General
Basic Approach to Experimentally Determining Organic Reaction Mechanisms
Deducing Reaction Mechanism: A Guide for Students, Researchers, and Instructors. J. Chem. Educ. 2016, 93, 275–286.
Why Study Mechanisms?
A Mechanistic Insight Leads to a Greatly Improved Osmium-Catalyzed Asymmetric Dihydroxylation Process. J. Am. Chem. Soc. 1989 111, 1123–1125.
Hard Soft Acid Base Theory
The Hard Soft Acids Bases (HSAB) Principle and Organic Chemistry. Chem. Rev. 1975, 75, 1–20.
Kinetics – Reaction Progress Analysis
Reaction Progress Analysis Review
“Reaction Progress Kinetic Analysis: A Powerful Methodology for Mechanistic Studies of Complex Catalytic Reactions.” https://doi.org/10.1002/anie.200462544
Reaction Progress Analysis Perspective
“Investigations of Pd-Catalyzed ArX Coupling Reactions Informed by Reaction Progress Kinetic Analysis.” https://pubs.acs.org/doi/10.1021/jo052409i
Reaction Progress Example
“Mechanistic Insights into the Pd(BINAP)-Catalyzed Amination of Aryl Bromides: Kinetic Studies under Synthetically Relevant Conditions.” https://pubs.acs.org/doi/10.1021/ja026885r
Same/Different Excess
“A Role for Pd(IV) in Catalytic Enantioselective C−H Functionalization with Monoprotected Amino Acid Ligands under Mild Conditions.” https://pubs.acs.org/doi/10.1021/jacs.7b03716
Kinetics – Normalized Time
Visual method to determine catalyst order
“A Simple Graphical Method to Determine the Order in Catalyst” https://doi.org/10.1002/anie.201508983
“Kinetic Treatments for Catalyst Activation and Deactivation Processes based on Variable Time Normalization Analysis” https://doi.org/10.1002/anie.201903878
Kinetics – Examples
First Order, Gas Absorption Kinetics
“Oxygenation of Nitrogen-Coordinated Palladium(0): Synthetic, Structural, and Mechanistic Studies and Implications for Aerobic Oxidation Catalysis.” https://pubs.acs.org/doi/abs/10.1021/ja015683c
Dimeric Catalyst that is First Order
“Highly Enantioselective Inverse-Electron-Demand Hetero-Diels-Alder Reactions of alpha,beta-Unsaturated Aldehydes”
https://doi.org/10.1002/1521-3757(20020816)114:16<3185::AID-ANGE3185>3.0.CO;2-S
Second Order Catalyst
“On the Mechanism of Asymmetric Nucleophilic Ring-Opening of Epoxides Catalyzed by (Salen)CrIII Complexes” https://doi.org/10.1021/ja962600x
Single Turnover on Non-Rate Limiting Step
“Chromium-Salen Catalyzed Cross-Coupling of Phenols: Mechanism and Origin of the Selectivity.” https://pubs.acs.org/doi/10.1021/jacs.9b03890
Burst vs Steady State Kinetics
“Mechanistic Study of Asymmetric Oxidative Biaryl Coupling: Evidence for Self-Processing of the Copper Catalyst to Achieve Control of Oxidase vs Oxygenase Activity.” https://doi.org/10.1021/ja804570b
Dissecting Combined First and Second Order Catalysts
“Cooperative Asymmetric Catalysis with Dimeric Salen Complexes.” https://pubs.acs.org/doi/abs/10.1021/ja982683c
Second Order Catalyst
“Asymmetric Ring Opening of Meso Epoxides with TMSCN Catalyzed by (pybox)lanthanide Complexes” https://doi.org/10.1021/ol005721h
Second Order -> First Order Catalyst
“Polymer-Supported Chiral Co(Salen) Complexes: Resolution of Terminal Epoxides” https://doi.org/10.1021/ja984410n
“Cooperative Asymmetric Catalysis with Dendrimeric [Co(salen)] Complexes”
