Publications

244. Kays, L.: Intano Jr., I.; Wachtel, Z.; Russell, V.; Mosey, R.A.; Carroll, B.; Lopez, L.; Phillips, M.; Sanford, M.S.*; Minteer, S.D.* “Electrochemical Alcohol Oxidation: An Accessible Electrosynthesis Experiment for Sophomore-Level Organic Chemistry” J. Chem. Educ. 2026

Three scientists hold jars: left—an electrocatalytic setup; center—a color-changing solution with electrodes; right—an infographic with chemical structures. Labels read Electrocatalytic Alcohol Oxidation, Visualization, and Structure-Reactivity.

243. Noel, A. N.; Greco, S. G.; Horikawa, M.; Spiller, T. E.; Nichols, D. L.; Witek, J. A.; Brooks, A. F.; Scott, P. J. H.*; Sanford, M. S.* “18F Labelling of (Hetero)aryl Halides via Sequential Miyaura Borylation/Copper Mediated Radiofluorination”
Chem. Sci. 2026,

A schematic shows a two-step reaction converting aryl halides to 18F-labeled arenes via borylation and copper-mediated radiofluorination, with key features and relevant publications listed below the diagram.

242. McCarthy, C.; Müller, M.; Ma, R.; Battisti, M. U.; Wright, J.; Webb, E.; Sanford, M. S.*; Herth, M.; Scott, P. J. H.* “Friedel-Crafts-Type Electrophilic Radiocyanation of (Hetero)Arenes” Org. Lett. 2026, 28, 2421-2426

Chemical reaction scheme: An aromatic compound with [M] reacts with 11C-labeled cyanide, producing Ar-11CN. Notes: shelf-stable precursors, C-H activation, and transition metal-free process.

241. Wright, J. S.; Ma, R.; McCarthy, C. J.; Kaup, G.; George, E.; Priest, J. D.; Webb. E. W.; Cheng, K.; Bowden, G. D.; Brooks, A. F.; Shao, X.; Sanford, M. S.*; Scott, P. J. H.* “Organosilicon Precursors for Efficient Aromatic Copper-Mediated Radiocyanation” Chem 2026, 12, 102707

A chemical reaction scheme showing pathways for radiolabeling molecules using silicon, copper, fluorine, and cyanide isotopes, with key reaction components and benefits listed in a blue text box below.

240. Carneiro, S. N.; Bento, J. V.; Zimmerman, P. M.; Sanford, M. S.* “Deaminative Fluorination of Sulfonamides via Aminocyclopropenium Activation” Org. Lett. 2026, 28, 15, 4801–4805

A diagram shows a sulfonamide converting to a sulfonyl fluoride using KF, via a cyclopropenium-activated isolable RSO2+ synthon. Key points: 22 examples, bioactive sulfonamides, tosyl deprotection.

239. Rodrigo, S.; Sanford, M. S.*; Luo, L. “Electrochemical Trifluoromethylchlorosulfonylation of Alkenes via Copper-Mediated SO_CI Radical Transfer” Adv. Syn. Catal. 2025, 367,

238. Wolesensky, R. M.; Morales-Colon, M. T.; Sanford, M. S.* “Initiation of Palladium Precatalysts: Efficiency and Product Selectivity as a Function of Ligand, Substrate, and Reaction Conditions” ACS Catal. 2025, 15, 21, 18758–18768

Reaction scheme: A Pd(II) complex reacts with ArB(OH)₂, base, and solvent to give a PR₃–Pd⁰ complex and organic products. The study examines yield, rate, and products as a function of PR₃, Ar, base, and solvent.

237. Hall, J. R.; Romer, N. P.; Spiller, T. E.; Sigman, M. S.; Sanford, M. S.* “Pd-catalyzed desulfonylative fluorination of electron-deficient (hetero)aryl sulfonyl fluorides” Chem. Sci., 2025, 16, 18936-18941

A chemical reaction scheme shows a sulfonyl fluoride converted to a fluoroarene using Pd₂(dba)₃ and a phosphine ligand in toluene, with SO₂ as a byproduct. Key features: no exogenous fluoride, telescoped S_NAr, data science methods.

236. Wachtel, Z. E.; Thedford, J.; Carneiro, S. N.; Sanford, M. S.* “Flash Communication: Cyclopropenium Radical Dication as an Outer-Sphere Oxidant for Group 10 Metal Complexes” Organometallics 2025, 44, 18, 2003–2006

A chemical reaction scheme: a metal complex reacts with a red, three-pronged nitrogen molecule, then forms an ion pair, followed by product formation with an aromatic ring bonded to a blue X group.

235. Brandes, D. S.; Lasky, M. R.; Lisboa A. V. R. D.; Liu, E.; Remy M. S.; Sanford, M. S.* “Photoactivation of Electron Donor–Acceptor Complexes for C(sp2)–H Amination of Arenes Using an Organocatalytic Acceptor”
Org. Lett. 2025, 27, 36, 10011–10015

A reaction scheme: an aromatic aldehyde reacts with a secondary amine in the presence of a pyridinium catalyst, acid, oxygen, and light to form an aryl amine, proceeding via a catalytic acceptor intermediate.

234. Gu, F.; Lalloo, N.; Wearing, E. R.; Sanford, M. S.* “Palladium-Catalyzed Decarbonylative CH Difluoromethylation of Azoles” Org. Lett. 2025, 27, 30, 8144–8148

Chemical reaction: Pyridine reacts with a trifluoromethyl-substituted anhydride in the presence of a Pd catalyst and XantPhos, releasing CO and forming a trifluoromethylated pyridine product.

233. Reich, S. M.; Lasky, M. R.; Sanford, M. S.* “Visible-Light SNAr Pyridination of Aryl Halides and Triflates with Acridine-Lewis Acid Photocatalysts” J. Org. Chem. 2025, 90, 29, 10332–10337

Reaction scheme: Aromatic compound with a leaving group reacts with pyridine under blue light (440 nm) and an in situ photocatalyst to form a pyridinium salt; photocatalyst structure shown in a box. LG = Cl, Br, OTf.

232. Bunnell, A.; Milbauer, M. W.; Bento, J. V.; Taimoory, S. M.; Zimmerman, P. M.; Kalyani, D.; Piou, T.*; Sanford, M. S.* “Mechanism-Guided Development of Directed C–H Functionalization of Bicyclo[1.1.1]pentanes”
J. Am. Chem. Soc. 2025, 147, 23, 20159–20167

Chemical reaction scheme: a bicyclic amide reacts via palladium catalyst and Ar• radical, then is esterified, forming a methoxy-substituted bicyclic product. A 3D molecular structure is shown above the reaction arrow.

231. Thedford, J.; Sanford, M. S.* “Mechanistic Organometallic Studies Drive Reagent Selection and Catalyst Design for the Palladium-Catalyzed Trifluoromethylthiolation of Aryl Electrophiles” Organometallics 2025, 44, 11, 1210-1216

Reaction scheme: An aryl halide reacts with Pd(0) catalyst and MSCF3 to form an aryl-SCF3 product. Mechanistic study box shows L–Pd(II) aryl intermediate. Text: detailed studies of role of M, L, and Pd source..

230. Liu, E.; Reich, S. M.; Tanwar, M.; Neurock, M.*; Luo, L.; Sanford, M. S.* “Electro-oxidative Deoxyfluorination of Arenes with NEt3·3HF” J. Org. Chem 2025, 90, 5, 1889–1894

Reaction scheme: An aryl ether with CF3 and F groups undergoes electrooxidative deoxyfluorination (MeNO2:HFIP 9:1, 1.5 M NEt3·3HF, RVC, Pt) to yield a fluorinated arene.

229. Nolan, L. E.; Qu F.; Sanford M. S.* “Exploration of Organometallic Cobalt Intermediates in an Aminoquinoline-Directed Dehydrogenative Dimerization Reaction” Organometallics 2024, 43, 19, 2165–2168

Chemical reaction scheme showing a fluorinated compound reacting with a cobalt catalyst, base, and oxidant to form a new compound with two indole groups added, via cobalt intermediates.

228. Spiller, T. E.; Donabauer, K.; Brooks, A. F.; Witek, J. A.; Bowden, G. D.; Scott, P. J. H; Sanford, M. S.* “Room-Temperature Photochemical Copper-Mediated Fluorination of Aryl Iodides” Org. Lett. 2024, 26, 30, 6433–6437

Reaction scheme: An aryl iodide reacts with Cu(II), Ag, and 18/19F under visible light at room temperature to yield an aryl fluoride, showing Cu(III) as an intermediate.

227. Nolan, E. L.; Blythe, I. M.; Qu, F.; Kampf, J. W.; Sanford, M. S.* “Speciation and Reactivity of Mono- and Binuclear Ni Intermediates in Aminoquinoline-Directed C–H Arylation and Benzylation” J. Am. Chem. Soc. 2024, 146, 26, 18128–18135

A chemical scheme showing Ni(III)-mediated arylation and benzylation reactions with labeled intermediates, reaction pathways, and key products formed in acetone and toluene. Includes reaction highlights as symbols at the bottom.

226. Lasky, M. R.; Liu, E.; Remy, M. S.; Sanford, M. S.* “Visible-Light Photocatalytic C–H Amination of Arenes Utilizing Acridine–Lewis Acid Complexes” J. Am. Chem. Soc. 2024, 146, 21, 14799-14806

A reaction scheme showing aryl aldehyde and nitrogen nucleophile forming an amine using a Lewis acid catalyst, a blue LED light, and oxygen. Photocatalysts and Lewis acids are shown, with reaction conditions and key notes beneath.

225. Carneiro, S. N.; Lafoon, J. D.; Luo, L.*; Sanford,M. S.* “Benchmarking Trisaminocyclopropeniums as Mediators for Anodic Oxidation Reactions” J. Org. Chem. 2024, 89, 9, 6389–6394

Three chemical structures labeled A, B, and C are shown. The graph displays three corresponding cyclic voltammograms, with current vs. potential curves labeled to match each compound.

224. Duran-Camacho, G.; Bland, D. C.; Li, F.; Neufeldt, S. R.*; Sanford, M. S.* “Nickel-Based Catalysts for the Selective Monoarylation of Dichloropyridines: Ligand Effects and Mechanistic Insights” ACS Catal. 2024, 14, 9, 6404-6412

A reaction scheme showing a Ni-catalyzed arylation of a dichloropyridine, leading to different products via ligand substitution or oxidative addition, depending on phosphine ligands used.

223. Webb, E. W.; Cheng, K.; Winton W. P.; Klein, B. J. C.; Bowden, G. D.; Horikawa, M.; Liu, S. W.; Wright J. S.; Verhoog, S; Kalyani, D.; Wismer, M.; Krska, S. W.; Sanford, M. S.*; Scott, P. J. H.* “Development of High-Throughput Experimentation Approaches for Rapid Radiochemical Exploration” J. Am. Chem. Soc. 2024, 146, 15, 10581–10590

Diagram shows a high-throughput radiochemistry workflow: a reaction with Cu and [18F], commercial equipment with stacked plates, separation of ionic 18F– and product, and a colorful data grid for rapid analysis.

222. Lisboa, A. V. R. D.; Duran-Camacho, G.; Ehrlacher, A. K.; Lasky M. R.; Sanford, M. S* “Deoxyfluorination of Carboxylic Acids via an In Situ Generated Trifluoromethoxide Salt” Org. Lett. 2023, 25, 50, 9025-9029

A chemical reaction scheme showing deoxyfluorination using an OCF3 reagent, a carboxylic acid, and mild conditions (25°C, 1 h) to yield a product with a fluorine atom. Three reaction benefits are listed at right.

221. Pancoast, A. R.; Mccormack, S.; Galinat, S.; Walser-Kuntz, R.; Jett, B.; Sanford, M. S.; Sigman, M. S. “Data Science Enabled Discovery of a Highly Soluble 2,2’-Bipyrimidine Anolyte for Application in a Flow Battery” 
Chem. Sci. 2023, 14, 13734-13742

A chemical reaction scheme for a battery is on the left, with a graph on the right showing stable capacity and Coulombic efficiency over 100 cycles. Capacity fade is 4.5%, Coulombic efficiency is 99%.

