH
02/2012
Mechanistic Rationalization of Unusual Kinetics in Pd-Catalyzed C–H Olefination
RESEARCH
06/2012
Insight into Mechanistic Features of Ruthenium(II)-Pybox Catalyzed C-H Amination
RESEARCH
12/2011
Key Mechanistic Features of Enantioselective C-H Bond Activation Reactions Catalyzed by [N-Protected AA-Pd(II)] Complexes
RESEARCH
11/2011
D2-Symmetric Dirhodium Catalyst Derived from a 1,2,2-triarylcyclopropane carboxylate Ligand: Design, Synthesis and Application
RESEARCH
08/2011
Computationally-Guided Stereocontrol of the Combined C-H Functionalization/Cope Rearrangement
RESEARCH
03/2011
On the Mechanism of the C−H Activation / Cope Rearrangement
RESEARCH