https://doi.org/10.1002/1521-3773(20001016)39:20<3604::AID-ANIE3604>3.0.CO;2-9
Change in Rate Limiting Step Depending on Concentration
“Mechanistic Investigations of the Palladium-Catalyzed Aerobic Oxidative Kinetic Resolution of Secondary Alcohols Using (-)-Sparteine”
https://doi.org/10.1021/ja034262n
Steady State
“Insertion of Isonitriles into the M−C Bonds of Group 4 Dialkyl Complexes” https://pubs.acs.org/doi/10.1021/jacs.8b05377
Negative Catalysis
“Catalytic, Enantioselective, Intramolecular Carbosulfenylation of Olefins. Mechanistic Aspects: A Remarkable Case of Negative Catalysis”
https://pubs.acs.org/doi/10.1021/ja413270h
Competitive Inhibition
“Chorismate-utilizing enzymes isochorismate synthase, anthranilate synthase, and p-aminobenzoate synthase: mechanistic insight through inhibitor design” https://pubs.acs.org/doi/abs/10.1021/ja00113a002
Calculations of ring strain that determine mechanism
“Grob-Type Fragmentation Releases Paracyclophane Ring Strain in a Late-Stage Precursor of Haouamine A” https://doi.org/10.1021/acs.orglett.9b00424
Photochemical mechanistic study
“Characterizing chain processes in visible light photoredox catalysis”https://doi.org/10.1039/c5sc02185e
Proposing mechanism with reaction order and isolation of intermediates
“Nickel-Catalyzed Amination of Aryl Thioethers: A Combined Synthetic and Mechanistic Study” https://doi.org/10.1021/acscatal.0c00393
Energy Span
“What is the Rate-Limiting Step of a Multistep Reaction?” https://doi.org/10.1021/ed058p32
“How to Conceptualize Catalytic Cycles? The Energetic Span Model” https://pubs.acs.org/doi/10.1021/ar1000956
Hammond Postulate
“The Mechanistic Basis for Electronic Effects on Enantioselectivity in the (salen)Mn(III)-Catalyzed Epoxidation Reaction”
Kinetic Isotope Effects (KIE)
Review PowerPoint
“Kinetic Isotope Effects in Organic Chemistry” http://chemlabs.princeton.edu/macmillan/wp-content/uploads/sites/6/RRK-KIE.pdf
Parallel vs Intermolecular vs Intramolecular
“On the Interpretation of Deuterium Kinetic Isotope Effects in C_H Bond Functionalizations by Transition-Metal Complexes”
https://doi.org/10.1002/anie.201107334
Inter- vs Intramoelcular KIE
“Mechanism of N-Fluorobenzenesulfonimide Promoted Diamination and Carboamination Reactions: Divergent Reactivity of a Pd(IV) Species”
https://pubs.acs.org/doi/10.1021/jo0347361
Tunneling
“Quantum Tunneling in Chemical Reactions” https://macmillan.princeton.edu/wp-content/uploads/DEC_tunneling.pdf
“Halogen-atom and group transfer reactivity enabled by hydrogen tunneling” https://www.science.org/doi/epdf/10.1126/science.abq8663
KIE vs Hammett
“The Mechanistic Basis for Electronic Effects on Enantioselectivity in the (salen)Mn(III)-Catalyzed Epoxidation Reaction”
https://pubs.acs.org/doi/abs/10.1021/ja973468j
Inter- vs Intramolecular, Light Dependent
“On the Mechanism of C-H Bond Activation in the Photochemical Arylation of Rhenium(V) Oxo Iodide Complexes” https://doi.org/10.1021/om980216y
Computed KIE
“Theoretical Secondary Kinetic Isotope Effects and the Interpretation of Transition State Geometries. 2. The Diels-Alder Reaction Transition State Geometry” https://pubs.acs.org/doi/abs/10.1021/ja00100a037
Deuterium and 13C
