Fluorination of arylboronic esters enabled by bismuth redox catalysis

  title={Fluorination of arylboronic esters enabled by bismuth redox catalysis},
  author={Oriol Planas and Feng Wang and Markus Leutzsch and Josep Cornella},
  pages={313 - 317}
Teaching bismuth to make and break bonds One major reason why transition metals are good catalysts is that they can shuttle between oxidation states. This flexibility lets them slide in and out of chemical bonds; so, for instance, they can snip a bond between carbon and boron and then stitch a carbonfluorine bond in its place. Planas et al. now report that bismuth can also orchestrate such bond-swapping events. They implement a fully catalytic cycle for fluorination of aryl boronates, in which… 
Redox-Neutral Organometallic Elementary Steps at Bismuth: Catalytic Synthesis of Aryl Sulfonyl Fluorides
It is demonstrated that the organobismuth(III) catalysts bearing a bis-aryl sulfone ligand backbone revolve through different canonical organometallic steps within the catalytic cycle without modifying the oxidation state.
Dialkyl Ether Formation at High-Valent Nickel
The results of this article indicate that the use of F+ oxidants permits the challenging C(sp3)–OC( sp3) bond formation at a high-valent nickel center to proceed in good yields while minimizing deleterious elimination reactions.
Tris(2-pyridyl) Bismuthines: Coordination Chemistry, Reactivity, and Anion-Triggered Pyridyl Coupling.
Structural studies of Li+ and Ag+ complexes show that the coordination to metal ions using their pyridyl-N atoms and to anions using the Lewis acidity of their Bi(III) centers can be modified by the presence of substituents within the 2-pyridol rings, especially at the 6- or 3-positions.
Bismuth Redox Catalysis: An Emerging Main-Group Platform for Organic Synthesis
Bismuth has recently been shown to be able to maneuver between different oxidation states, enabling access to unique redox cycles that can be harnessed in the context of organic synthesis. Indeed,
Bismuth-Catalyzed Oxidative Coupling of Arylboronic Acids with Triflate and Nonaflate Salts
A Bi-catalyzed cross-coupling of arylboronic acids with perfluoroalkyl sulfonate salts based on a Bi(III)/Bi(V) redox cycle using commercially available NaOTf and KONf as coupling partners is presented.
Mechanism of the Aryl-F Bond-Forming Step from Bi(V) Fluorides.
In this article, we describe a combined experimental and theoretical mechanistic investigation of the C(sp2)-F bond formation from neutral and cationic high-valent organobismuth(V) fluorides,
Dibismuthanes in catalysis: from synthesis and characterization to redox behavior towards oxidative cleavage of 1,2-diols†
A family of aryl dinuclear bismuthane complexes has been successfully synthesized and characterized and the synergy between bismUTH centers in catalysis has been studied by applying dinuclearbismuthanes 5–8 to the catalytic oxidative cleavage of 1,2-diols.
Bimetallic cooperation across the periodic table
Organometallic chemistry and its applications in homogeneous catalysis have been dominated by mononuclear transition-metal complexes. The catalytic performance and physico-chemical properties of
Electrochemical Studies of the Cycloaddition Activity of Bismuth(III) Acetylides Towards Organic Azides Under Copper(I)-Catalyzed Conditions
Time-dependent monitoring of the reactive intermediates provides valuable information about the mechanism of a synthetic transformation. However, the process frequently involves intermediates with
Catalytic Activation of N2O at a Low-Valent Bismuth Redox Platform
This protocol represents a distinctive example of a main-group redox cycling for the catalytic activation of N2O at a BiI⇄BiIII redox platform and features remarkably mild conditions and high turnover numbers and turnover frequencies.


Bismuth Compounds in Radical Catalysis: Transition Metal Bismuthanes Facilitate Thermally-Induced Cyclo-Isomerizations.
The first catalytic application of transition metal bismuthane compounds with a Bi-TM bond is reported, establishing transition metalbismuthanes as a new class of (pre-)catalysts for controlled radical reactions.
Metal-free catalytic C-H bond activation and borylation of heteroarenes
It is demonstrated that the borane (1-TMP-2-BH2-C6H4)2 (TMP, 2,2,6,6-tetramethylpiperidine) can activate the C-H bonds of heteroarenes and catalyze the borylation of furans, pyrroles, and electron-rich thiophenes.
Bismuth-Mediated Organic Reactions
Bismuth Catalysts in Aqueous Media, by Shu Kobayashi, Masaharu Ueno and Taku Kitanosono.- Pentavalent Organobismuth Reagents in Organic Synthesis: Alkylation, Alcohol Oxidation and Cationic
Silylation of C–H bonds in aromatic heterocycles by an Earth-abundant metal catalyst
It is found that readily available and inexpensive potassium tert-butoxide catalyses the direct silylation of aromatic heterocycles with hydrosilanes, furnishing heteroarylsilanes in a single step, and is scalable to greater than 100 grams under optionally solvent-free conditions.
Imine hydrogenation with simple alkaline earth metal catalysts
AbstractHydrogenation of unsaturated bonds is dominated by transition metal catalysis. Compared with transition metals, the use of other metals is less explored, especially so for the s-block
Heterobiaryl synthesis by contractive C–C coupling via P(V) intermediates
Phosphorus proves a versatile coupling agent for nitrogen heterocycles in pharmaceutical and agrochemical synthesis and enables convergent coupling of drug fragments and late-stage heteroarylation of pharmaceuticals.
Catalytic Vicinal Dichlorination of Unactivated Alkenes
Over a century after the initial discovery of the Willgerodt reagent (PhICl2), an operationally simple, catalytic alternative has been validated and preliminary validation of an enantiomeric variant is established.
Fluorotetraphenylbismuth: a new reagent for efficient regioselective alpha-phenylation of carbonyl compounds.
The results imply the vast potential of organobismuth(V) compounds of type 1 and 2 as useful precursors of a wide variety of pentavalent organOBismuth compounds based on the utilization of the eminent fluorine-silicon interaction or the inherent basicity of the fluorine atom.
Coordination Complexes of Bismuth(III) Involving Organic Ligands with Pnictogen or Chalcogen Donors
Publisher Summary The chapter presents an overview of the structural diversity demonstrated by complexes of bismuth(III) with organic-based ligands involving the elements of Groups 15 (pnictogens)
Catalytic oxidative coupling promoted by bismuth TEMPOxide complexes.
These compounds are active catalysts for oxidative coupling of TEMPO and silane substrates, believed to proceed via metathesis of Bi-O and Si-H bonds followed by decomposition of bismuth-hydride intermediate species.