Bulky Phosphine Ligands Promote Palladium-Catalyzed Protodeboronation

Ser, Cher Tian; Hao, Han; Pablo-García, Sergio; Jorner, Kjell; Li, Shangyu; Pollice, Robert; Aspuru-Guzik, Alán

doi:10.1021/jacs.5c14153

Title: Bulky Phosphine Ligands Promote Palladium-Catalyzed Protodeboronation

Journal Article · Mon Nov 17 00:00:00 UTC 2025 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.5c14153 · OSTI ID:3023783

^[1]; Hao, Han ^[2];

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University of Toronto, ON (Canada); Vector Institute for Artificial Intelligence, Toronto, ON (Canada)
University of Toronto, ON (Canada); Acceleration Consortium, Toronto, ON (Canada)
University of Toronto, ON (Canada); Vector Institute for Artificial Intelligence, Toronto, ON (Canada); Acceleration Consortium, Toronto, ON (Canada)
University of Toronto, ON (Canada); ETH Zurich (Switzerland)
University of Toronto, ON (Canada); Harvard University, Cambridge, MA (United States)
University of Toronto, ON (Canada); University of Groningen (The Netherlands)
University of Toronto, ON (Canada); Vector Institute for Artificial Intelligence, Toronto, ON (Canada); Acceleration Consortium, Toronto, ON (Canada); Canadian Institute for Advanced Research (CIFAR), Toronto, ON (Canada); Institute of Medical Science, Toronto, ON (Canada)

The Suzuki-Miyaura cross-coupling reaction is plagued by protodeboronation, an undesirable side reaction with water that consumes the boronic acid derivatives required for the cross-coupling reaction. Meticulous mechanistic studies have previously established protodeboronation to be highly sensitive to the nature of the boronic reagent and reaction conditions. Particularly, the presence of bases, which are essential for the Suzuki-Miyaura coupling, is known to catalyze protodeboronation. However, protodeboronation catalyzed by palladium-phosphine complexes, the benchmark catalyst system for Suzuki-Miyaura cross-coupling, has been understudied compared to its base-catalyzed counterpart. Here, we demonstrate, using automated high-throughput experimentation, comprehensive computational mechanistic analyses and kinetic modeling, that protodeboronation is accelerated by palladium(II) complexes bound to bulky phosphine ligands. While sterically hindered ligands are typically used to facilitate difficult cross-couplings, these ligands can instead paradoxically impede cross-coupling product formation, requiring careful and judicious consideration when choosing ligands for Suzuki-Miyaura cross-couplings.

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Research Organization:: University of Minnesota, Minneapolis, MN (United States)

Sponsoring Organization:: DARPA; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0023454

OSTI ID:: 3023783

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 47 Vol. 147; ISSN 0002-7863; ISSN 1520-5126

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (82)