“Chromium-Salen Catalyzed Cross-Coupling of Phenols: Mechanism and Origin of the Selectivity”
https://pubs.acs.org/doi/10.1021/jacs.9b03890
Parallel, Intermolecular, Deuterium Incorporation
“Mechanistic Study of a Re-Catalyzed Monoalkylation of Phenols”
Natural Abundance 13C KIE
“High-Precision Simultaneous Determination of Multiple Small Kinetic Isotope Effects at Natural Abundance” https://pubs.acs.org/doi/10.1021/ja00141a030
“Sensitive and Accurate 13C Kinetic Isotope Effect Measurements Enabled by Polarization Transfer” https://doi.org/10.1021/jacs.6b10621
“Chromium-Salen Catalyzed Cross-Coupling of Phenols: Mechanism and Origin of the Selectivity” https://pubs.acs.org/doi/10.1021/jacs.9b03890
Curtin-Hammett
“Curtin–Hammett principle” https://en.wikipedia.org/wiki/Curtin–Hammett_principle
“Mechanism and Stereoselectivity of Asymmetric Hydrogenation” https://science.sciencemag.org/content/217/4558/401
Exhaustive Hammett parameter table
“A Survey of Hammett Substituent Constants and Resonance and Field Parameters” https://doi.org/10.1021/cr00002a004
Eyring Analysis
Eyring to explore entropy vs enthalpy effects
“The Mechanistic Basis for Electronic Effects on Enantioselectivity in the (salen)Mn(III)-Catalyzed Epoxidation Reaction” https://pubs.acs.org/doi/abs/10.1021/ja973468j
Eyring to help determine RDS
“A Role for Pd(IV) in Catalytic Enantioselective C−H Functionalization with Monoprotected Amino Acid Ligands under Mild Conditions”
https://pubs.acs.org/doi/10.1021/jacs.7b03716
Measuring activation parameters
“Mechanistic Investigations of the Palladium-Catalyzed Aerobic Oxidative Kinetic Resolution of Secondary Alcohols Using (-)-Sparteine”
https://doi.org/10.1021/ja034262n
Using Eyring analysis to design ligands
“Lowering the Barrier to C−H Activation at Ir(III) through Pincer Ligand Design” https://doi.org/10.1021/acs.organomet.1c00080
Calculations
Best-Practice DFT Protocols
“Best-Practice DFT Protocols for Basic Molecular Computational Chemistry” https://doi.org/10.1002/ange.202205735
Computation vs Experiment
“Quantum Mechanical Predictions of the Stereoselectivities of Proline-Catalyzed Asymmetric Intermolecular Aldol Reactions” https://pubs.acs.org/doi/abs/10.1021/ja028812d
“Computational Organic Chemistry: Bridging Theory and Experiment in Establishing the Mechanisms of Chemical Reactions” https://doi.org/10.1021/ja5112749
“Can Contemporary Density Functional Theory Predict Energy Spansin Molecular Catalysis Accurately Enough To Be Applicable for inSilico Catalyst Design? A Computational/Experimental Case Study for the Ruthenium-Catalyzed Hydrogenation of Olefins” https://pubs.acs.org/doi/abs/10.1021/jacs.5b11997
Be Careful with Calculations (Singleton critique)
“A Case Study of the Mechanism of Alcohol-Mediated Morita Baylis−Hillman Reactions. The Importance of Experimental Observations”
https://pubs.acs.org/doi/10.1021/ja5111392
Singleton reply:
“Mechanism and reactivity in the Morita–Baylis–Hillman reaction: the challenge of accurate computations” https://doi.org/10.1039/C7CP06508F
Computational Pitfalls
“Pitfalls in Computational Modeling of Chemical Reactions and How To Avoid Them.” https://pubs.acs.org/doi/pdf/10.1021/acs.organomet.8b00456
Molecular Mechanics