220. Horikawa, M.; Joy, S. T.; Sharninghausen, L. S.; Shao, X.; Mapp, A. K.; Scott, P. J. H.; Sanford, M. S. “C-H Radiocyanation of Bioactive Molecules Via Sequential Iodination/Copper-Mediated Cross-Coupling” Chem. Sci. 2023, 14, 12068-12072

A chemical reaction scheme showing the radiocyanation of an aromatic amide, where a hydrogen atom is replaced with a ^11CN group using I+ and ^11CN as reagents.

219. Jett, B.; Flynn, A.; Sigman, M.; Sanford, M. S.* “Identifying Structure-Function Relationships to Modulate Crossover in Nonaqueous Redox Flow Batteries” J. Mater. Chem. A, 2023, 11, 22288-22294

Flowchart showing chemical structures, a graph of crossover rates, a QSPR modeling plot, and a tethered molecule. Text notes slow crossover and over 20 molecules tested.

218. Bunnell, A.; Lalloo, N.; Brigham, C., Sanford, M. S.* ”Palladium-Catalyzed Decarbonylative Coupling of (Hetero) Aryl Boronate Esters with Difluorobenzyl Glutarimides” Org. Lett. 2023, 25, 41, 7584-7588

Chemical reaction: A boronic ester and a fluorinated aromatic compound undergo a palladium-catalyzed reaction to produce a biaryl compound with two fluorines and carbon monoxide as a byproduct.

217. Zhang, W.; Walser-Kuntz, R.; Tracy, J. S.; Shee, J.; Chen, G.; Helms, B. A.; Schramm, T. K.; Head-Gordon, M.; Sanford, M. S.; Toste, F. D. “Indolo[2.3-b]quinoxaline as a Low Reduction Potential and High Stability Anolyte for Non-Aqueous Redox Flow Battery” J. Am. Chem. Soc. 2023, 145, 34, 18877-18887

Chemical structure modifications highlighted, with key properties listed: low reduction potential (E1/2 = –2.01 V vs Fc/Fc+), high stability (0.056% capacity fade/hour), and high solubility (>2.7 M in acetonitrile).


216. Blythe, I. M.; Xu, J.; Fernandez-Odell, J. S., Kampf, J.; Bowring, M.A.; Sanford, M. S.* “Characterization and Reactivity of Copper(II) and Copper(III) σ-Aryl Intermediates in Aminoquinoline-Directed C–H Functionalization” 
J. Am. Chem. Soc. 2023, 145, 33, 18253-18259

A reaction scheme shows a copper complex with quinone ligands reacting to form products, with or without NO2-. Product structures and the departing quinone are highlighted in red. FcBF4 and no exogeneous nucleophile are labeled.

215. Kassie, A. A.; Castro De la Torre, I. Y.; Remy M. S.; Mukhopadhyay S.; Kampf, J.; Qu, F.; Sanford, M. S.* “Metal Identity Effects in the Pincer Complex-Catalyzed Dehydrogenative Coupling of Formamides with Alcohols to Form Carbamates” Organometallics 2023, 42, 10, 1030-1036

Aldehyde reacts with alcohol in presence of a metal catalyst, forming an acetal. Boxed area shows two proposed metal-alkoxide intermediates. Caption notes the impact of metal choice (Fe, Ru, Mn) on the reaction.

214. Walser-Kuntz, R.; Yan, Y.; Sigman, M. S.*; Sanford, M. S.* “A Physical Organic Chemistry Approach to Developing Cyclopropenium-Based Energy Storage Materials for Redox Flow Batteries” Acc. Chem. Res 2023, 56 ,10, 1030-1036

Timeline of chemical structures (with various side groups) showing developments from 2017 to 2022 in redox potential, solubility, multi-electron capacity, and cross-over resistance, labeled with brief descriptors.

213. Aguilera, E. Y.; Liu, E.; Thullen, S. M.; and Sanford, M. S.* “Transannular Functionalization of Multiple C(sp3)–H Bonds of Tropane via an Alkene-Bridged Palladium(I) Dimer” Organometallics 2023, 42, 8, 627-631

A chemical reaction scheme shows a starting material with a cyclopropane ring, reacting with Pd catalyst, forming a Pd dimer complex, then producing a product where X replaces the original cyclopropane position.

212. Hall, J. R.; Blythe, I. M.; Sharninghausen, L. S.; Sanford, M. S.* “Copper-Mediated Fluoroalkylation of Aryl Bromides and Chlorides Enabled by Directing Groups” Organometallics 2023, 42, 7, 543-546

A copper complex with RF group reacts with a benzene ring containing a directing group and halide to form a new aryl compound with RF and DG groups; DG and RF definitions shown at right.

211. Kaur, T.; Shao, X.; Horikawa, M.; Sharninghausen, L. S.; Preshlock, S.; Brooks, A. F.; Henderson, B. D.; Koeppe, R. A; DaSilva, A. F.; Sanford, M. S*; Scott, P. J. H* “Strategies for the Production of [11C]LY2795050 for Clinical Use” 
OPR&D 2023, 27, 2, 373-381

A chemical scheme shows the synthesis of [11C]LY2795050, a κ-opioid receptor antagonist, and a PET brain scan image indicating its clinical imaging use.

210. Lalloo, N.; Brigham, C. E.; Bunnell, A.; Sanford, M. S. “Mechanism-Driven Development of Group 10 Metal-Catalyzed Decarbonylative Coupling Reactions” Acc. Chem. Res 2022, 55, 23, 3430-3444

A schematic shows a nickel or palladium-catalyzed reaction replacing RX with R1, along with three example molecules in red, blue, and green, highlighting modular, tunable, and atom-economical features.

209. Yan, Y.; Zhang, L.; Walser-Kuntz, R.; Vogt, D. B.: Sigman, M. S.; Yu, G.; Sanford, M. S. “Benzotriazoles as Low-Potential Anolytes for Non-aqueous Redox Flow Batteries” Chem. Mater. 2022, 34, 23, 10594-10605

Two chemical structures: left shows a benzothiazole (with S), labeled previous work. Right shows a benzotriazole (with N–R), labeled this work, with added text noting improved potential, solubility, and stability.

208. Milbauer, M. W.; Kampf, J. W.; Sanford, M. S. “Nickel(IV) Intermediates in Aminoquinoline-Directed C(sp2)–C(sp3) Coupling” J. Am. Chem. Soc. 2022, 144, 46, 21030-21034

A chemical reaction scheme shows Ni-catalyzed arylation using fluorinated reagents, forming a Ni complex and releasing a fluorinated product; includes reaction conditions and a 3D molecular structure.

207. Vaid, T. P.; Cook, M.; Scott, J.; Carazo, M. B.; Ruchti, J.; Minteer, S.; Sigman, M.; McNeil, A.; Sanford, M. S. “Theoretical and Experimental Investigation of Functionalized Cyanopyridines Yield an Extremely Low-Reduction-Potential Anolyte for Nonaqueous Redox Flow Batteries” Chem. Eur. J. 2022, 28, 70

Two chemical structures: a blue neutral molecule on the left and a red anion radical on the right, with reversible electron transfer indicated. A boxed label above reads E1/2 = −2.50 V vs Fc+/0.

206. Lasky, M. R.; Salvador, T. K.; Mukhopadhyay, S.; Remy, M. S.; Vaid, T. P.; Sanford, M. S. “Photochemical C(sp2)–H Pyridination via Arene–Pyridinium Electron Donor–Acceptor Complexes” Angew. Chem. Int. Ed. 2022, 61, 46

Scheme showing pyridine plus aniline forms an EDA complex that, with O2, HBF4·Et2O, and black light in MeCN, yields a pyridine-aniline adduct. Mechanism inset highlights donor-acceptor roles and SET process.

205.  Sharninghausen, L. S.; Preshlock, S.; Joy, S. T.; Horikawa, M.; Shao, X.; Winton, W. P.; Stauff, J.; Kaur, T.; Koeppe, R. A.; Mapp, A. K.; Scott, P. J. H.; Sanford, M. S. “Copper Mediated Radiocyanation of Unprotected Amino Acids and Peptides”  
 J. Am. Chem. Soc. 2022, 144, 16, 7422-7429

Diagram showing ^11C-labeling of a peptide, injection into a subject, and brain imaging. Notes highlight easy labeling, minimal peptide change, flexible insertion, and successful PET analysis.

204.  Kim, D.; Sanford M.S.; Vaid, T.P.; McNeil, A. “A Nonaqueous Redox-Matched Flow Battery with Charge Storage in Insoluble Polymer Beads” Chem. Eur. J. 2022, 28, 25

Diagram of a redox flow battery: anolyte and catholyte tanks with colored ions flow through a central cell, exchanging electrons via mediators. Text below highlights polymer-supported redox molecules and matched mediators.

203. Yan, Y.; Walser-Kuntz, R.; Sanford M.S. “Targeted Optimization of Phenoxazine Redox Center for Nonaqueous Redox Flow Batteries” ACS Materials 2022, 4, 4, 733-739

Molecule structure labeled catholyte for non-aqueous redox flow batteries; graph shows discharge capacity (black, slightly decreasing) and coulombic efficiency (red, stable near 100%) over 200 cycles.

202. Lalloo, N.; Malapit, C.A.; Taimoory, S.M.; Brigham, C.E.; Sanford, M. S.* “Decarbonylative Fluoroalkylation at Palladium(II): From Fundamental Organometallic Studies to Catalysis” J. Am. Chem. Soc. 2021, 143, 44, 18617-18625

Reaction scheme: Ar-F and F2HC=O form Ar-CHF2 using Pd catalyst and SPhos at 150°C. A Pd complex intermediate is shown, with pathways highlighting oxidative addition and CO loss.

201. Yan, Y.; Vogt, D.B.; Vaid, T.P.; Sigman, M.S.; Sanford M.S. “Development of High Energy Density Diaminocyclopropenium-Phenothiazine Hybrid Catholytes for Non-Aqueous Redox Flow Batteries” 
Angew. Chem. Int. Ed. 2021, 60, 52, 27039-27045

Chemical reaction scheme: a naphthalene-thiophene derivative is converted to a methoxy-substituted, nitrogen-containing heterocycle with text highlighting high solubility, high potential, and two-electron transfer abilities.

200. Lee, S.J.; Morales-Colon M.T.; Brooks, A.F.; Wright, K.J.; Scott, P.J.H.*; Sanford, M.S.* “SNAr Radiofluorination with In Situ Generated [18F] Tetramethylammonium Fluoride” J. Org. Chem. 2021, 86, 20, 14121-14130

A chemical scheme shows fluorination of aromatic rings using [18F]KF, K2.2.2, Me4NHCO3, yielding [18F]Me4NF. X = Cl, NO2, OTf; Y = CH, N. Fluorinated products formed in up to 97% yield (25 examples).

199. Yan, Y.; Robinson, S.G.; Vaid, T.P.; Sigman, M.S.; Sanford M.S.* “Simultaneously Enhancing the Redox Potential and Stability of Multi-Redox Organic Catholytes by Incorporating Cyclopropenium Substituents” J. Am. Chem. Soc. 2021, 143, 33, 13450-13459

A chemical structure on the left labeled one-electron transfer, low potential points to a larger structure on the right labeled two-electron transfer, extremely high potential..

198. Mantell, M.A.; Lasky, M.R.; Lee, M.; Remy, M.; Sanford M.S. “SNAr and C–H Amination of Electron Rich Arenes with Pyridine as a Nucleophile Using Photoredox Catalysis” Org. Lett. 2021, 23, 13, 5213-5217

Reaction scheme showing a methoxy-chlorobenzene reacting with a photocatalyst under blue light to give different products with LiPF6 under anaerobic or aerobic conditions; products feature blue-highlighted nitrogen atoms.

197. Duran-Camacho, G.; Ferguson, D.M.; Kampf, J.W.; Bland, D.C.; Sanford M.S. “Isolable Pyridinium Trifluoromethoxide Salt for Nucleophilic Trifluoromethoxylation” Org. Lett. 2021, 23, 13, 5138-5142

A chemical reaction scheme showing conversion of a nitrobenzene with OCF3 to an SN2 reagent, plus a 3D ball-and-stick molecular model of the product on the right. Text highlights its use in SN2 reactions.

