Research summary
A review of C-H activation for C-B bond construction surveyed transition-metal-catalyzed direct borylation of alkanes and arenes, classifying mechanisms and substrate scope [1]. Methodological commentary on deuterium kinetic isotope effects in C-H functionalizations argued that a primary KIE from H/D substitution does not by itself imply C-H bond cleavage during the rate-determining step, with care needed in experiment design and interpretation [2]. A retrospective traced the evolution of four catalyst generations for palladium-catalyzed amination and thioetherification of aryl halides, displacing classical synthetic routes (nitration/reduction, copper chemistry, benzyne, nucleophilic aromatic substitution) for arylamine pharmaceutical and materials synthesis [3]. The mechanism of Pd-catalyzed C-N and C-O bond formation was framed in terms of oxidative addition and reductive elimination from four-coordinate 16-electron amido aryl or alkoxide aryl complexes, with chelating ligands such as DPPF suppressing competing beta-hydride elimination [4]. Ir(I) precursors with bipyridine ligands catalyzed arene borylation with high turnover numbers; [Ir(COE)2Cl]2 plus 4,4-di-t-butylbipyridine reached room-temperature reactivity for both electron-rich and electron-poor arenes and gave high turnovers for hydrocarbon functionalization at 100 degrees C [5]. An account on carbon-heteroatom bond-forming reductive eliminations summarized the formation of amines, ethers and sulfides from organopalladium amido, alkoxide and thiolate intermediates [6]. A platform review of C-H borylation and silylation surveyed reagent classes, ligand effects and site-selectivity strategies for synthesizing functionalized organic molecules with high turnover and broad functional-group tolerance [7]. An account on Pd-catalyzed alpha-arylation of carbonyl compounds and nitriles described how sterically hindered electron-rich alkylphosphines and N-heterocyclic carbenes broadened scope across ketones, amides, esters, aldehydes, nitriles, malonates and related anions [8]. A 1995 study established that aryl halides plus secondary amines with silylamide base and tri-o-tolylphosphine Pd complexes gave arylamine products without tin reagents, by cleaving palladium aryl halide dimers with secondary amines [9].
Recent publications
- C鈭扝 Activation for the Construction of C鈭払 BondsDOI
- On the Interpretation of Deuterium Kinetic Isotope Effects in CH Bond Functionalizations by Transition鈥怣etal ComplexesDOI
- Evolution of a Fourth Generation Catalyst for the Amination and Thioetherification of Aryl HalidesDOI
- Transition Metal Catalyzed Synthesis of Arylamines and Aryl Ethers from Aryl Halides and Triflates: Scope and MechanismDOI
- Mild Iridium-Catalyzed Borylation of Arenes. High Turnover Numbers, Room Temperature Reactions, and Isolation of a Potential IntermediateDOI
- Carbon鈭扝eteroatom Bond-Forming Reductive Eliminations of Amines, Ethers, and SulfidesDOI
- Borylation and Silylation of C鈥揌 Bonds: A Platform for Diverse C鈥揌 Bond FunctionalizationsDOI
- Carbon鈥揾eteroatom bond formation catalysed by organometallic complexesDOI
- Palladium-Catalyzed 伪-Arylation of Carbonyl Compounds and NitrilesDOI
- Palladium-catalyzed synthesis of arylamines from aryl halides. Mechanistic studies lead to coupling in the absence of tin reagentsDOI
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Email John F. Hartwig 6-12 months before your application deadline. Read several recent papers and reference specific work in your message. Use our how to email a Japanese professor guide for the proven email structure.
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External profiles
- ORCID: https://orcid.org/0000-0002-4157-468X
- OpenAlex: openalex.org
Profile compiled from public sources (Researchmap, OpenAlex, Hokkaido University faculty directory). Last refreshed 2026-05. Report incorrect information.