“Molecular mechanics calculations on conjugated nitrogen-containing heterocycles” https://doi.org/10.1021/ja00215a006
Ab initio methods
“Ab initio quantum chemistry: Methodology and applications” https://doi.org/10.1073/pnas.0408036102
“Ab Initio Molecular Dynamics Simulations of the SN1/SN2 Mechanistic Continuum in Glycosylation Reactions” https://doi.org/10.1021/jacs.0c12096
“Ab initio and post-ab initio quantum chemical study of the heme spin states in electron transfer reactions” https://doi.org/10.1016/j.cplett.2005.12.067
“Gas-Phase Acidities of Some Neutral Brønsted Superacids: A DFT and ab Initio Study”
https://doi.org/10.1021/ja0000753
“Structure and Properties of Benzene-Containing Molecular Clusters: Nonempirical ab Initio Calculations and Experiments” https://doi.org/10.1021/cr00031a002
DFT methods
“Introduction to Density Functional Theory: Calculations by Hand on the Helium Atom”
https://doi.org/10.1021/ed5004788
“The devil in the details: A tutorial review on some undervalued aspects of density functional theory calculations” https://doi.org/10.1002/qua.26332
“Effects of Dispersion in Density Functional Based Quantum Mechanical/Molecular Mechanical Calculations on Cytochrome P450 Catalyzed Reactions” https://doi.org/10.1021/ct300329h
Time-dependent DFT for excited state calculations
“The calculations of excited-state properties with Time-Dependent Density Functional Theory”
https://doi.org/10.1039/C2CS35394F
Electron correlation
“Electron Correlation: Nature's Weird and Wonderful Chemical Glue” https://doi.org/10.1002/ijch.202100111
“Electron Correlation Effects in Molecules” https://doi.org/10.1021/jp953749i
HOMO Localization vs Mechanism
“Chromium-Salen Catalyzed Cross-Coupling of Phenols: Mechanism and Origin of the Selectivity” https://pubs.acs.org/doi/10.1021/jacs.9b03890
TSFF vs DFT, virtual ligand screening
“Transition State Force Field for the Asymmetric Redox-Relay Heck Reaction” https://doi.org/10.1021/jacs.0c01979
Computational modeling of activation strain
“Analyzing Reaction Rates with the Distortion/Interaction-Activation Strain Model” - https://doi.org/10.1002/anie.201701486
Using computations to aid in ligand design
“Mechanistically Guided Design of Ligands That Significantly Improve the Efficiency of CuH-Catalyzed Hydroamination Reactions” https://doi.org/10.1021/jacs.8b09565
QSSR
“A Priori Theoretical Prediction of Selectivity in Asymmetric Catalysis: Design of Chiral Catalysts by Using Quantum Molecular Interaction Fields” https://doi.org/10.1002/anie.200600329
QSSR with low computational cost
“Quantum Mechanical Models Correlating Structure with Selectivity: Predicting the Enantioselectivity of β-Amino Alcohol Catalysts in Aldehyde Alkylation”https://doi.org/10.1021/ja0293195
Computing van der waals, sterics, and hydrogen bonds
“NCIPLOT: A Program for Plotting Noncovalent Interaction Regions” https://doi.org/10.1021/ct100641a
Computation to determine mechanism
“Nickel-Catalyzed Cross-Coupling of Photoredox-Generated Radicals: Uncovering a General Manifold for Stereoconvergence in Nickel-Catalyzed Cross-Couplings”https://doi.org/10.1021/ja513079r
Bifurcated Transition States
“Do we fully understand what controls chemical selectivity?”