196. Morales-Colon, M.T.; See, Y.Y; Lee, S.J.; Scott, P.J.H; Bland, D.C; Sanford M.S. “Tetramethylammonium Fluoride Alcohol Adducts for SNAr Fluorination” Org. Lett. 2021, 23, 11, 4493–4498

A chemical reaction scheme showing a heteroaromatic ring with X converting to the same ring with F, using Me₄NF and t-AmylOH in DMSO at 80°C.

195. Wright, J.S.; Sharninghausen, L.S.; Preshlock, S.; Brooks A. F.; Sanford M.S.*; Scott, P.J.H.* “Sequential Ir/Cu-Mediated Method for the Meta-Selective C–H Radiofluorination of (Hetero)Arenes,” J. Am. Chem. Soc. 2021, 143, 6915-6921

Reaction scheme for radiofluorination of GW405833: Ir-catalyzed borylation produces a boronate intermediate, which is then fluorinated with copper to yield the ^18F-labeled product (60 ± 3% RCY). Key features are highlighted.

194. Aguilera, E.Y.; Sanford, M.S. “Palladium‐Mediated Cγ−H Functionalization of Alicyclic Amines,” 
Angew. Chem. Int. Ed. 2021, 60, 20, 11227-11230

A diagram showing a benzene ring with a directing group (DG) and different substituents: F, Cl, Br, I, NR₂, SPh₂, BPIn₂, and OAc, labeled under each structure. An inset highlights a reaction mechanism.

193. Yan, Y.; Vaid T.P.; Sanford, M.S.*“Bis(diisopropylamino)cyclopropenium-arene Cations as High Oxidation Potential and High Stability Catholytes for Non-aqueous Redox Flow Batteries,” J. Am. Chem. Soc. 2020, 10, 17564–17571

A chemical structure is modified via molecular design and computational analysis, resulting in a new structure with a trifluoromethyl and carbonyl group. Three benefits are listed in red text.

192. See, Y.; Morales-Colon, M.T.; Bland, D.C.; Sanford, M.S. “Development of SNAr Nucleophilic Fluorination: A Fruitful Academia-Industry Collaboration,” Acc. Chem. Res. 2020, 10, 2372–2383

Timeline of fluorination methods from 2013 to 2020, showing chemical structures, reagents, improvements, and new transformations from CsF to Me4NF and Me4N⁺/SO2F2, inspired by industrial applications.

191. Brigham, C.; Malapit, C.; Lalloo, N.; Sanford, M.S. “Nickel-Catalyzed Decarbonylative Synthesis of Fluoroalkyl Thioethers,” ACS Catalysis. 2020, 10, 8315-8320

A scheme shows decarbonylative fluorothiolations using fluoroalkyl carboxylic acids and thiols, catalyzed by nickel. Key features: inexpensive, stable, non-toxic, and compatible with aryl/alkyl thiols.

190. Wright, J.; Kaur, T.; Preshlock, S.; Tanzey, S.; Winton, W.; Sharninghausen, L.; Weisner, N.; Brooks, A.; Sanford, M.S.; Scott, P. “Copper-mediated late-stage radiofluorination: five years of impact on preclinical and clnical PET imaging,”
Clinical and Translational Imaging 2020, 8, 167-206

189. Sharninghausen, L.S.; Brooks, A.F.; Winton W.; Makaravage, K.J.; Scott, P.J.H.; Sanford, M.S. “NHC-Copper Mediated Ligand-Directed Radiofluorination of Aryl Halides,” J. Am. Chem. Soc. 2020, 142, 16, 7362-7367

A chemical reaction scheme shows a copper-catalyzed fluorination, converting an aryl halide into a fluorinated compound, leading to the synthesis of ^18F-PH-089 (MK-2 inhibitor).

188. See, Y.Y.; Sanford, M.S.“C-H Amination of Arenes with Hydroxylamine,” Org. Lett. 2020, 22, 8, 2931–2934

Chemical reaction scheme showing a methylated naphthalene derivative reacting with hydroxylamine to form an aminated product, which is then converted to tamibarotene, a carboxamide compound.

187. Malapit, C.A.; Borrell, M; Milbauer, M.W.; Brigham, C.E.; Sanford, M.S. “Nickel-Catalyzed Decarbonylative Amination of Carboxylic Acid Esters,” J. Am. Chem. Soc. 2020, 142, 13, 5918-5923

A schematic of a decarbonylative amination reaction using Ni catalysis. Two chemical structures react to form a product, with a nickel complex as catalyst. Mechanistic structures are shown below with labeled ligands.

186. Shrestha, A.; Hendriks, K.; Sigman, M.; Minteer, S.; Sanford, M.S. “Realization of an Asymmetric Non‐Aqueous Redox Flow Battery through Molecular Design to Minimize Active Species Crossover and Decomposition,” 
Chemistry – A European Journal 2020, 26, 24, 5369-5373

A graph shows improved battery capacity retention after molecular redesign of electrolytes, with less than 5% decay for next-gen versus 62% decay for first-gen. Chemical structures and checklists highlight enhanced features.

185. Bour, J.; Pronay, R.; Canty, A.; Kampf, J.; Sanford, M.S. “Oxidatively Induced Aryl-CF3 Coupling at Diphosphine Nickel Complexes,” Organometallics 2019, 39, 1, 3-7

A nickel complex with a blue CF3 group reacts with ferrocenium hexafluorophosphate at room temperature to yield trifluorotoluene, highlighting the transfer of the CF3 group to benzene.

184. Roy, P.; Bour, J. R.; Sanford, M. S. “Catalytically Relevant Intermediates in the Ni-Catalyzed C(sp2)–H and C(sp3)–H Functionalization of Aminoquinoline Substrates,” J. Am. Chem. Soc. 2019, 141, 17382-17387

Chemical reaction scheme: A Ni(II) complex reacts with AgOTf to form a Ni(III) complex, which then reacts with an organic molecule at 140°C. A molecular structure model is shown on the right.

183. Mossine, A. V.; Tanzey, S. S.; Brooks, A. F.; Makavarage, K. J.; Ichiishi, N.; Miller, J.; Henderson, B. D.; Skaddan, M.; Sanford, M. S.; Scott, P. J. H. “One-Pot Synthesis of High Specific Activity 6-[18F]Fluoro-L-DOPA Suitable for Human Use by Cu-Mediated Fluorination of a Bpin Precursor,” Org. Biomol. Chem. 2019, 17, 8701-8705

Chemical reaction scheme showing the synthesis of [18F]FDOPA from a protected precursor using [18F]TBAF and CuPy4. Notes indicate good yield, easy automation, mild deprotection, and clinical validation.

182. Roberts, C. C.; Chong, E.; Kampf, J. W.; Canty, A. J.; Ariafard, A.; Sanford, M. S. “Nickel(II/IV) Manifold Enables Room Temperature C(sp3)–H Functionalization,” J. Am. Chem. Soc. 2019, 141, 49, 19513–19520

A catalytic cycle showing Ni(II) species for oxidative C–H activation, forming Ni(IV) intermediate, then reductive elimination with a nucleophile yields product and regenerates Ni(II) under mild conditions.

181. Thompson, S.; Lee, S. J.; Jackson, I. M.; Ichiishi, N.; Brooks, A. F.; Sanford, M. S.; Scott, P. J. H. “Synthesis of [18F]-y-fluoro-a,B-unsaturated Esters and Ketones via Vinylogous 18F-fluorination of a-Diazoacetates with [18F]AgF,”  Synthesis 2019, 51, 4401-4407

A diagram showing α-diazoacetate precursors undergoing vinylogous ^18F-fluorination to yield ^18F-fluoro-α,β-unsaturated esters/ketones, including aromatic, aliphatic, and difluorinated derivatives with 2–44% yield.

180. Malapit, C. A.; Bour, J. R.; Laursen, S. R.; Sanford, M. S. “Mechanism and Scope of Nickel-Catalyzed Decarbonylative Borylation of Carboxylic Acid Fluorides,” J. Am. Chem. Soc. 2019, 141, 17322-17330

A schematic shows a CO2H to F transformation, nickel catalysis, and B(OR)2 addition. An inset displays a Ni catalyst structure labeled as an air-stable, transmetallation-active intermediate.

179. Meucci, E. A.; Ariafard, A.; Canty, A. J.; Kampf, J. W.; Sanford, M. S. “Aryl–Fluoride Bond-Forming Reductive Elimination from Nickel(IV) Centers,” J. Am. Chem. Soc. 2019, 141, 13261-13267

Diagram showing Ni(IV)-F fluorination: various Ni(II) complexes convert to a Ni(IV)-F species, which transfers fluorine to an aromatic group, forming an aryl fluoride and regenerating Ni(II).

178. Yan, Y.; Robinson, S. G.; Sigman, M. S.; Sanford, M. S. “Mechanism-Based Design of a High-potential Catholyte Enables a 3.2 V All-organic Non-aqueous Redox Flow Battery,” J. Am. Chem. Soc. 2019, 141, 15301-15306

Graph of discharge capacity vs. cycle number, showing stable capacity over 150 cycles. Includes chemical structures, redox reaction, and key features, such as high potential and efficiency, for all-organic NRFB.

177. Meucci, E. A.; Nguyen, S. N.; Camasso, N. M.; Chong, E.; Ariafard, A.; Canty, A. J.; Sanford, M. S. “Nickel(IV)-Catalyzed C–H Trifluoromethylation of (Hetero)Arenes,” J. Am. Chem. Soc. 2019, 141, 12872-12879

A chemical reaction scheme shows an aromatic compound reacting with a CF3 source and a Ni(IV) catalyst to yield an aryl-CF3 product at room temperature using 5 mol% catalyst.

176. Ferguson, D. M.; Melvin, P. R.; Sanford, M. S. “Deoxyfluorination of (Hetero)aryl Aldehydes Using Tetramethylammonium Fluoride and Perfluorobutanesulfonyl Fluoride or Trifluoromethanesulfonic Anhydride,”
 Isr. J. Chem. 2019, 51, 1-5

Flowchart diagrams showing previous work, a proposed mechanism, and current work on aryl sulfonyl fluoride synthesis, highlighting the roles of leaving groups and electron withdrawing groups. Chemical structures and reaction arrows are included.

175. Robinson, S. G.; Yan, Y.; Hendriks, K. H.; Sanford, M. S.; Sigman, M. S. “Developing a Predictive Solubility Model for Monomeric and Oligomeric Cyclopropenium Flow Battery Catholytes,” J. Am. Chem. Soc. 2019, 141, 10171-10176

Flowchart showing monomer solubility measurement, model prediction (scatter plot of predicted vs. measured solubility), and predicted solubility for a new dimer structure.

174. Verhoog, S.; Brooks, A. F.; Winton, W. P.; Viglianti, B. L.; Sanford, M. S.; Scott, P. J. H. “Ring-Opening of Epoxides with [18F]FeF Species to Produce Fluorohydrin PET Imaging Agents,” Chem. Commun. 2019, 55, 6361-6364

A chemical reaction shows a steroid with a ketone converting to a labeled ^18F alcohol using [^18F]F^−, Fe(acac)_3, dioxane at 120°C for 20 minutes; ^18F is highlighted in red.

173. Bour, J. R.; Ferguson, D. M.; McClain, E. J.; Kampf, J. W.; Sanford, M. S. “Connecting Organometallic Ni(III) and Ni(IV): Reactions of Carbon-Centered Radicals with High-Valent Organonickel Complexes,” J. Am. Chem. Soc. 2019, 141, 8914-8920

A reaction scheme showing Ni(III) with R group, forming Ni(IV)–R by radical addition, then radical C–C coupling yields R–R and Ni(II).

172. Roberts, C. R.; Camasso, N. M.; Bowes, E. G.; Sanford, M. S. “Impact of Oxidation State on Reactivity and Selectivity Differences between Nickel(III) and Ni(IV) Alkyl Complexes,” Angew. Chem. Int. Ed. 2019, 58, 9104-9108

Diagram comparing Ni(III)-alkyl and Ni(IV)-alkyl complexes, both cationic and 6-coordinate, showing possible reactions and questioning if reactivity differs by oxidation state.