Factors Determining the Selection of Organic Reactions by Medicinal Chemists and the Use of These Reactions in Arrays (Small Focused Libraries) Cooper, Tony W. J.; Campbell, Ian B.; Macdonald, Simon J. F. Angewandte Chemie International Edition, Vol. 49, Issue 44 https://doi.org/10.1002/anie.201002238	journal	September 2010
Palladium-Catalyzed Cross-Coupling: A Historical Contextual Perspective to the 2010 Nobel Prize Johansson Seechurn, Carin C. C.; Kitching, Matthew O.; Colacot, Thomas J. Angewandte Chemie International Edition, Vol. 51, Issue 21, p. 5062-5085 https://doi.org/10.1002/anie.201107017	journal	May 2012
Computational Kinetics of Cobalt-Catalyzed Alkene Hydroformylation Rush, Laura E.; Pringle, Paul G.; Harvey, Jeremy N. Angewandte Chemie International Edition, Vol. 53, Issue 33 https://doi.org/10.1002/anie.201402115	journal	April 2014
Kinetic Data for the Transmetalation/Reductive Elimination in Palladium-Catalyzed Suzuki-Miyaura Reactions: Unexpected Triple Role of Hydroxide Ions Used as Base Amatore, Christian; Jutand, Anny; Le Duc, Gaëtan Chemistry - A European Journal, Vol. 17, Issue 8 https://doi.org/10.1002/chem.201001911	journal	January 2011
Hartree–Fock exchange fitting basis sets for H to Rn Weigend, Florian Journal of Computational Chemistry, Vol. 29, Issue 2 https://doi.org/10.1002/jcc.20702	journal	January 2007
Effect of the damping function in dispersion corrected density functional theory Grimme, Stefan; Ehrlich, Stephan; Goerigk, Lars Journal of Computational Chemistry, Vol. 32, Issue 7 https://doi.org/10.1002/jcc.21759	journal	March 2011
Spin-component-scaled double hybrids: An extensive search for the best fifth-rung functionals blending DFT and perturbation theory Kozuch, Sebastian; Martin, Jan M. L. Journal of Computational Chemistry https://doi.org/10.1002/jcc.23391	journal	July 2013
NBO 7.0 : New vistas in localized and delocalized chemical bonding theory Glendening, Eric D.; Landis, Clark R.; Weinhold, Frank Journal of Computational Chemistry https://doi.org/10.1002/jcc.25873	journal	June 2019
In Situ Generated Palladium Nanoparticles for Catalytic Dehalogenation of Aryl Halides and Deboronation of Arylboronic acids Lai, Rung‐Yi; Chen, Chuan‐Lin; Liu, Shiuh‐Tzung Journal of the Chinese Chemical Society, Vol. 53, Issue 4 https://doi.org/10.1002/jccs.200600130	journal	August 2006
Etude des pK_a et de la protodéboronation des acides furanneboroniques Florentin, D.; Fournié‐Zaluski, M. C.; Callanquin, M. Journal of Heterocyclic Chemistry, Vol. 13, Issue 6 https://doi.org/10.1002/jhet.5570130624	journal	December 1976
Software update: the ORCA program system, version 4.0: Software update Neese, Frank Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 8, Issue 1 https://doi.org/10.1002/wcms.1327	journal	July 2017
Microkinetic modeling in homogeneous catalysis Besora, Maria; Maseras, Feliu Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 8, Issue 6 https://doi.org/10.1002/wcms.1372	journal	June 2018
Software update: The ORCA program system—Version 5.0 Neese, Frank WIREs Computational Molecular Science, Vol. 12, Issue 5 https://doi.org/10.1002/wcms.1606	journal	March 2022
The ORCA program system: The ORCA program system Neese, Frank Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 1 https://doi.org/10.1002/wcms.81	journal	June 2011
Optimized accurate auxiliary basis sets for RI-MP2 and RI-CC2 calculations for the atoms Rb to Rn Hellweg, Arnim; Hättig, Christof; Höfener, Sebastian Theoretical Chemistry Accounts, Vol. 117, Issue 4 https://doi.org/10.1007/s00214-007-0250-5	journal	January 2007
Study on the synthesis of nonracemic C2-symmetric 1,1′-binaphthyl-2,2′-diyl bridged ferrocene. Stereochemical result of the cross-coupling reactions controlled by Pd(II) or Pd(IV) complex intermediacy Kasák, P.; Mikláš, R.; Putala, M. Journal of Organometallic Chemistry, Vol. 637-639 https://doi.org/10.1016/S0022-328X(01)00926-3	journal	December 2001