https://doi.org/10.1039/C1CP22565K
Post-transition state bifurcations gain momentum – current state of the field https://doi.org/10.1515/pac-2017-0104
Hammett Parameters
Enantioselectivity, Redox Values, KIE
“The Mechanistic Basis for Electronic Effects on Enantioselectivity in the (salen)Mn(III)-Catalyzed Epoxidation Reaction” https://pubs.acs.org/doi/abs/10.1021/ja973468j
What is Electron Donating vs Withdrawing
“Stereoelectronic Chameleons: The Donor–Acceptor Dichotomy of Functional Groups” https://doi.org/10.1002/chem.201603491
Change in Hammett Depending on Rate Limiting Step
“Mechanistic Investigations of the Palladium-Catalyzed Aerobic Oxidative Kinetic Resolution of Secondary Alcohols Using (-)-Sparteine” https://doi.org/10.1021/ja034262n
pKa vs Rate
“On the Mechanism of the Palladium-Catalyzed tert-Butylhydroperoxide-Mediated Wacker-Type Oxidation of Alkenes Using Quinoline-2-Oxazoline Ligands” https://pubs.acs.org/doi/abs/10.1021/ja2017043
Parameters to Assess Catalytic Reactions
“Parametrization of Catalytic Organic Reactions with Convex Hammett Plots” https://pubs.acs.org/doi/pdf/10.1021/acsorginorgau.2c00050
QSSR for determining catalyst quality
“Quantum Mechanical Models Correlating Structure with Selectivity: Predicting the Enantioselectivity of alpha-Amino Alcohol Catalysts in Aldehyde Alkylation” https://doi.org/10.1021/ja0293195
QSSR supported by experimentation
“A Priori Theoretical Prediction of Selectivity in Asymmetric Catalysis: Design of Chiral Catalysts by Using Quantum Molecular Interaction Fields” https://doi.org/10.1002/anie.200600329
Studying ligand properties to guide Suzuki reactions
“Enantiodivergent Pd-catalyzed C–C bond formation enabled through ligand parameterization” https://doi.org/10.1126/science.aat2299
ML to determine catalyst success
“Predicting Reaction Performance in C-N Cross-Coupling Using Machine Learning” http://science.sciencemag.org/content/360/6385/186
“Response to Comment on ‘Predicting Reaction Performance in C-N Cross-Coupling Using Machine Learning”
http://science.sciencemag.org/content/362/6416/eaat8763
Limitations of ML
“Cautionary Guidelines for Machine Learning Studies with Combinatorial Datasets” https://doi.org/10.1021/acscombsci.0c00118
Walkthrough of using computations to develop catalysts
“Development of a Computer-Guided Workflow for Catalyst Optimization. Descriptor Validation, Subset Selection, and Training Set Analysis”https://dx.doi.org/10.1021/jacs.0c04715
HTE to study reactions
“Molecular-level insight in supported olefin metathesis catalysts by combining surface organometallic chemistry, high throughput experimentation, and data analysis” https://doi.org/10.1039/D0SC02594A
QSPR in method development
“Enantioselective Allenoate-Claisen Rearrangement Using Chiral Phosphate Catalyst” https://pubs.acs.org/doi/pdf/10.1021/jacs.0c01637
Linear Free Energy Relationships (LFER) or Quantitative Structure Property Relationships (QSPR)
The Database
“Mayr's Database Of Reactivity Parameters” https://www.cup.lmu.de/oc/mayr/reaktionsdatenbank/
Account
“Pi-Nucleophilicity in Carbon-Carbon Bond-Forming Reactions.” https://doi.org/10.1021/ar020094c
Calculation of parameters
“Quantification of the Electrophilic Reactivities of Aldehydes, Imines, and Enones” https://doi.org/10.1021/ja200820m
Mayr parameters in SN2 reactions
“Towards a General Scale of Nucleophilicity?” https://doi.org/10.1002/anie.200600542