171. Lee, S. J.; Brooks, A. F.; Ichiishi, N.; Makaravage, K. J.; Mossine, A. V.; Sanford, M. S.; Scott, P. J. H. “C–H [18F]Fluorination of 8-Methylquinolines with Ag18F,” Chem. Commun. 2019, 55, 2976-2879

170. Ferguson, D. M.; Malapit, C. M.; Bour, J. R.; Sanford, M. S. “Palladium-Catalyzed Difluoromethylation of Aryl Chlorides and Bromides with TMSCF2H,” J. Org. Chem. 2019, 84, 3735-3740

Aryl halide reacts with TMSCF3 and CsF using Pd catalysts in dioxane at 100–120°C to give aryl-CF3. Highlights: two Pd systems, no pre-formed reagent, TMSCF3 is commercial, no co-catalyst.

169. Melvin, P. R.; Ferguson, D. M.; Schimler, S. D.; Bland, D. C.; Sanford, M. S. “Room Temperature Deoxyfluorination of Benzaldehydes and a-Ketoesters with Sulfuryl Fluoride and Tetramethylammonium Fluoride,” 
Org. Lett. 2019, 21, 1350-1353

168. Lee, S. J.; Makaravage, K. J.; Brooks, A. F.; Sanford, M. S.; Scott, P. J. H. “Cu-Mediated Aminoquinoline-Directed Radiofluorination of Aromatic C–H Bonds with KF,” Angew. Chem. Int. Ed. 2019, 58, 3119-3122

Chemical reaction scheme showing fluorination of a quinoline compound using [18F], with a product labeled as [18F]AC251066. Reagents and conditions: Cu, NMM, DBU, K222, DMF, 90–110°C, 30 min.

167. Ferguson, D. M.; Bour, J. R.; Canty, A. J.; Kampf, J. W.; Sanford, M. S. “Aryl–CF3 Coupling from Phosphinoferrocene-Ligated Palladium(II) Complexes,” Organometallics 2019, 38, 519-526

166. Aguilera, E. Y.; Sanford, M. S. “Model Complexes for the Palladium-Catalyzed Transannular C–H Functionalization of Alicyclic Amines,” Organometallics 2019, 38, 138-142

165. Vaid, T. P.; Sanford, M. S. “An Organic Super-Electron Donor as a High Energy Density Negative Electrolyte for Nonaqueous Flow Batteries,” Chem. Commun. 2019, 55, 11037-11040

164. Bour, J. R.; Ferguson, D. M.; McClain, E. J.; Kampf, J. W.; Sanford, M. S. “Connecting Organometallic Ni(III) and Ni(IV): Reactions of Carbon-Centered Radicals with High-Valent Organonickel Complexes,” J. Am. Chem. Soc. 2019, 141, 8914–8920

163. Lee, M.; Adams, A.; Cox, P. B.; Sanford, M. S. “Access to 3D Alicyclic Amine-Containing Fragments through Transannular C–H Arylation,” SynLett 2019, 30, 417–422

162. Ferguson, D. M.; Bour, J. R.; Canty, A. J.; Kampf, J. W.; Sanford, M. S. “Aryl–CF3 Coupling from Phosphinoferrocene-Ligated Palladium(II) Complexes,” Organometallics 2019, 38, 519–526

161. Lee, S. J.; Makaravage, K. J.; Brooks, A. F.; Scott, P. J. H.; Sanford, M. S. “Cu‐Mediated Aminoquinoline‐Directed Radiofluorination of Aromatic C–H Bonds with K18F,” Angew. Chem. Int. Ed. 2019, 58, 1–5

A chemical reaction scheme shows ^18F radiolabeling of heterocycles, forming a product, ^18F-AC261066, with its structure highlighted on the right in a dashed box. Reaction conditions and reagents are listed above the arrow.

160. Yang, L.; Brooks, A. F.; Makaravage, K. J.; Zhang, H.; Sanford, M. S.; Scott, P. J. H.; Shao, X. “Radiosynthesis of [11C]LY2795050 for Preclinical and Clinical PET Imaging Using Cu(II)-Mediated Cyanation,” 
ACS Med. Chem. Lett. 2018, 9, 1274–1279

159. Malapit, C. A.; Bour, J. R.; Brigham, C. E.; Sanford, M. S. “Base-free nickel-catalysed decarbonylative Suzuki–Miyaura coupling of acid fluorides,” Nature 2018, 563, 100–104

158. Mantell, M.; Kampf, J. W.; Sanford, M. S. “Improved Synthesis of [CpRRhCl2]2 Complexes,” 
Organometallics 2018, 37, 3240–3242

157. Schimler, S. D.; Froese, R. D. J.; Bland, D. C.; Sanford, M. S. “Reactions of Arylsulfonate Electrophiles with NMe4F: Mechanistic Insight, Reactivity, and Scope,” J. Org. Chem. 2018 83, 11178–11190

156. Cabrera, P. J.; Lee, M.; Sanford, M. S. “Second-Generation Palladium Catalyst System for Transannular C–H Functionalization of Azabicycloalkanes,” J. Am. Chem. Soc. 2018, 140, 5599–5606

155. Makaravage, K. J.; Shao, X.; Brooks, A. F.; Yang, L.; Sanford, M. S.; Scott, P. J. H. “Copper(II)-Mediated [11C]Cyanation of Arylboronic Acids and Arylstannanes,” Org. Lett. 2018, 20, 1530–1533

154. Hendriks, K. H.; Robinson, S. G.; Braten, M. N.; Sevov, C. S.; Helms, B. A.; Sigman, M. S.; Minteer, S. D.; Sanford, M. S. “High-Performance Oligomeric Catholytes for Effective Macromolecular Separation in Nonaqueous Redox Flow Batteries,” ACS Cent. Sci. 2018, 4, 189–196

153. James, B. R.; Boissonnault, J. A.; Wong-Foy, A. G.; Matzger, A. J.; Sanford, M. S. “Structure activity relationships in metal–organic framework catalysts for the continuous flow synthesis of propylene carbonate from CO2 and propylene oxide,” RSC Adv. 2018, 8, 2132–2137

152. Mossine, A. V.; Brooks, A. F.; Bernard-Gauthier, V.; Bailey, J. J.; Ichiishi, N.; Schirrmacher, R.; Sanford, M. S.; Scott, P. J. H. “Automated Synthesis of PET Radiotracers by Copper-mediated 18F-Fluorination of Organoborons: Importance of the Order of Addition and Competing Protodeborylation,” J. Label. Compd. Radiopharm. 2017, 1–9

151. Shrestha, A.; Lee, M.; Dunn, A. L.; Sanford, M. S. “Palladium-Catalyzed C–H Bond Acetoxylation via Electrochemical Oxidation,” Org. Lett. 2017, 20, 204–207

150. Ichiishi, N.; Malapit, C. A.; Wozniak, L.; Sanford, M. S. “Palladium- and Nickel-Catalyzed Decarbonylative C–S Coupling to Convert Thioesters to Thioethers,” Org. Lett. 2017, 20, 44–47

149. Sevov, C. S.; Hendriks, K. H.; Sanford, M. S. “Low-Potential Pyridinium Anolyte for Aqueous Redox Flow Batteries,” 
J. Phys. Chem. C 2017, 121, 24376–24380

148. Camasso, N. M.; Canty, A. J.; Ariafard, A.; Sanford, M. S. “Experimental and Computational Studies of High-Valent Nickel and Palladium Complexes,” Organometallics 2017, 36, 4382–4393

147. Hendriks, K. H.; Sevov, C. S.; Cook, M. E.; Sanford, M. S. “Multielectron Cycling of a Low-Potential Anolyte in Alkali Metal Electrolytes for Nonaqueous Redox Flow Batteries,” ACS Energy Lett. 2017, 2, 2430–2435

146. Ferguson, D. M. Bour, J. R.; Canty, A. J.; Kampf, J. W.; Sanford, M. S. “Stoichiometric and Catalytic Aryl–Perfluoroalkyl Coupling at Tri-tert-butylphosphine Palladium(II) Complexes,” J. Am. Chem. Soc. 2017, 139, 11662–11665

145. Malapit, C. A.; Ichiishi, N.; Sanford, M. S. “Pd-Catalyzed Decarbonylative Cross-Couplings of Aroyl Chlorides,” 
Org. Lett. 2017, 19, 4142–4145

144. McCammant, M. S.; Thompson, S.; Brookes, A. F.; Krska, S. W.; Scott, P. J. H.; Sanford, M. S. “Cu-Mediated C–H 18F-Fluorination of Electron-Rich (Hetero)arenes,” Org. Lett. 2017, 19, 3939–3942

143. Cismesia, M. A.; Ryan, S. J.; Bland, D. C.; Sanford, M. S. “Multiple Approaches to the In Situ Generation of Anhydrous Tetraalkylammonium Fluoride Salts for SNAr Fluorination Reactions,” J. Org. Chem. 2017, 82, 5020–5026

142. Chong, E.; Kampf, J. W.; Ariafard, A.; Canty, A. J.; Sanford, M. S. “Oxidatively Induced C–H Activation at High Valent Nickel,” J. Am. Chem. Soc. 2017, 139, 6058–6061

141. Bour, J. R.; Kariofillis, S. K.; Sanford, M. S. “Synthesis, Reactivity, and Catalytic Applications of Isolable (NHC)Cu(CHF2) Complexes,” Organometallics 2017, 36, 1220–1223

140. Mossine, A. V.; Brooks, A. F.; Ichiishi, N.; Makaravage, K. J.; Sanford, M. S.; Scott, P. J. H. “Development of Customized [18F]Fluoride Elution Techniques for the Enhancement of Copper-Mediated Late-Stage Radiofluorination,” 
Scientific Reports 2017, 7, 233

139. Canty, A. J.; Ariafard, A.; Camasso, N. M.; Higgs, A. T.; Yates, B. F.; Sanford, M. S. “Computational study of C(sp3)–O bond formation at a PdIV centre,” Dalton Trans. 2017, 46, 3742–3748

138. Sevov, C. S.; Hickey, D. P.; Cook, M. E.; Robinson, S. G.; Barnett, S.; Minteer, S. D.; Sigman, M. S.; Sanford, M. S. “Physical Organic Approach to Persistent, Cyclable, Low-Potential Electrolytes for Flow Battery Applications,” 
J. Am. Chem. Soc. 2017, 139, 2924–2927

137. Schimler, S. D.; Cismesia, M. A.; Hanley, P. S.; Froese, R. D. J.; Jansma, M. J.; Bland, D. C.; Sanford, M. S. “Nucleophilic Deoxyfluorination of Phenols via Aryl Fluorosulfonate Intermediates,” J. Am. Chem. Soc. 2017, 139, 1452–1455

136. Lee, M.; Sanford, M. S. “Remote C(sp3)–H Oxygenation of Protonated Aliphatic Amines with Potassium Persulfate,” Org. Lett. 2017, 19, 572–575

135. Lotz, M. D.; Camasso, N. M.; Canty, A. J.; Sanford, M. S. “Role of Silver Salts in Palladium-Catalyzed Arene and Heteroarene C–H Functionalization Reactions,” Organometallics 2017, 36, 165–171

134. Meucci, E. A.; Camasso, N. M.; Sanford, M. S. “An Organometallic NiIV Complex That Participates in Competing Transmetalation and C(sp2)–O Bond-Forming Reductive Elimination,” Organometallics 2017, 36, 247–250

133. Bour, J. R.; Camasso, N. M.; Meucci, E. A.; Kampf, J. W.; Canty, A. J.; Sanford, M. S. “Carbon–Carbon Bond-Forming Reductive Elimination from Isolated Nickel(III) Complexes,” J. Am. Chem. Soc. 2016, 138, 16105–16111

132. Sevov, C. S.; Samaroo, S. K.; Sanford, M. S. “Cyclopropenium Salts as Cyclable, High-Potential Catholytes in Nonaqueous Media,” Adv. Energy Mater. 2016, 1602027

131. Sevov, C. S.; Fisher, S. L.; Thompson, L. T.; Sanford, M. S. “Mechanism-Based Development of a Low-Potential, Soluble, and Cyclable Multielectron Anolyte for Nonaqueous Redox Flow Batteries,” J. Am. Chem. Soc. 2016, 138, 15378–15384