Base-free oxidative homocoupling of arylboronic esters Yoshida, Hiroto; Yamaryo, Yasuhito; Ohshita, Joji Tetrahedron Letters, Vol. 44, Issue 8 https://doi.org/10.1016/S0040-4039(03)00023-6	journal	February 2003
An affordable platform for automated synthesis and electrochemical characterization Pablo-García, Sergio; García, Ángel; Akkoc, Gun Deniz Device, Vol. 3, Issue 2 https://doi.org/10.1016/j.device.2024.100567	journal	February 2025
ChemOS 2.0: An orchestration architecture for chemical self-driving laboratories Sim, Malcolm; Vakili, Mohammad Ghazi; Strieth-Kalthoff, Felix Matter https://doi.org/10.1016/j.matt.2024.04.022	journal	May 2024
Recent developments in libxc — A comprehensive library of functionals for density functional theory Lehtola, Susi; Steigemann, Conrad; Oliveira, Micael J. T. SoftwareX, Vol. 7 https://doi.org/10.1016/j.softx.2017.11.002	journal	January 2018
GFN2-xTB—An Accurate and Broadly Parametrized Self-Consistent Tight-Binding Quantum Chemical Method with Multipole Electrostatics and Density-Dependent Dispersion Contributions Bannwarth, Christoph; Ehlert, Sebastian; Grimme, Stefan Journal of Chemical Theory and Computation, Vol. 15, Issue 3 https://doi.org/10.1021/acs.jctc.8b01176	journal	January 2019
Cobalt-Catalyzed Protodeboronation of Aryl and Vinyl Boronates Li, Ninglin; Xiong, Fuqiang; Gao, Ke The Journal of Organic Chemistry, Vol. 86, Issue 2 https://doi.org/10.1021/acs.joc.0c02570	journal	January 2021
Multidirectional Synthesis of Substituted Indazoles via Iridium-Catalyzed C–H Borylation Sadler, Scott A.; Hones, Andrew C.; Roberts, Bryan The Journal of Organic Chemistry, Vol. 80, Issue 10 https://doi.org/10.1021/acs.joc.5b00452	journal	May 2015
Gold-Catalyzed Proto- and Deuterodeboronation Barker, Graeme; Webster, Stacey; Johnson, David G. The Journal of Organic Chemistry, Vol. 80, Issue 20 https://doi.org/10.1021/acs.joc.5b01041	journal	July 2015
Investigations into the Kinetic Modeling of the Direct Alkylation of Benzylic Amines: Dissolution of K₂CO₃ Is Responsible for the Observation of an Induction Period Pollice, Robert; Schnürch, Michael The Journal of Organic Chemistry, Vol. 80, Issue 16 https://doi.org/10.1021/acs.joc.5b01335	journal	August 2015
Harnessing C–H Borylation/Deborylation for Selective Deuteration, Synthesis of Boronate Esters, and Late Stage Functionalization Kallepalli, Venkata A.; Gore, Kristin A.; Shi, Feng The Journal of Organic Chemistry, Vol. 80, Issue 16 https://doi.org/10.1021/acs.joc.5b01588	journal	August 2015
Kinetic and Mechanistic Investigations to Enable a Key Suzuki Coupling for Sotorasib Manufacture─What a Difference a Base Makes Murray, James I.; Zhang, Liang; Simon, Adam Organic Process Research & Development, Vol. 27, Issue 1 https://doi.org/10.1021/acs.oprd.2c00332	journal	December 2022
Bismuth Acetate as a Catalyst for the Sequential Protodeboronation of Di- and Triborylated Indoles Shen, Fangyi; Tyagarajan, Sriram; Perera, Damith Organic Letters, Vol. 18, Issue 7 https://doi.org/10.1021/acs.orglett.6b00356	journal	March 2016
Scope and Challenge of Computational Methods for Studying Mechanism and Reactivity in Homogeneous Catalysis Harvey, Jeremy N.; Himo, Fahmi; Maseras, Feliu ACS Catalysis, Vol. 9, Issue 8 https://doi.org/10.1021/acscatal.9b01537	journal	June 2019
Palladium-Catalyzed Suzuki−Miyaura Cross-Coupling Reactions Employing Dialkylbiaryl Phosphine Ligands Martin, Ruben; Buchwald, Stephen L. Accounts of Chemical Research, Vol. 41, Issue 11 https://doi.org/10.1021/ar800036s	journal	November 2008
Palladium-Catalyzed Cross-Coupling Reactions of Organoboron Compounds Miyaura, Norio.; Suzuki, Akira. Chemical Reviews, Vol. 95, Issue 7 https://doi.org/10.1021/cr00039a007	journal	November 1995
Transmetalation of Unsaturated Carbon Nucleophiles from Boron-Containing Species to the Mid to Late d-Block Metals of Relevance to Catalytic C−X Coupling Reactions (X = C, F, N, O, Pb, S, Se, Te) Partyka, David V. Chemical Reviews, Vol. 111, Issue 3 https://doi.org/10.1021/cr1002276	journal	March 2011