“Scales of Lewis Basicities toward C‑Centered Lewis Acids (Carbocations)” https://pubs.acs.org/doi/abs/10.1021/ja511639b
Account
“A Practical Guide for Estimating Rates of Heterolysis Reactions” https://doi.org/10.1021/ar100091m
Benchmarking
“The nucleophilicity N index in organic chemistry” https://doi-org.proxy.library.upenn.edu/10.1039/C1OB05856H
Application
“Nucleophilicity and Electrophilicity Parameters for Predicting Absolute Rate Constants of Highly Asynchronous 1,3-Dipolar Cycloadditions of Aryldiazomethanes” https://pubs.acs.org/doi/pdf/10.1021/jacs.8b09995
Site Nucleophilicities for Phenols
“Chromium-Salen Catalyzed Cross-Coupling of Phenols: Mechanism and Origin of the Selectivity” https://pubs.acs.org/doi/10.1021/jacs.9b03890
“Electrophilicities of Benzaldehyde-Derived Iminium Ions: Quantification of the Electrophilic Activation of Aldehydes by Iminium Formation” https://doi.org/10.1021/ja401106x
Mayr Nucleophilicity/ Electrophilicity Parameters
Hydrogen Bonding Parameters
“Quantification of Electrophilic Activation by Hydrogen-Bonding Organocatalysts” https://pubs.acs.org/doi/abs/10.1021/ja5086244
“NMR Quantification of Hydrogen-Bond-Activating Effects for Organocatalysts including Boronic Acids” https://doi.org/10.1021/acs.joc.8b02389
“Rapid Quantification of the Activating Effects of Hydrogen-Bonding Catalysts with a Colorimetric Sensor” https://doi.org/10.1021/ja3050663
Review of KR
“Practical Considerations in Kinetic Resolution Reactions” https://doi.org/10.1002/1615-4169(20010129)343:1<5::AID-ADSC5>3.0.CO;2-I
Kinetic Resolution in Synthesis
“Total Synthesis of (+)-Isoschizandrin Utilizing a Samarium(II) Iodide-Promoted 8-Endo Ketyl-Olefin Cyclization” https://doi.org/10.1021/jo0347361
Dynamic Thermodynamic Resolution
“Dynamic Thermodynamic Resolution: Control of Enantioselectivity through Diastereomeric Equilibration” https://pubs.acs.org/doi/10.1021/ar000077s
KR in catalysis
“A Practical Oligomeric [(salen)Co] Catalyst for Asymmetric Epoxide Ring-Opening Reactions”
https://doi.org/10.1002/1521-3773(20020415)41:8%3C1374::aid-anie1374%3E3.0.co;2-8
“Asymmetric Catalysis of Epoxide Ring-Opening Reactions” https://doi.org/10.1021/ar960061v
Kinetic Resolution (KR), Dynamic Kinetic Resolution (DKR), Dynamic Kinetic Asymmetric Transformation (DyKAT), Dynamic Thermodynamic Resolution
Nonlinear Effects
Example
“Self and Nonself Recognition of Asymmetric Catalysts. Nonlinear Effects in the Amino Alcohol-Promoted Enantioselective Addition of Dialkylzincs to Aldehydes” https://pubs.acs.org/doi/abs/10.1021/ja00122a013
Good explanation of NLE in different systems
“Nonlinear Effects in Asymmetric Catalysis” https://doi.org/10.1021/ja00100a004
Reservoir Effects
“Catalysis of the Michael Addition Reaction by Late Transition Metal Complexes of BINOL-Derived Salens” https://doi.org/10.1021/jo025993t
NLE in Transition Metal Systems
“Mechanistic Applications of Nonlinear Effects in First-Row Transition-Metal Catalytic Systems”
Cyclic Voltammetry
“A Role for Pd(IV) in Catalytic Enantioselective C−H Functionalizationwith Monoprotected Amino Acid Ligands under Mild Conditions”
https://pubs.acs.org/doi/10.1021/jacs.7b03716
A Practical Beginner’s Guide to Cyclic Voltammetry
Stirring Rate Effects
“A Role for Pd(IV) in Catalytic Enantioselective C−H Functionalizationwith Monoprotected Amino Acid Ligands under Mild Conditions”