130. Makaravage, K. J.; Brooks, A. F.; Mossine, A. V.; Sanford, M. S.; Scott, P. J. H. “Copper-Mediated Radiofluorination of Arylstannanes with [18F]KF,” Org. Lett. 2016, 18, 5440–5443

129. Schimler, S. D.; Sanford, M. S. “Copper-Mediated Functionalization of Aryl Trifluoroborates,” 
Synlett. 2016, 27, 2279–2284

128. Rezayee, N. M.; Samblanet, D. C.; Sanford, M. S. “Iron-Catalyzed Hydrogenation of Amides to Alcohols and Amines,” ACS Catal. 2016, 6, 6377–6383

127. Mbofana, C. T.; Chong, E.; Lawniczak, J.; Sanford, M. S. “Iron-Catalyzed Oxyfunctionalization of Aliphatic Amines at Remote Benzylic C–H Sites,” Org. Lett. 2016, 18, 4258–4261

126. Pendleton, I. M.; Pérez-Temprano, M. H.; Sanford, M. S.; Zimmerman, P. M. “Experimental and Computational Assessment of Reactivity and Mechanism in C(sp3)–N Bond-Forming Reductive Elimination from PdIV,” 
J. Am. Chem. Soc. 2016, 138, 6049–6060

125. Genna, D. T.; Pfund, L. Y.; Samblanet, D. C.; Wong-Foy, A. G.; Matzger, A. J.; Sanford, M. S. “Rhodium Hydrogenation Catalysts Supported in Metal Organic Frameworks: Influence of the Framework on Catalytic Activity and Selectivity,” 
ACS Catal. 2016, 6, 3569–3574

124. Brewster, T. P.; Rezayee, N. M.; Culakova, Z.; Sanford, M. S.; Goldberg, K. I. “Base-Free Iridium-Catalyzed Hydrogenation of Esters and Lactones,” ACS Catal. 2016, 6, 3113–3117

123. Cook, A. K.; Schimler, S. D.; Matzger, A. J.; Sanford, M. S. “Catalyst-Controlled Selectivity in the C–H Borylation of Methane and Ethane,” Science 2016, 351, 1421–1424

122. Sanford, M. S.; Scott, P. J. H. “Moving Metal-Mediated 18F‐Fluorination from Concept to Clinic,” 
ACS Cent. Sci. 2016, 2, 128–130

121. Topczewski, J. T.; Cabrera, P. J.; Saper, N. I.; Sanford, M. S. “Palladium-Catalysed Transannular C–H Functionalization of Alicyclic Amines,” Nature 2016, 531, 220–224

120. Schimler, S. D.; Ryan, S. J.; Bland, D. C.; Anderson, J. E.; Sanford, M. S. “Anhydrous Tetramethylammonium Fluoride for Room-Temperature SNAr Fluorination,” J. Org. Chem. 2015, 80, 12137–12145

119. Mossine, A. V.; Brooks, A. F.; Makaravage, K. J.; Miller, J. M.; Ichiishi, N.; Sanford, M. S.; Scott, P. J. H. “Synthesis of [18F]Arenes via the Copper-Mediated [18F]Fluorination of Boronic Acids,” Org. Lett. 2015, 17, 5780–5783.

118. Sevov, C. S.; Brooner, R. E. M.; Chénard, E.; Assary, R. S.; Moore, J. S.; Rodríguez-López, J.; Sanford, M. S. “Evolutionary Design of Low Molecular Weight Organic Anolyte Materials for Applications in Nonaqueous Redox Flow Batteries,” 
J. Am. Chem. Soc. 2015, 137, 14465–14472.

117. Cabrera, P. J.; Yang, X.; Suttil, J. A.; Brooner, R. E. M.; Thompson, L. T.; Sanford, M. S. “Evaluation of Tris-Bipyridine Chromium Complexes for Flow Battery Applications: Impact of Bipyridine Ligand Structure on Solubility and Electrochemistry,” Inorg. Chem. 2015, 54, 10214–10223.

116. Cook, A.; Sanford, M. S. “C–Hal Bond Formation by Arene C–H Activation,”
In Catalytic Transformations via C-H Activation, Vol. 2; Science of Synthesis, Yu, J.-Q., 2015, 183–219.

115. Lee, M.; Sanford, M. S. “Platinum-Catalyzed, Terminal-Selective C(sp3)–H Oxidation of Aliphatic Amines,” 
J. Am. Chem. Soc. 2015, 137, 12796–12799.

114. Bour, J. R.; Camasso, N. M.; Sanford, M. S. “Oxidation of NiII to NiIV with Aryl Electrophiles Enables Ni-Mediated Aryl–CF3 Coupling,” J. Am. Chem. Soc. 2015, 137, 8034–8037.

113. Cabrera, P. J.; Yang, X.; Suttil, J. A.; Hawthorne, K. L. Brooner, R. E. M.; Sanford, M. S.; Thompson, L. T. “Complexes Containing Redox Noninnocent Ligands for Symmetric, Multielectron Transfer Nonaqueous Redox Flow Batteries, ” 
J. Phys. Chem. C 2015, 119, 15882–15889.

Diagram showing a Cr metal coordination complex, grid-scale energy storage, and a smart grid system with a house, solar panels, and a building, illustrating smart grid technology integration.

112. Ryan, S. J.; Schimler, S. D.; Bland, D. C.; Sanford, M. S. “Acyl Azolium Fluorides for Room Temperature Nucleophilic Aromatic Fluorination of Chloro- and Nitroarenes,” Org. Lett. 2015, 17, 1866–1869.

111. Suttil, J. A.; Kucharyson, J. F.; Escalante-Garcia, I. L.; Cabrera, P. J.; James, B. R.; Savinell, R. F.; Sanford, M. S.; Thompson, L. T. “Metal Acetylacetonate Complexes for High Energy Density Non-Aqueous Redox Flow Batteries,” 
J. Mater. Chem. A 2015, 3, 7929–7938.

110. Canty, A. J.; Ariafard, A.; Yates, B. F.; Sanford, M. S. “Computational Study of Intramolecular Arene Palladation at a Palladium(IV) Center,” Organometallics 2015, 34, 1085–1090.

109. Cook, A. K.; Sanford, M. S. “Mechanism of the Palladium-Catalyzed Arene C–H Acetoxylation: A Comparison of Catalysis and Ligand Effects,” J. Am. Chem. Soc. 2015, 137, 3109–3118.

108. Camasso, N. M.; Sanford, M. S. “Design, Synthesis, and Carbon-Heteroatom Coupling Reactions of Organometallic Nickel (IV) Complexes,” Science 2015, 347, 1218–1220.

107. Rezayee, N. M.; Huff, C. A.; Sanford, M. S. “Tandem Amine and Ruthenium-Catalyzed Hydrogenation of CO2 to Methanol,” J. Am. Chem. Soc. 2015, 137, 1028–1031.

106. Topczewski, J. J.; Sanford, M. S. “Carbon–Hydrogen (C–H) Bond Activation at PdIV: A Frontier in C–H Functionalization Catalysis,” Chem. Sci. 2014, 6, 70–76.

105. Ichiishi, N.; Canty, A. J.; Yates, B. F.; Sanford, M. S. “Mechanistic Investigations of Cu-Catalyzed Fluorination of Diaryliodonium Salts: Elaborating the CuI/CuIII Manifold in Copper Catalysis,” Organometallics 2014, 33, 5525–5534.

104. Brooks, A. F.; Topczewski, J. J.; Ichiishi, N.; Sanford, M. S.; Scott, P. J. H. “Late-Stage [18F]Fluorination: New Solutions to Old Problems,” Chem. Sci. 2014, 5, 4545–4553.

103. Camasso, N. M.; Pérez-Temprano, M. H.; Sanford, M. S. “C(sp3)–O Bond-Forming Reductive Elimination from PdIV with Diverse Oxygen Nucleophiles,” J. Am. Chem. Soc. 2014, 136, 12771–12775.

102. Allen, L. J.; Lee, S. H.; Cheng, Y.; Hanley, P. S.; Muhuhi, J. M.; Kane, E.; Powers, S. L.; Anderson, J. E.; Bell, B. M.; Roth, G. A.; Sanford, M. S.; Bland, D. C. “Developing Efficient Nucleophilic Fluorination Methods and Application to Substituted Picolinate Esters,” Org. Process Res. Dev. 2014, 18, 1045–1054.

101. Maleckis, A.; Sanford, M. S. “Synthesis of Fluoroalkyl Palladium and Nickel Complexes via Decarbonylation of Acylmetal Species” Organometallics 2014, 33, 3831–3839.

100. Ichiishi, N.; Brooks, A. F.; Topczewski, J. J.; Rodnick, M. E.; Sanford, M. S.; Scott, P. J. H. “Copper-Catalyzed [18F]Fluorination of (Mesityl)(aryl)iodonium Salts,” Org. Lett. 2014, 16, 3224–3227.

99. Lotz, M. D.; Remy, M. S.; Lao, D. B.; Ariafard, A.; Yates, B. F.; Canty, A. J.; Mayer, J. M.; Sanford, M. S. “Formation of Ethane from Mono-Methyl PalladiumII Complexes,” J. Am. Chem. Soc. 2014, 136, 8237–8242.

A palladium complex reacts with an oxidant to form ethane (H3C–CH3). The caption reads: Key step in conversion of methane to ethane..

98. Allen, L. J.; Muhuhi, J. M.; Bland, D. C.; Merzel, R.; Sanford, M. S. “Mild Fluorination of Chloropyridines with In Situ Generated Anhydrous Tetrabutylammonium Fluoride,” J. Org. Chem. 2014, 79, 5827–5833.

Reaction scheme: A pyridine ring with phenyl, isopropyl carboxylate, and chlorine groups reacts with anhydrous NBu4F in DMSO, DMF, DMAc, or MeCN to yield the fluorinated analog at room temperature.

97. Maleckis, A.; Sanford, M. S. “Catalytic Cycle for Palladium-Catalyzed Decarbonylative Trifluoromethylation using Trifluoroacetic Esters as the CF3 Source,” Organometallics 2014, 33, 2653–2660.

96. Allen, L. J.; Cabrera, P. J.; Lee, M.; Sanford, M. S. “N-Acyloxyphthalimides as Nitrogen Radical Precursors in the Visible Light Photocatalyzed Room Temperature C–H Amination of Arenes and Heteroarenes,” 
J. Am. Chem. Soc. 2014, 136, 5607–5610.

95. Pérez-Temprano, M. H.; Racowski, J. M.; Kampf, J. W.; Sanford, M. S. “Competition Between sp 3-C–N vs sp 3-C–F Reductive Elimination from PdIV Complexes,” J. Am. Chem. Soc. 2014, 136, 4097–4100.

94. Wagner, A. M.; Sanford, M. S. “Transition-Metal-Free Acid-Mediated Synthesis of Aryl Sulfides from Thiols and Thioethers,” J. Org. Chem. 2014, 79, 2263–2267.

A chemical reaction scheme shows thioether and diaryliodonium salt forming a new thioether in 1,4-dioxane at 110°C for 15 h, with yields of 37-90% across 16 examples.

93. Ye, Y.; Schimler, S. D.; Hanley, P. S.; Sanford, M. S. ” Cu(OTf)2-Mediated Fluorination of Aryltrifluoroborates with Potassium Fluoride, ” J. Am. Chem. Soc. 2013, 135, 16292–16295.

92. Wagner, A. M. ; Hickman, A. J. ; Sanford, M. S. “Platinum-Catalyzed C–H Arylation of Simple Arenes,” 
J. Am. Chem. Soc. 2013, 135, 15710–15713.

91. Cook, A. K.; Emmert, M. H.; Sanford, M. S. “Steric Control of Site Selectivity in the Pd-Catalyzed C–H Acetoxylation of Simple Arenes,” Org. Lett. 2013, 15, 5428–5431.

90. Lehman, M. C.; Gary, J. B.; Boyle, P. D.; Sanford, M. S.; Ison, E. A. “Effect of Solvent and Ancillary Ligands on the Catalytic H/D Exchange Reactivity of Cp*IrIII(L) Complexes,” ACS Catalysis. 2013, 3, 2304–2310.