Emergence of Palladium(IV) Chemistry in Synthesis and Catalysis Sehnal, Petr; Taylor, Richard J. K.; Fairlamb, Ian J. S. Chemical Reviews, Vol. 110, Issue 2 https://doi.org/10.1021/cr9003242	journal	February 2010
Antisymbiosis and the trans effect Pearson, Ralph G. Inorganic Chemistry, Vol. 12, Issue 3 https://doi.org/10.1021/ic50121a052	journal	March 1973
Electrophilic Displacement Reactions. XVI. Metal Ion Catalysis in the Protodeboronation of Areneboronic Acids^1-3 Kuivila, Henry G.; Reuwer, Joseph F.; Mangravite, John A. Journal of the American Chemical Society, Vol. 86, Issue 13 https://doi.org/10.1021/ja01067a031	journal	July 1964
The Fluidity of Dioxane—Water Mixtures¹ Geddes, John A. Journal of the American Chemical Society, Vol. 55, Issue 12 https://doi.org/10.1021/ja01339a017	journal	December 1933
Electrophilic Displacement Reactions. X. General Acid Catalysis in the Protodeboronation of Areneboronic Acids^1-3 Kuivila, Henry G.; Nahabedian, K. V. Journal of the American Chemical Society, Vol. 83, Issue 9 https://doi.org/10.1021/ja01470a028	journal	May 1961
Electrophilic Displacement Reactions. XII. Substituent Effects in the Protodeboronation of Areneboronic Acids^1-3 Nahabedian, K. V.; Kuivila, Henry G. Journal of the American Chemical Society, Vol. 83, Issue 9 https://doi.org/10.1021/ja01470a030	journal	May 1961
Catalysts for Suzuki−Miyaura Coupling Processes: Scope and Studies of the Effect of Ligand Structure Barder, Timothy E.; Walker, Shawn D.; Martinelli, Joseph R. Journal of the American Chemical Society, Vol. 127, Issue 13 https://doi.org/10.1021/ja042491j	journal	April 2005
Mechanism of the Palladium-Catalyzed Homocoupling of Arylboronic Acids: Key Involvement of a Palladium Peroxo Complex Adamo, Carlo; Amatore, Christian; Ciofini, Ilaria Journal of the American Chemical Society, Vol. 128, Issue 21 https://doi.org/10.1021/ja0569959	journal	May 2006
Protodeboronation of Tertiary Boronic Esters: Asymmetric Synthesis of Tertiary Alkyl Stereogenic Centers Nave, Stefan; Sonawane, Ravindra P.; Elford, Tim G. Journal of the American Chemical Society, Vol. 132, Issue 48 https://doi.org/10.1021/ja1084207	journal	November 2010
Distinguishing Between Pathways for Transmetalation in Suzuki−Miyaura Reactions Carrow, Brad P.; Hartwig, John F. Journal of the American Chemical Society, Vol. 133, Issue 7 https://doi.org/10.1021/ja1108326	journal	January 2011
Protodeboronation of (Hetero)Arylboronic Esters: Direct versus Prehydrolytic Pathways and Self-/Auto-Catalysis Hayes, Hannah L. D.; Wei, Ran; Assante, Michele Journal of the American Chemical Society, Vol. 143, Issue 36 https://doi.org/10.1021/jacs.1c06863	journal	August 2021
Potassium Trimethylsilanolate-Promoted, Anhydrous Suzuki–Miyaura Cross-Coupling Reaction Proceeds via the “Boronate Mechanism”: Evidence for the Alternative Fork in the Trail Delaney, Connor P.; Marron, Daniel P.; Shved, Alexander S. Journal of the American Chemical Society, Vol. 144, Issue 10 https://doi.org/10.1021/jacs.1c08283	journal	March 2022
A Comprehensive Discovery Platform for Organophosphorus Ligands for Catalysis Gensch, Tobias; dos Passos Gomes, Gabriel; Friederich, Pascal Journal of the American Chemical Society, Vol. 144, Issue 3 https://doi.org/10.1021/jacs.1c09718	journal	January 2022
Protodeboronation of Heteroaromatic, Vinyl, and Cyclopropyl Boronic Acids: pH–Rate Profiles, Autocatalysis, and Disproportionation Cox, Paul A.; Leach, Andrew G.; Campbell, Andrew D. Journal of the American Chemical Society, Vol. 138, Issue 29 https://doi.org/10.1021/jacs.6b03283	journal	July 2016
Structural, Kinetic, and Computational Characterization of the Elusive Arylpalladium(II)boronate Complexes in the Suzuki–Miyaura Reaction Thomas, Andy A.; Wang, Hao; Zahrt, Andrew F. Journal of the American Chemical Society, Vol. 139, Issue 10 https://doi.org/10.1021/jacs.6b13384	journal	March 2017
