Bismuth in Radical Chemistry and Catalysis

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(8)

Опубликована: Ноя. 22, 2023

Abstract Whereas indications of radical reactivity in bismuth compounds can be traced back to the 19 th century, preparation and characterization both transient persistent bismuth‐radical species has only been established recent decades. These advancements led emergence field chemistry, mirroring progress seen for other main‐group elements. The seminal fundamental studies this area have ultimately paved way development catalytic methodologies involving intermediates, a promising approach that remains largely untapped broad landscape synthetic organic chemistry. In review, we delve into milestones eventually present state‐of‐the‐art Our focus aims at outlining intrinsic discoveries inorganic/organometallic chemistry contextualizing their practical applications synthesis catalysis.

Язык: Английский

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Synthesis, Isolation, and Characterization of Two Cationic Organobismuth(II) Pincer Complexes Relevant in Radical Redox Chemistry

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(10), С. 5618 - 5623

Опубликована: Фев. 28, 2023

Herein, we report the synthesis, isolation, and characterization of two cationic organobismuth(II) compounds bearing N,C,N pincer frameworks, which model crucial intermediates in bismuth radical processes. X-ray crystallography uncovered a monomeric Bi(II) structure, while SQUID magnetometry combination with NMR EPR spectroscopy provides evidence for paramagnetic S = 1/2 state. High-resolution multifrequency at X-, Q-, W-band enable precise assignment full g- 209Bi A-tensors. Experimental data DFT calculations reveal both complexes are metal-centered radicals little delocalization onto ligands.

Язык: Английский

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Ligand-Enabled Oxidative Fluorination of Gold(I) and Light-Induced Aryl–F Coupling at Gold(III)

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Апрель 12, 2024

MeDalphos Au(I) complexes featuring aryl, alkynyl, and alkyl groups readily react with electrophilic fluorinating reagents such as

Язык: Английский

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Development and Scale-Up of a New Sulfone-Based Bismacycle as a Universal Precursor for Bi(V)-Mediated Electrophilic Arylation

Organic Process Research & Development, Год журнала: 2024, Номер 28(2), С. 632 - 639

Опубликована: Фев. 7, 2024

The scope and practical utility of bismuth(V)-mediated electrophilic arylation have been greatly improved by the recent development user-friendly protocols based on modular bismacycle reagents. Here, we report scalable synthesis a new bench-stable bromide demonstrate that it can be used as "universal precursor" in arylation. Relative to established syntheses related bismacycles, protocol benefits from step- vessel-economy, reduced production time, complete elimination cryogenic temperatures undesirable solvents (Et

Язык: Английский

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Molecular Bismuth Compounds: Ligand Design and Reactivity

Structure and bonding, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Язык: Английский

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Nitrogen-Based Organofluorine Functional Molecules: Synthesis and Applications

Chemical Reviews, Год журнала: 2025, Номер unknown

Опубликована: Апрель 22, 2025

Fluorine and nitrogen form a successful partnership in organic synthesis, medicinal chemistry, material sciences. Although fluorine-nitrogen chemistry has long rich history, this field received increasing interest made remarkable progress over the past two decades, driven by recent advancements transition metal organocatalysis photochemistry. This review, emphasizing contributions from 2015 to 2023, aims update state of art synthesis applications nitrogen-based organofluorine functional molecules chemistry. In dedicated sections, we first focus on fluorine-containing reagents organized according type groups attached nitrogen, including N-F, N-RF, N-SRF, N-ORF. review also covers nitrogen-linked building blocks, catalysts, pharmaceuticals, agrochemicals, underlining these components' broad applicability growing importance modern

Язык: Английский

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Transition-metal-catalyzed C–H bond activation as a sustainable strategy for the synthesis of fluorinated molecules: an overview

Beilstein Journal of Organic Chemistry, Год журнала: 2023, Номер 19, С. 448 - 473

Опубликована: Апрель 17, 2023

The last decade has witnessed the emergence of innovative synthetic tools for synthesis fluorinated molecules. Among these approaches, transition-metal-catalyzed functionalization various scaffolds with a panel groups (XR

Язык: Английский

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Bismuth‐Catalyzed Amide Reduction

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(32)

Опубликована: Июнь 7, 2023

In this article we report that a cationic version of Akiba's BiIII complex catalyzes the reduction amides to amines using silane as hydride donor. The catalytic system features low catalyst loadings and mild conditions, en route secondary tertiary aryl- alkylamines. tolerates functional groups such alkene, ester, nitrile, furan thiophene. Kinetic studies on reaction mechanism result in identification network with an important product inhibition is agreement experimental profiles.

Язык: Английский

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Theoretical Study on Bismuth(III) Catalysts for Synthesis of Phenylsulfonyl Fluoride: Reasons of Their Catalysis

ACS Catalysis, Год журнала: 2024, Номер 14(4), С. 2758 - 2774

Опубликована: Фев. 7, 2024

Bismuth(III) complex with diarylsulfone ligand (diAr-SO2) is a non-transition metal catalyst reported recently for the synthesis of arylsulfonyl fluorides. We investigated this catalytic reaction using DFT and SCS-MP2 calculations geometries energies, respectively. This occurs through transmetalation between (BF4)Bi(diAr-SO2) phenylboronic acid (PhB(OH)2), SO2 insertion into Bi–Ph bond (Ph)Bi(diAr-SO2), fluorination PhOSO group (PhOSO)Bi(diAr-SO2) by Selectfluor. The rate-determining step diAr-SO2 (CH3, CH3) (CF3, CF3) but either or CF3), where (R1, R2) means has R1 R2 substituents on its aryl groups. activation energy (ΔG°‡) increases in order < CF3). increasing consistent experimentally observed substituent effects activity. difficult to occur absence potassium phosphate (K3PO4) moderate presence K3PO4 because activates B–Ph σ-bond stabilizes dissociating B(OH)2 moiety electrostatic interaction. play an important role transmetalation; when strongly interacts Bi(diAr-SO2) species form overly stable adduct enlarge considerably ΔG°‡ value. When CH3), stabilization similar each other, destabilization more largely upon going asymmetric transition state from case than case. Thus, use favorable transmetalation. (Ph)Bi(diAr-SO2) value, whereas sulfone (SO2) replaced CH2 group. via nucleophilic attack Ph SO2. However, not most reactive only HOMO also factors such as Biδ+–(C6H3R)δ− (R = CH3 dipole moment Bi–C6H3R strength participate determining reactivity C6H3R part diArSO2. value extremely negative ΔG° Its hardly depends diAr-SO2. are key activity bismuth catalyst.

Язык: Английский

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Hydrobismuthation: Insertion of Unsaturated Hydrocarbons into the Heaviest Main Group Element Bond to Hydrogen

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(1), С. 19 - 23

Опубликована: Янв. 2, 2024

The bismuth hydride (2,6-Mes2H3C6)2BiH (1, Mes = 2,4,6-trimethylphenyl), which has a Bi–H 1H NMR spectroscopic signal at δ 19.64 ppm, was reacted with phenylacetylene 60 °C in toluene to yield [(2,6-Mes2C6H3)2BiC(Ph)=CH2] (2) after 15 min. Compound 2 characterized by 1H, 13C NMR, and UV–vis spectroscopy, single crystal X-ray crystallography, calculations employing density functional theory. is the first example of hydrobismuthation addition product displays Markovnikov regioselectivity. Computational methods indicated that it forms via radical mechanism an associated Gibbs energy activation 91 kJ mol–1 reaction −90 mol–1.

Язык: Английский

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