89. Huff, C. A.; Sanford, M. S. “Catalytic CO2 Hydrogenation to Formate by a Ruthenium Pincer Complex,” 
ACS Catalysis. 2013, 3, 2412–2416.

A chemical scheme shows CO2 and H2 reacting with a base to form a formate anion, catalyzed by a ruthenium complex. Yield is listed as TON up to 23,000. A molecular structure is labeled Putative Catalytic Intermediate..

88. Ichiishi, N.; Canty, A. J.; Yates, B. F.; Sanford, M. S. “Cu-Catalyzed Fluorination of Diaryliodonium Salts With KF,” 
Org. Lett. 2013, 15, 5134–5137.

Scheme of copper-catalyzed fluorination of aryl groups, using 1.1 equivalents KF and 18-crown-6 in DMF at 60–85°C, yielding fluoroarenes with fast rate, high yield, and no regioisomers (26 examples).

87. Genna, D. T.; Wong-Foy, A. G.; Matzger, A. J.; Sanford, M. S. “Heterogenization of Homogeneous Catalysts in Metal–Organic Frameworks Via Cation Exchange,” J. Am. Chem. Soc. 2013, 135, 10586–10589.

Diagram showing NH2Me2+ ions (orange) in a crystal structure being replaced by cationic transition metal complexes (teal) within a symmetric molecular framework; purple highlights possible binding sites.

86. Huff, C. A.; Kampf, J. W.; Sanford, M. S. “Reversible Carbon-Carbon Bond Formation Between Carbonyl Compounds and a Ruthenium Pincer Complex,” Chem. Commun. 2013, 49, 7147–7149.

85. Sanhueza, I. A.; Wagner, A. M.; Sanford, M. S.; Schoenebeck, F. “On the Role of Anionic Ligands in the Site-Selectivity of Oxidative C–H Functionalization Reactions of Arenes.” Chem. Sci. 2013, 4, 2767–2775.

84. Gary, J. B.; Cook, A. K.; Sanford, M. S. “Palladium Catalysts Containing Pyridinium-Substituted Pyridine Ligands for the C–H Oxygenation of Benzene with K2S2O8,” ACS Catalysis. 2013, 3, 700–703.

Chemical reaction scheme: benzene, K2S2O8, and acetic anhydride give an arylated product via a palladium catalyst. Product features aryl groups and a BF4 counterion, with Ar as 4-tert-butylphenyl.

83. Seigerman, C. K.; Micyus, T. M.; Neufeldt, S. R.; Sanford, M. S. “Palladium-Catalyzed C–H Arylation Using Aryltrifluoroborates in Conjunction with a MnIII Oxidant under Mild Conditions,” Tetrahedron. 2013, 69, 5580–5587.

A chemical reaction scheme shows a pyrroloquinoline compound with substituents R and R undergoing arylation (Aryl in red) using Pd(OAc)2, Aryl–BF3K, Mn(OAc)3 in TFE/AcOH at 50°C to form an arylated product.

82. Maleckis, A.; Kampf, J. W.; Sanford, M. S. “A Detailed Study of Acetate-Assisted C–H Activation at Palladium (IV) Centers,” J. Am. Chem. Soc. 2013, 135, 6618–6625.

Chemical reaction showing acetate-assisted C-H activation at palladium(IV). A palladium complex reacts with MOAc, losing HOAc to form a new Pd complex with an additional phenyl ring linked to the palladium center.

81. Neufeldt, S. R.; Seigerman, C. K.; Sanford, M. S. “Mild Palladium-Catalyzed C–H Alkylation Using Potassium Alkyltrifluoroborates in Combination with MnF3,” Org. Lett. 2013, 15, 2302–2305.

Reaction scheme: A C–H bond (with ligand L, either pyridine or anilide) is converted to a C–R bond (R = Me or primary alkyl) using Pd(OAc)₂, RBF₃K, MnF₃ in TFE/H₂O/AcOH at 25–40°C.

80. Ye, Y.; Sanford, M. S. “Mild Copper-Mediated Fluorination of Aryl Stannanes and Aryl Trifluoroborates,” 
J. Am. Chem. Soc. 2013, 135, 4648–4651.

Reaction scheme: an aromatic compound (R–M) reacts with a copper catalyst and fluorine oxidant, forming a para-fluoroarene. The oxidant structure is shown, labeled as F⁺ Oxidant..

79. Canty, A. J.; Ariafard, A.; Sanford, M. S.; Yates, B. F. “Mechanism of Pd-Catalyzed Ar-Ar Bond Formation Involving Ligand-Directed C-H Arylation and Diaryliodonium Oxidants: Computational Studies of Orthopalladation at Binuclear PdII Centers, Oxidation To Form Binuclear Palladium (III) Species, and Ar···Ar Reductive Coupling, ” Organometallics 2013, 32, 544–555.

A catalytic cycle diagram showing palladium complexes reacting with Ph2I, forming intermediates, and regenerating the initial complex through a series of arrowed steps.

78. Neufeldt, S. R.; Sanford, M. S. “Asymmetric Chiral Ligand-Directed Alkene Dioxygenation,” Org. Lett. 2013, 15, 46≠49.

A chemical reaction converts an allylic oxime to a dioxylated product using Pd catalyst and PhI(OBz)₂, yielding up to 90:10 diastereomeric ratio. OBz groups are highlighted in red on the product.

77. McMurtrey, K. B.; Sanford, M. S. “C–F Bond-Forming Reactions,”
In Cross-Coupling and Heck-Type Reactions from the Science of Synthesis Reference Library. Vol. 2, John P. Wolfe, Ed., Thieme, 2012.

76. Neufeldt, S. R.; Sanford, M. S. “Combining Transition Metal Catalysis with Radical Chemistry: Dramatic Acceleration of Palladium-Catalyzed C–H Arylation with Diaryliodonium Salts,” Adv. Synth. Catal. 2012, 354, 3517–3522.

75. Ye,Y.; Kuenzi, S. A.; Sanford, M. S. “Practical Method for the Cu-Mediated Trifluoromethylation of Arylboronic Acids with CF3 Radicals Derived from NaSO2CF3 and tert-Butyl Hydroperoxide (TBHP),” Org. Lett. 2012, 14, 4979–4981.

Reaction scheme: A boronic acid reacts with NaSO₂CF₃ and TBHP, catalyzed by copper, to yield an arene with a CF₃ group. The process is done at room temperature with simple setup; 24 examples are noted.

74. Stowers, K. J.; Kubota, A.; Sanford, M. S. “Nitrate as a Redox Co-Catalyst for the Aerobic Pd-Catalyzed Oxidation of Unactivated sp3-C–H Bonds,” Chem. Sci. 2012, 3, 3192–3195.

A reaction scheme showing catalytic oxidation: O2, NO, and NaNO3 produce intermediates that react with Pd(OAc)2, leading to C–H activation and formation of an acetoxylated product, with arrows depicting the process.

73. McMurtrey, K. B.; Racowski, J. M.; Sanford, M. S. “Pd-Catalyzed C-H Fluorination with Nucleophilic Fluoride,” 
Org. Lett. 2012, 14, 4094–4097.

Chemical reaction scheme: a quinoline derivative reacts under Pd-catalysis with PhI(OPiv)₂ and AgF in CH₂Cl₂ at 60°C, yielding a fluorinated quinoline, where fluorine replaces a hydrogen atom.

72. Powers, D. C.; Lee, E.; Ariafard, A.; Sanford, M. S.; Yates, B. F.; Canty, A. J.; Ritter, T. “Connecting Binuclear PdIII and Mononuclear PdIV Chemistry by Pd-Pd Bond Cleavage,” J. Am. Chem. Soc. 2012, 134, 12002–12009.

71. Ye, Y.; Sanford, M. S. “Investigations into Transition-Metal-Catalyzed Arene Trifluoromethylation Reactions,” Synlett. 2012, 23, 2005–2013.

70. Gary, J. B; Carter, T. J.; Sanford, M. S. “RhIII Pyridinium Substituted Bipyridine Complexes as Catalysts for Arene H/D Exchange,” Top. Catal. 2012, 55, 565–570.

69. Huff, C. A.; Kampf, J. W.; Sanford, M. S. “Role of a Noninnocent Pincer Ligand in the Activation of CO2 at (PNN)Ru(H)(CO),” Organometallics 2012, 31, 4643–4635.

A diagram shows reversible CO₂ activation by a ruthenium pincer complex, forming a kinetic product and then converting to a thermodynamic product, both labeled with CO₂ and structural changes.

68. Hickman, A. J.; Sanford, M. S. “High-Valent Organometallic Copper and Palladium in Catalysis,” 
Nature 2012, 484, 177–185.

67. Ye, Y.; Sanford, M. S. “Merging Visible-Light Photocatalysis and Transition-Metal Catalysis in the Copper-Catalyzed Trifluoromethylation of Boronic Acids with CF3I,” J. Am. Chem. Soc. 2012, 134, 9034–9037.

A chemical reaction scheme shows a copper-catalyzed process forming a trifluoromethylated benzene ring. A photoredox cycle with Ru(bpy)₃ and light generates a CF₃ radical, which reacts with a boronic acid.

66. Neufeldt, S. R.; Sanford, M. S. “Controlling Site Selectivity in Palladium-Catalyzed C–H Bond Functionalization” 
Acc. Chem. Res. 2012, 45, 936–946.

Reaction scheme shows Pd(II)-catalyzed functionalization of R3C–H to R3C–X. Below, strategies for site selectivity include directing groups and use of different catalysts A and B for selectivity at distinct positions.

65. Kubota, A.; Emmert, M. H.; Sanford, M. S. “Pyridine Ligands as Promoters in PdII/0-Catalyzed C–H Olefination Reactions” Org. Lett. 2012, 14, 1760–1763.

A reaction scheme showing a benzene ring with R group and an α,β-unsaturated ester yielding a substituted cinnamate in the presence of Pd(OAc)₂, pyridine, PhCO₃-tBu, and AcOH at 100°C.

64. Hickman, A. J.; Cismesia, M. A.; Sanford, M. S. “Structure-Activity Relationship Study of Diimine PtII Catalysts for H/D Exchange” Organometallics 2012, 31, 1761–1766.

Reaction scheme shows C6H6 with a Pt catalyst and RCO2D forming C6HnD6–n, alongside structures of three Pt complexes with arrows indicating increasing catalyst activity.

63. Racowski, J. M.; Gary, B. G.; Sanford, M. S. “Carbon(sp3)–Fluorine Bond-Forming Reductive Elimination from Palladium (IV)” Angew. Chem. Int. Ed 2012, 51, 3414–3417

Chemical reaction scheme showing a Pd(IV) complex with pyridine and fluorine ligands converting to a new Pd complex with a fused ring structure when treated with CH2Cl2 at 80°C for 30 min, yielding a single product.

62. Park, T.-H.; Hickman, A. J.; Koh, K.; Martin, S.; Wong-Foy, A. G.; Sanford, M. S.; Matzger, A. J. “Highly Dispersed Palladium (II) in a Defective MOF: Application to C–H Activation and Functionalization,” J. Am. Chem. Soc. 2011, 133, 20138–20141.

Schematic showing MOF-5 crystal structure before and after loading with Pd(II), with images of crystals and labeled microporous cage and carboxylate sites. Yellow circles indicate Pd(II) ions.

61. Maleckis, A; Sanford, M. S. “Facial Tridentate Ligands for Stabilizing Palladium (IV) Complexes,” Organometallics 2011, 30, 6617–6627.

Chemical reaction scheme showing palladium complex transformations, with reagents and products indicated. The process includes ligand exchanges, use of AgOTf, and introduction of an isocyanide group to the palladium center.

60. Kalyani, D.; McMurtrey, K. B.; Neufeldt, S. R.; Sanford, M. S. “Room-Temperature C–H Arylation: Merger of Pd-Catalyzed C–H Functionalization and Visible-Light Photocatalysis,” J. Am. Chem. Soc. 2011, 133, 18566–18569.

Reaction scheme: A diazonium group on benzene loses N2 under Ru(bpy)3Cl2, visible light, 25°C, making a benzene radical, which reacts with L–C–H and Pd(OAc)2 at 25°C to yield L–C–benzene.