Woodward Hoffman Rules
Original Woodward Hoffman Paper
“The Conservation of Orbital Symmetry” https://doi.org/10.1002/anie.196907811
Theoretical basis for WH rules
“Dynamic correlation diagrams for sigmatropic reactions based on orbital phase conservation theory” https://doi.org/10.1142/S0219633617500559
Radicals
Radical philicity review
“Radical philicity and its role in selective organic transformations” https://www.nature.com/articles/s41570-021-00284-3
Calculating radical philicity
“Electrophilicity and Nucleophilicity Index for Radicals” https://doi.org/10.1021/ol071038k
Curran Review of radicals in total synthesis
“Radical reactions in natural product synthesis”https://doi.org/10.1021/cr00006a006
Radical mechanism example
“Nickel-Catalyzed Cross-Coupling of Photoredox-Generated Radicals: Uncovering a General Manifold for Stereoconvergence in Nickel-Catalyzed Cross-Couplings” https://doi.org/10.1021/ja513079r
Case Studies
Kinetics, KIE, Hammett, Cyclic Voltammetry, Hammond Postulate, Eyring
“The Mechanistic Basis for Electronic Effects on Enantioselectivity in the (salen)Mn(III)-Catalyzed Epoxidation Reaction” https://pubs.acs.org/doi/abs/10.1021/ja973468j
Kinetics, KIE, Natural Abundance 13C KIE, Calculations
“Chromium-Salen Catalyzed Cross-Coupling of Phenols: Mechanism and Origin of the Selectivity”
https://pubs.acs.org/doi/10.1021/jacs.9b03890
Burst and Steady State Kinetics
“Mechanistic Study of Asymmetric Oxidative Biaryl Coupling: Evidence for Self-Processing of the Copper Catalyst to Achieve Control of Oxidase vs Oxygenase Activity” https://doi.org/10.1021/ja804570b
Kinetics, Hammett vs Change in Rate Limiting Step, Eyring
“Mechanistic Investigations of the Palladium-Catalyzed Aerobic Oxidative Kinetic Resolution of Secondary Alcohols Using (-)-Sparteine” https://doi.org/10.1021/ja034262n
Kinetics, Hammett, pKa vs Rate
“On the Mechanism of the Palladium-Catalyzed tert-Butylhydroperoxide-Mediated Wacker-Type Oxidation of Alkenes Using Quinoline-2-Oxazoline Ligands” https://pubs.acs.org/doi/abs/10.1021/ja2017043
Kinetics, KIE
“Mechanistic Study of a Re-Catalyzed Monoalkylation of Phenols”
https://pubs.acs.org/doi/10.1021/acs.organomet.8b00543
DFT, Hammett parameters
“Electronic Effects in (salen)Mn-Based Epoxidation Catalysts” https://pubs.acs.org/doi/10.1021/jo034059a
Kinetics, KIE, Hammett
“Mechanism of Copper(I)/TEMPO-Catalyzed Aerobic Alcohol Oxidation” https://pubs.acs.org/doi/10.1021/ja3117203
Kinetic resolutions, calculations
“Catalytic Kinetic Resolution of Disubstituted Piperidines by Enantioselective Acylation: Synthetic Utility and Mechanistic Insights” https://doi.org/10.1021/jacs.5b07201
Mechanism, Eyring, computation, mechanism
“Mild Aromatic Palladium-Catalyzed Protodecarboxylation: Kinetic Assessment of the Decarboxylative Palladation and the Protodepalladation Steps”https://pubs.acs.org/doi/10.1021/jo400222c
Mechanism, KIE
“N‐Acyl Amino Acid Ligands for Ruthenium(II)-Catalyzed meta-C−H tert-Alkylation with Removable Auxiliaries” https://doi.org/10.1021/jacs.5b08435
Mechanism, KIE, Kinetics
“Kinetics and Mechanism of the (-)-Sparteine-Mediated Deprotonation of (E)-N-Boc-N-(p-methoxyphenyl)-3-cyclohexylallylamine” https://doi.org/10.1021/ja001955k
Mechanism, Kinetics, Hammett
“Mechanistic Investigations of Cooperative Catalysis in the Enantioselective Fluorination of Epoxides” https://doi.org/10.1021/ja207256s