Base-Catalyzed Aryl-B(OH) ₂ Protodeboronation Revisited: From Concerted Proton Transfer to Liberation of a Transient Aryl Anion Cox, Paul A.; Reid, Marc; Leach, Andrew G. Journal of the American Chemical Society, Vol. 139, Issue 37 https://doi.org/10.1021/jacs.7b07444	journal	September 2017
Elucidating the Role of the Boronic Esters in the Suzuki–Miyaura Reaction: Structural, Kinetic, and Computational Investigations Thomas, Andy A.; Zahrt, Andrew F.; Delaney, Connor P. Journal of the American Chemical Society, Vol. 140, Issue 12 https://doi.org/10.1021/jacs.8b00400	journal	March 2018
Application of the Suzuki Reaction as the Key Step in the Synthesis of a Novel Atropisomeric Biphenyl Derivative for Use as a Liquid Crystal Dopant Cammidge, Andrew N.; Crépy, Karen V. L. The Journal of Organic Chemistry, Vol. 68, Issue 17 https://doi.org/10.1021/jo034652s	journal	July 2003
C7-Derivatization of C3-Alkylindoles Including Tryptophans and Tryptamines Loach, Richard P.; Fenton, Owen S.; Amaike, Kazuma The Journal of Organic Chemistry, Vol. 79, Issue 22 https://doi.org/10.1021/jo502062z	journal	November 2014
Use of Solution-Phase Vibrational Frequencies in Continuum Models for the Free Energy of Solvation Ribeiro, Raphael F.; Marenich, Aleksandr V.; Cramer, Christopher J. The Journal of Physical Chemistry B, Vol. 115, Issue 49 https://doi.org/10.1021/jp205508z	journal	December 2011
Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G. The Journal of Physical Chemistry B, Vol. 113, Issue 18, p. 6378-6396 https://doi.org/10.1021/jp810292n	journal	May 2009
Rates and Mechanism of the Formation of Zerovalent Palladium Complexes from Mixtures of Pd(OAc)2 and Tertiary Phosphines and Their Reactivity in Oxidative Additions Amatore, Christian; Carre, Emmanuelle; Jutand, Anny Organometallics, Vol. 14, Issue 4 https://doi.org/10.1021/om00004a039	journal	April 1995
Water facilitation of palladium-mediated coupling reactions Zhang, Han Cheng; Daves, G. Doyle Organometallics, Vol. 12, Issue 5 https://doi.org/10.1021/om00029a005	journal	May 1993
Evidence of the formation of zerovalent palladium from Pd(OAc)2 and triphenylphosphine Amatore, Christian; Jutand, Anny; M'Barki, Mohamed Amine Organometallics, Vol. 11, Issue 9 https://doi.org/10.1021/om00045a012	journal	September 1992
Formation of Palladium(0) Complexes from Pd(OAc) ₂ and a Bidentate Phosphine Ligand (dppp) and Their Reactivity in Oxidative Addition Amatore, Christian; Jutand, Anny; Thuilliez, Audrey Organometallics, Vol. 20, Issue 15 https://doi.org/10.1021/om0101137	journal	July 2001
The Difficulty of Coordinating Mutually trans Phosphine and Aryl Ligands in Palladium Complexes and Its Relation to Important Coupling Processes. Syntheses and Crystal Structures of a Family of Palladium Phosphino, Triflato, Perchlorato, and Aquo-2-(arylazo)aryl Complexes Vicente, José; Arcas, Aurelia; Bautista, Delia Organometallics, Vol. 16, Issue 10 https://doi.org/10.1021/om961094h	journal	May 1997
Fluoride-Catalyzed Reduction of Palladium(II) to Palladium(0)−Phosphine Complexes McLaughlin, Patrick A.; Verkade, John G. Organometallics, Vol. 17, Issue 26 https://doi.org/10.1021/om980490s	journal	December 1998
High-valent organometallic copper and palladium in catalysis Hickman, Amanda J.; Sanford, Melanie S. Nature, Vol. 484, Issue 7393 https://doi.org/10.1038/nature11008	journal	April 2012
Synthesis of hydroxyphthioceranic acid using a traceless lithiation–borylation–protodeboronation strategy Rasappan, Ramesh; Aggarwal, Varinder K. Nature Chemistry, Vol. 6, Issue 9 https://doi.org/10.1038/nchem.2010	journal	July 2014
Expanding the medicinal chemistry synthetic toolbox Boström, Jonas; Brown, Dean G.; Young, Robert J. Nature Reviews Drug Discovery, Vol. 17, Issue 10 https://doi.org/10.1038/nrd.2018.116	journal	August 2018
Phase transfer catalysts shift the pathway to transmetalation in biphasic Suzuki-Miyaura cross-couplings Shi, Yao; Derasp, Joshua S.; Maschmeyer, Tristan Nature Communications, Vol. 15, Issue 1 https://doi.org/10.1038/s41467-024-49681-4	journal	June 2024