59. Huff, C. A.; Sanford, M. S. “Cascade Catalysis for the Homogeneous Hydrogenation of CO2 to Methanol,” 
J. Am. Chem. Soc. 2011, 133, 18122–18125.

58. Gary, J. B.; Sanford, M. S. “Participation of Carbonyl Oxygen in Carbon-Carboxylate Bond-Forming Reductive Elimination from Palladium,” Organometallics 2011, 30, 6143–6149.

Reaction mechanism diagram comparing a favored 5-membered palladium transition state with a disfavored 3-membered one, showing Pd coordination to a benzene ring and an acetate group.

57. Racowski, J. M.; Ball, N. D.; Sanford, M. S. “C–H Bond Activation at Palladium (IV) Centers,” 
J. Am. Chem. Soc. 2011, 133, 18022–18025.

A chemical reaction scheme shows a Pd(IV) complex reacting with C6B5Cl2 to form a new Pd(IV) complex, then losing HCl to form a cyclized product with fused aromatic rings.

56. Ye, Y.; Lee, S.; Sanford, M. S. “Silver-Mediated Trifluoromethylation of Arenes Using TMSCF3,” 
Org. Lett. 2011, 13, 5464–5467.

Arenes react with Me₃Si–CF₃, AgOTf, and KF in DCE under N₂ at 85°C for 24 h to yield aryl–CF₃ products, showing a trifluoromethylation reaction.

55. Emmert, M. H.; Cook, A. K.; Xie, Y. J.; Sanford, M. S. “Remarkably High Reactivity of Pd(OAc)2/Pyridine Catalysts: Nondirected C–H Oxygenation of Arenes,” Angew. Chem. Int. Ed. 2011, 50, 9409–9412.

A reaction scheme shows a benzene ring with an R group and hydrogen reacting with palladium acetate and a red ligand to yield an aryl acetate. Blue text notes enhanced rate, scope, and selectivity.

54. Lanci, M. P.; Remy, M. S.; Lao, D. B.; Sanford, M. S.; Mayer, J. M. “Modulating Sterics in Trimethylplatinum (IV) Diimine Complexes to Achieve C–C Bond-Forming Reductive Elimination,” Organometallics 2011, 30, 3704–3707.

Chemical reaction showing a Pt(IV) complex converting to a Pt(II) complex with ethane as a product; a checkmark by a ligand structure and an X by an alternate ligand representation.

53. Kubota, A; Sanford, M. S. “Palladium-Catalyzed Ligand-Directed Oxidative Functionalization of Cyclopropanes,”  Synthesis 2011, 16, 2579–2589.

52. Loy, R. N.; Sanford, M. S. “Palladium-Catalyzed C–H Perfluoroalkylation of Arenes,” Org. Lett. 2011, 13, 2548–2551.

A chemical reaction scheme: a substituted benzene reacts with C10F21 under Pd2dba3, BINAP, and Cs2CO3, at 40–100°C for 15–24 h, yielding benzene substituted with C10F21.

51. Ball, N. D.; Gary, J. B.; Ye, Y.; Sanford, M. S. “Mechanistic and Computational Studies of Oxidatively-Induced Aryl–CF3 Bond-Formation at Pd: Rational Design of Room Temperature Aryl Trifluoromethylation,”
 J. Am. Chem. Soc. 2011, 133, 7577–7584.

A palladium complex with CF3 reacts to make trifluoromethylated benzene. Two box conditions: 80°C with three-ring ligand, and 23°C with two six-membered ring ligands and one five-membered ligand. Mechanistic study is highlighted.

50. Stowers, K. J.; Fortner, K. C.; Sanford, M. S. “Aerobic Pd-Catalyzed sp3 C–H Olefination: A Route to Both N-Heterocyclic Scaffolds and Alkenes,” J. Am. Chem. Soc. 2011, 133, 6541–6544.

Reaction scheme: Pyridine and a substituted alkene react with Pd and polyoxometallate catalysts in air to give pyridine derivatives, which yield two different products after treatment with base and reducing agent.

49. Racowski, J.; Sanford, M. S. “Carbon-Heteroatom Bond Forming Reductive Elimination from Palladium (IV) Complexes,” In Topics in Organometallic Chemistry, Vol. 53, Allan Canty, Ed., Springer, 2011, 61-84.

48. Satterfield, A. D.; Kubota, A.; Sanford, M. S. “Palladium-Catalyzed 1,1-Aryloxygenation of Terminal Olefins,” 
Org. Lett. 2011, 13, 1076–1079.

Chemical reaction scheme showing an alkene, an aryl stannane, and PhI(O₂CR)₂ reacting with PdCl₂(PhCN)₂ catalyst in toluene to give an arylated carbonyl compound. 21 examples is noted.

47. Lyons, T. W.; Hull, K. L.; Sanford M. S. “Controlling Site Selectivity in Palladium-Catalyzed C–H Oxidative Cross-Coupling,” J. Am. Chem. Soc. 2011, 133, 4455–4464.

Chemical reaction scheme showing two pathways for a bipyridine compound with MeO groups, leading to major products with different selectivity, depending on the X group (OAc or CO3^2−) used with a Pd catalyst.

46. Hickman, A. J.; Sanford, M. S. “Catalyst Control of Site Selectivity in the PdII/IV-Catalyzed Direct Arylation of Naphthalene,” ACS Catal. 2011, 1, 170–174.

Schematic of a Pd-catalyzed reaction converting 1-phenylnaphthalene to two isomers (A and B) with product ratio 71:1 and 70% yield, using a Pd complex and NO₂Ph at 130°C for 16 hours.

45. Wagner, A. M.; Sanford, M. S. “Palladium-Catalyzed C–H Arylation of 2,5-Disubstituted Pyrroles,” 
Org. Lett. 2011, 13, 288–291.

A chemical reaction scheme showing imidazole reacting with an aryl diazonium salt in the presence of Pd catalyst and DCE at 84°C for 2 hours, yielding an arylated imidazole product.

44. Ye, Y.; Ball, N. D.; Kampf, J. W.; Sanford, M. S. “Oxidation of Catalytically Relevant Palladium Dimer with “CF3+“: Formation and Reactivity of a Monomeric Palladium (IV) Aquo Product,” J. Am. Chem. Soc. 2010, 132, 14682–14687.

Reaction scheme: Palladium complexes react with CF3+ to give a Pd(IV) intermediate, which upon heating yields a CF3-functionalized aromatic product. Text: Kinetically competent catalyst for C–H functionalization..

43. Higgs, A. T.; Zinn, P. J.; Sanford, M. S. “Synthesis and Reactivity of (Phpy)2Ni (Phpy = 2-Phenylpyridine),”  Organometallics 2010, 29, 5446–5449.

Chemical reaction diagram: a nickel complex and N-bromosuccinimide react, forming three biaryl ligands, a bipyridyl product, and succinimide with a bromine substituent. Arrow indicates conversion from reactants to products.

42. Emmert, M. H.; Villalobos, J. M.; Gary, J. B.; Sanford, M. S. “Pt and Pd Complexes Containing Cationic Ligands as Catalysts for Arene H/D Exchange and Oxidation,” Angew. Chem. Int. Ed. 2010, 49, 5884–5886.

A chemical reaction scheme shows aryl C-H activation with deuterium or aryl incorporation, catalyzed by Pt or Pd, using PhI(OAc)₂ and [D4]AcOH, with R as EWG, EDG, or H.

41. Kalyani, D.; Satterfield, A. D.; Sanford, M. S. “Palladium-Catalyzed Oxidative Arylhalogenation of Alkenes: Synthetic Scope and Mechanistic Insights,” J. Am. Chem. Soc. 2010, 132, 8419–8427.

Diagram shows a Pd-catalyzed reaction where a Ph ethyl chloride reacts with Bu3Sn–Ph to give Ph ethylphenyl and byproducts involving metal halides like CuCl2 or CuBr2 in THF or Et2O.

40. Ball, N. D.; Kampf, J. W.; Sanford, M. S. “Aryl-CF3 Bond-Forming Reductive Elimination from Palladium (IV),” 
J. Am. Chem. Soc. 2010, 132, 2878–2879.

A chemical scheme shows a palladium complex reacting with aryl fluoride and triflate to make a Pd(IV) intermediate, which then produces trifluoromethylbenzene upon heating.

39. Remy, M. S.; Cundari, T.; Sanford, M. S. “Computational and Experimental Studies of Methyl Group Exchange Between Group 10 Metal Centers,” Organometallics 2010, 29, 1522–1525.

Chemical reaction scheme showing oxidative oligomerization of methane using a palladium catalyst, producing ethane and water. Below, a key step depicts two methyl complexes interacting with Pd in a reversible process.

38. Neufeldt, S. R.; Sanford, M. S. “O-Acetyl Oximes as Transformable Directing Groups for Pd-Catalyzed C–H Functionalization,” Org. Lett. 2010, 12, 532–535.

A chemical reaction scheme shows a phenylpropylamine converted to an acyloxy product, then transformed to a carboxylic acid, with directing group transformation indicated.

37. Villalobos, J. M.; Hickman, A. J.; Sanford, M. S. “Platinum (II) Complexes Containing Quaternized Nitrogen Ligands: Synthesis, Stability, and Evaluation as Catalysts for Methane and Benzene H/D Exchange,” 
Organometallics 2010, 29, 257–262.

A chemical reaction scheme showing a platinum complex reacting with a ligand in DMSO and MeOH, forming an intermediate, then reacting with CF3CO2D to yield a new platinum complex with a CF3CO2 ligand.

36. Ball, N. D.; Kampf, J. W.; Sanford, M. S. “Synthesis and Reactivity of Palladium (II) Fluoride Complexes Containing Nitrogen Donor Ligands,” Dalton Trans. 2010, 39, 632–640.

35. Lyons, T. W.; Sanford, M. S. “Palladium-Catalyzed Ligand-Directed C–H Functionalization Reactions,” 
Chem. Rev. 2010, 110, 1147–1169.

34. Higgs, A. T.; Zinn, P. J.; Simmons, S. J.; Sanford, M. S. “Oxidatively Induced Carbon-Halogen Bond-Forming Reactions at Nickel,” Organometallics 2009, 28, 6142–6144.

A chemical reaction showing a Ni(II) complex with bipyridine and Br, reacting with CuBr₂, forming an intermediate, then yielding a bipyridyl-Br product at 25°C.

33. Lanci, M. P.; Remy, M. S.; Kaminsky, W.; Mayer, J. M.; Sanford, M. S. “Oxidatively Induced Reductive Elimination from (tBu2bpy)Pd(Me)2: Palladium (IV) Intermediates in a One Electron Oxidation Reaction,” J. Am. Chem. Soc. 2009, 131, 15618–15620.

Reaction scheme showing a methylated palladium complex reacting with Cp2Fe+ to form intermediates, releasing ethane, and yielding a final product; reaction observed by 1H NMR spectroscopy.

32. Stowers, K. J.; Sanford, M. S. “Mechanistic Comparison Between Palladium-Catalyzed C–H Acetoxylation and C–H Chlorination,” Org. Lett. 2009, 11, 4584–4587.

Two chemical structures interconvert; one has a chlorine substituent and the other an acetate. Different palladium catalysts enable the transformation. A box notes that the mechanism varies and cyclopalladation is turnover-limiting.

31. Arnold, P. L.; Sanford, M. S.; Pearson, S. M. “Chelating N-Heterocyclic Carbene-Alkoxide as a Supporting Ligand for PdII/IV C–H Bond Functionalization Catalysis,” J. Am. Chem. Soc. 2009, 131, 13912–13913.

Chemical reaction diagram showing catalytic carbene-alkoxide supported Pd(IV) enabling sp² C–H bond halogenation, converting a hydrogen on a fused-ring molecule to chlorine.

30. Hickman, A. J.; Villalobos, J. M.; Sanford, M. S. “A Quantitative Method to Assay Platinum Catalysts for Benzene H/D Exchange,” Organometallics 2009, 28, 5316–5322.

Reaction scheme showing benzene with a Pt catalyst and deuterated reagents producing deuterated benzene. Inset shows a structural diagram of the most active of 10 platinum catalysts tested.

29. Deprez, N. R.; Sanford, M. S. “Synthetic and Mechanistic Studies of Pd-Catalyzed C–H Arylation with Diaryliodonium Salts: Evidence for a Bimetallic High Oxidation State Pd Intermediate,” J. Am. Chem. Soc. 2009, 131, 11234–11241.

28. Racowski, J. M.; Dick, A. R.; Sanford, M. S. “Detailed Study of C–O and C–C Bond-Forming Reductive Elimination from Stable C2N2O2 Palladium (IV) Complexes,” J. Am. Chem. Soc. 2009, 131, 10974–10983.

A chemical reaction scheme shows esters and biphenyls reacting with Pd catalyst and NBu4(O2CAr) to form a palladium complex, then yielding a final product in quantitative yield with a 1.6:1 ester to biphenyl ratio.

27. Hull, K. L.; Sanford, M. S. “Mechanism of Benzoquinone-Promoted Palladium-Catalyzed Oxidative Cross Coupling Reactions,” J. Am. Chem. Soc. 2009, 131, 9651–9653.

26. Ball, N. D.; Sanford, M. S. “Synthesis and Reactivity of a Mono-σ-Aryl Palladium (IV) Fluoride Complex,” 
J. Am. Chem. Soc. 2009, 131, 3796–3797.

A chemical reaction scheme showing Pd complexes reacting with XeF2, leading to a fluorinated benzene product. A molecular structure diagram of a Pd complex with labeled atoms is included. Reaction conditions and times are indicated.

25. Lyons, T. W.; Sanford, M. S. “PdII/IV-Catalyzed Cyclopropanation Reactions: Scope and Mechanism,”  Tetrahedron 2009, 65, 3211–3221.

A chemical scheme shows a methyl-substituted alkyne reacting with Pd(OAc)₂ and PhI(OAc)₂, forming a bicyclic intermediate, then rearranging to a product with a methyl and phenyl substituent.

24. Desai, L. V.; Stowers, K. J.; Sanford, M. S. “Insights into Directing Group Ability in Palladium-Catalyzed C–H Bond Functionalization,”  J. Am. Chem. Soc. 2008, 130, 13285–13293.

Reaction scheme: Two quinoline derivatives react with Pd(OAc)₂ and PhI(OAc)₂ in AcOH/Ac₂O at 100°C. One product with aromatic acetoxylation (>99%), the other regioisomer formed in <1% yield.

23. Whitfield, S. R.; Sanford, M. S. “Reactions of Platinum (II) Complexes with Chloride-Based Oxidants: Routes to PtIV and PtIII Products,” Organometallics 2008, 27, 1683–1689.

Reaction schemes show palladium and platinum complexes reacting with a maleimide derivative in dichloromethane at 25°C for 5 minutes, each yielding a major product with the same core structure.

22. Kalyani, D.; Sanford, M. S. “Oxidatively Intercepting Heck Intermediates: Pd-Catalyzed 1,2- and 1,1-Arylhalogenation of Alkenes,” J. Am. Chem. Soc. 2008, 130, 2150–2151.

Reaction schemes showing how using CuCl₂ or PhICl₂ as oxidants with Pd catalyst and Ph–SnBu₃ produces different chlorination products from an OTBPS-protected alkene, with yields and selectivities indicated.

21. Whitfield, S. L.; Sanford, M. S. “Reactivity of PdII Complexes with Electrophilic Chlorinating Reagents: Isolation of PdIV Intermediates and Observation of C–Cl Bond-Forming Reductive Elimination,” 
J. Am. Chem. Soc. 2007, 129, 15142–15143.

A chemical reaction scheme shows two Pd(II) complexes forming a Pd(IV) intermediate, which on heating yields three organic products and regenerates Pd(II). Arrow directions and structures are depicted.

20. Hull, K. L.; Sanford, M. S. “Catalytic and Highly Regioselective Cross-Coupling of Aromatic C–H Substrates,” 
J. Am. Chem. Soc. 2007, 129, 11904–11905.

Chemical reaction scheme showing chloropyridine, quinoline, and benzene derivative as reactants, with catalysts and conditions, yielding a single regioisomeric product featuring a fused quinoline and pyridine structure.

19. Deprez, N. R.; Sanford, M. S. “Reactions of Hypervalent Iodine Reagents with Palladium: Mechanisms and Applications in Organic Synthesis,” Inorg. Chem. 2007, 46, 1924–1935.

Reaction scheme: A phenanthridine with pivaloyl and triflate groups reacts with palladium catalyst and phenylboronic acid in the presence of benzene to form three different phenanthridine derivatives.

18. Desai, L. V.; Sanford, M. S. “Construction of Tetrahydrofurans via PdII/IV-Catalyzed Aminooxygenation of Alkenes,”  Angew. Chem., Int. Ed. 2007, 46, 5737–5740.

17. Welbes, L. L.; Lyons, T. W.; Cychosz, K. A.; Sanford, M. S. “Synthesis of Cyclopropanes via PdII/IV-Catalyzed Reactions of Enynes,”  J. Am. Chem. Soc. 2007, 129, 5836–5837.

A chemical reaction scheme showing a methyl and phenyl substituted alkyne reacting to form a bicyclic compound via a palladium-catalyzed cyclization, with intermediates and loss of a palladium catalyst.

16. Dick, A. R.; Remy, M. S.; Kampf, J. W.; Sanford, M. S. “Carbon-Nitrogen Bond-Forming Reactions Between Palladacycles and Hypervalent Iodine Reagents,” Organometallics 2007, 26, 1365–1370.

A chemical reaction sequence showing a palladium-catalyzed amination of phenanthroline with PhI=NTs, forming a N-tosyl intermediate, followed by HCl treatment to yield N-aminated phenanthroline.

15. Kalyani, D.; Sanford, M. S. “Chelate-Directed Oxidative Functionalization of Carbon-Hydrogen Bonds: Synthetic Applications and Mechanistic Insights,”
In Topics in Organometallic Chemistry, Vol. 24, Naoto Chatani, Ed., Springer, 2007, 85–116.

14. Hull, K. L.; Lanni, E. L.; Sanford, M. S. “Highly Regioselective Catalytic Oxidative Coupling Reactions: Synthetic Scope and Mechanistic Insights,” J. Am. Chem. Soc. 2006, 128, 14047-14049.

A chemical scheme showing C–H activation reactions at Pd(II) and Pd(IV) using Pd(OAc)2 and Oxone, with organic molecules and reaction arrows, highlighting mechanistic pathways and intermediates.

13. Kalyani, D.; Dick, A. R.; Anani, W. Q.; Sanford, M. S. “Scope and Selectivity in Palladium-Catalyzed Directed C–H Bond Halogenation Reactions,”Tetrahedron 2006, 62, 11483–11498.

Reaction scheme showing a Pd-catalyzed aryl C–H halogenation mechanism with intermediates involving palladium(II) and palladium(IV) complexes, and an electrophilic halogenating reagent.

12. Kalyani, D.; Dick, A. R.; Anani, W. Q.; Sanford, M. S. “A Simple Catalytic Method for the Regioselective Halogenation of Arenes,” Org. Lett. 2006, 8, 2523–2526.

A chemical reaction scheme shows methylquinoline with Cl, H, Br, or I, converted using Pd(OAc)₂ and NCS, NBS, or NIS for chlorination, bromination, or iodination, respectively.

11. Hull, K. L.; Anani, W. Q.; Sanford, M. S. “Palladium-Catalyzed Fluorination of Carbon-Hydrogen Bonds,”
J. Am. Chem. Soc. 2006, 128, 7134–7135.

Chemical reaction: Pyridine with a trifluoromethyl group reacts with a fluorinated aryl tetrafluoroborate under Pd(OAc)₂ and microwave conditions to give a fluorinated pyridine product (75% yield).

10. Deprez, N. R.; Kalyani, D.; Krause, A.; Sanford, M. S. “Room Temperature Palladium-Catalyzed 2-Arylation of Indoles,”
 J. Am. Chem. Soc. 2006, 128, 4972–4973.

Chemical reaction scheme: indole and iodobenzene react using 5 mol% palladium(II) catalyst and acetic acid at room temperature to produce a 2-arylindole compound.

9. Desai, L. V.; Malik, H. A.; Sanford, M. S. “Oxone as an Inexpensive Safe and Environmentally Benign Oxidant for C–H Bond Oxygenation,” Org. Lett. 2006, 8, 1141–1144.

Reaction scheme: A brominated aromatic compound with a methoxyimino group is converted to its acetate derivative using Pd, Oxone, and AcOH, or to its methoxy analog with Pd, Oxone, and MeOH.

8. Kalberer, E. W.; Whitfield, S. R.; Sanford, M. S. “Application of Recyclable, Polymer-Immobilized IodineIII Oxidants in Catalytic C–H Bond Functionalization,” J. Mol. Catal. A. 2006, 251, 108–113.

Chemical reaction scheme: two organic compounds react with Pd(OAc)₂ and AcOH at 100°C for 12 hours, yielding two products, with further steps involving methanol precipitation and regeneration with CH₃CO₃H.

7. Dick, A. R.; Sanford, M. S. “Transition Metal Catalyzed Catalyzed Oxidative Functionalization of Carbon-Hydrogen Bonds,” Tetrahedron 2006, 62, 2439–2463.

Reaction scheme showing a central alkene with arrows to various transformations: amination, oxygenation, halogenation, borylation, and dehydrogenation, each with relevant catalysts and reagents indicated.

6. Dick, A. R.; Kampf, J. W.; Sanford, M. S. “Unusually Stable Palladium (IV) Complexes: Detailed Mechanistic Investigation of C–O Bond-Forming Reductive Elimination,” J. Am. Chem. Soc. 2005, 127, 12790–12791.

A chemical reaction scheme shows a Pd complex reacting with Ph(O2CPh)2 to form a Pd(IV) intermediate, then heating yields bipyridine and a Pd(II) complex with N(CD3)3, demonstrating C–O bond-forming reductive elimination.

5. Kalyani, D.; Sanford, M. S. “Regioselectivity in Palladium-Catalyzed C–H Activation/Oxygenation Reactions,” 
Org. Lett. 2005, 7, 4149–4152.

A chemical reaction scheme shows pyridine derivatives with different X groups reacting to form acetoxylated pyridines using Pd(OAc)₂ and PhI(OAc)₂, with yields of 59–83% and ortho-selectivity.

4. Kalyani, D.; Deprez, N. R.; Desai, L. V.; Sanford, M. S. “Oxidative C–H Activation/C–C Bond Forming Reactions: Synthetic Scope and Mechanistic Insights,” J. Am. Chem. Soc. 2005, 127, 7330–7331.

A reaction scheme shows phenylpyridine with reagents to give a biaryl product. A palladium(IV) intermediate is depicted, highlighting C–C bond formation via reductive elimination, with 88% yield indicated.

3. Dick, A. R.; Kampf, J. W.; Sanford, M. S. “Platinum Model Studies for Palladium-Catalyzed Oxidative Functionalization of C–H Bonds,” Organometallics 2005, 24, 482–485.

A chemical reaction scheme showing platinum complexes with CN and OR ligands reacting with PhI(OAc)2 to give a cyclic platinum dimer. CN is benzo[h]quinoline or 8-methylquinoline; OR groups vary (Me, Et, iPr).

2. Desai, L. V.; Hull , K. L.; Sanford, M. S. “Palladium-Catalyzed Oxygenation of Unactivated sp3 C–H Bonds,” 
J. Am. Chem. Soc. 2004, 126, 9542–9543.

A chemical reaction where a methoxy-substituted imine reacts with AcO2Pd catalyst, forming a palladium complex, leading to an acetoxy-substituted product in 77% yield.

1. Dick, A. R.; Hull, K. L.; Sanford, M. S. “A Highly Selective Catalytic Method for the Oxidative Functionalization of C–H Bonds,” J. Am. Chem. Soc. 2004, 126, 2300–2301.

Reaction scheme: o- or p-alkylated toluene (L) reacts with Pd(OAc)₂ and PhI(OAc)₂, converting the benzylic hydrogen to an acetate group (OAc) while retaining the alkyl group (L).