SciPy 1.0: fundamental algorithms for scientific computing in Python Virtanen, Pauli; Gommers, Ralf; Oliphant, Travis E. Nature Methods https://doi.org/10.1038/s41592-019-0686-2	journal	February 2020
Selection of boron reagents for Suzuki–Miyaura coupling Lennox, Alastair J. J.; Lloyd-Jones, Guy C. Chem. Soc. Rev., Vol. 43, Issue 1 https://doi.org/10.1039/C3CS60197H	journal	January 2014
Copper-catalyzed protodeboronation of arylboronic acids in aqueous media Liu, Chun; Li, Xinmin; Wu, Yonghua RSC Adv., Vol. 4, Issue 97 https://doi.org/10.1039/C4RA11659C	journal	October 2014
Base-promoted silver-catalyzed protodeboronation of arylboronic acids and esters Liu, Chun; Li, Xinmin; Wu, Yonghua RSC Advances, Vol. 5, Issue 20 https://doi.org/10.1039/C4RA16323K	journal	January 2015
Carbon–hydrogen (C–H) bond activation at Pd ^IV : a Frontier in C–H functionalization catalysis Topczewski, Joseph J.; Sanford, Melanie S. Chemical Science, Vol. 6, Issue 1 https://doi.org/10.1039/C4SC02591A	journal	January 2015
A look at the density functional theory zoo with the advanced GMTKN55 database for general main group thermochemistry, kinetics and noncovalent interactions Goerigk, Lars; Hansen, Andreas; Bauer, Christoph Physical Chemistry Chemical Physics, Vol. 19, Issue 48 https://doi.org/10.1039/C7CP04913G	journal	January 2017
Automated exploration of the low-energy chemical space with fast quantum chemical methods Pracht, Philipp; Bohle, Fabian; Grimme, Stefan Physical Chemistry Chemical Physics, Vol. 22, Issue 14 https://doi.org/10.1039/C9CP06869D	journal	January 2020
Vessel effects in organic chemical reactions; a century-old, overlooked phenomenon Nielsen, Michael Martin; Pedersen, Christian Marcus Chemical Science, Vol. 13, Issue 21 https://doi.org/10.1039/D2SC01125E	journal	January 2022
Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy Weigend, Florian; Ahlrichs, Reinhart Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305 https://doi.org/10.1039/b508541a	journal	January 2005
Accurate Coulomb-fitting basis sets for H to Rn Weigend, Florian Physical Chemistry Chemical Physics, Vol. 8, Issue 9 https://doi.org/10.1039/b515623h	journal	January 2006
Palladium catalyzed Suzuki C–C couplings in an ionic liquid: nanoparticles responsible for the catalytic activity Fernández, Fernando; Cordero, Beatriz; Durand, Jérôme Dalton Transactions, Issue 47 https://doi.org/10.1039/b713449e	journal	January 2007
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Pre-transmetalation intermediates in the Suzuki-Miyaura reaction revealed: The missing link Thomas, A. A.; Denmark, S. E. Science, Vol. 352, Issue 6283 https://doi.org/10.1126/science.aad6981	journal	April 2016
Closed-loop optimization of general reaction conditions for heteroaryl Suzuki-Miyaura coupling Angello, Nicholas H.; Rathore, Vandana; Beker, Wiktor Science, Vol. 378, Issue 6618 https://doi.org/10.1126/science.adc8743	journal	October 2022
Delocalized, asynchronous, closed-loop discovery of organic laser emitters Strieth-Kalthoff, Felix; Hao, Han; Rathore, Vandana Science, Vol. 384, Issue 6697 https://doi.org/10.1126/science.adk9227	journal	May 2024
Electrophilic Displacement Reactions: xv. Kinetics and Mechanism of the Base-Catalyzed Protodeboronation of Areneboronic Acids Kuivila, Henry G.; Reuwer Jr., Joseph F.; Mangravite, John A. Canadian Journal of Chemistry, Vol. 41, Issue 12 https://doi.org/10.1139/v63-451	journal	December 1963
GoodVibes: automated thermochemistry for heterogeneous computational chemistry data Luchini, Guilian; Alegre-Requena, Juan V.; Funes-Ardoiz, Ignacio F1000Research, Vol. 9 https://doi.org/10.12688/f1000research.22758.1	journal	January 2020
kallisto: A command-line interface to simplify computational modelling and the generation of atomic features Caldeweyher, Eike Journal of Open Source Software, Vol. 6, Issue 60 https://doi.org/10.21105/joss.03050	journal	April 2021