Bismuth Redox Catalysis: An Emerging Main-Group Platform for Organic Synthesis

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(2), P. 1382 - 1393

Published: Jan. 7, 2022

Bismuth has recently been shown to be able maneuver between different oxidation states, enabling access unique redox cycles that can harnessed in the context of organic synthesis. Indeed, various catalytic Bi platforms have discovered and revealed emerging opportunities field main group catalysis. The goal this perspective is provide an overview synthetic methodologies developed date, which capitalize on cycling. Recent methods via low-valent Bi(II)/Bi(III), Bi(I)/Bi(III), high-valent Bi(III)/Bi(V) couples are covered as well their underlying mechanisms key intermediates. In addition, we illustrate design strategies stabilizing bismuth species, highlight characteristic reactivity complexes, compared lighter p-block d-block elements. Although it not catalysis nature, also discuss a recent example non-Lewis acid, redox-neutral Bi(III) proceeding through organometallic steps. We close by discussing future directions hope Perspective will chemists with guiding principles for development transformations employing bismuth.

Language: Английский

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Advances in the construction of diverse SuFEx linkers

National Science Review, Journal Year: 2023, Volume and Issue: 10(6)

Published: April 29, 2023

Abstract Sulfur fluoride exchange (SuFEx), a new generation of click chemistry, was first presented by Sharpless, Dong and co-workers in 2014. Owing to the high stability yet efficient reactivity SVI–F bond, SuFEx has found widespread applications organic synthesis, materials science, chemical biology drug discovery. A diverse collection linkers emerged, involving gaseous SO2F2 SOF4 hubs; SOF4-derived iminosulfur oxydifluorides; O-, N- C-attached sulfonyl fluorides sulfonimidoyl fluorides; novel sulfondiimidoyl fluorides. This review summarizes progress these connectors, with an emphasis on analysing advantages disadvantages synthetic strategies connectors based concept, it is expected be beneficial researchers rapidly correctly understand this field, thus inspiring further development chemistry.

Language: Английский

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Sulfur(vi) fluorides as tools in biomolecular and medicinal chemistry

Organic & Biomolecular Chemistry, Journal Year: 2023, Volume and Issue: 21(7), P. 1356 - 1372

Published: Jan. 1, 2023

This review highlights key advances in the synthesis and biomolecular applications of sulfur( vi )-fluorides.

Language: Английский

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Selective Fluorosulfonylation of Thianthrenium Salts Enabled by Electrochemistry

Organic Letters, Journal Year: 2023, Volume and Issue: 25(4), P. 581 - 586

Published: Jan. 25, 2023

A practical electrochemically driven method for fluorosulfonylation of both aryl and alkyl thianthrenium salts has been disclosed. The strategy does not need external redox reagents or metal catalysts. In combination with C-H thianthrenation aromatics, this provides a new tool the site-selective drugs.

Language: Английский

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Direct electrochemical synthesis of arenesulfonyl fluorides from nitroarenes: a dramatic ionic liquid effect

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(6), P. 3435 - 3440

Published: Jan. 1, 2024

A practical electrosynthesis of aryl sulfonyl fluorides from nitroarenes is described. Cheap N -methylimidazolium p -toluenesulfonate has been found to be an effective additive, promoting the desired fluorosulfonylation under very mild conditions.

Language: Английский

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Photoredox catalytic radical fluorosulfonylation of olefins enabled by a bench-stable redox-active fluorosulfonyl radical precursor

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: June 11, 2022

Abstract Sulfonyl fluorides have attracted considerable and growing research interests from various disciplines, which raises a high demand for novel effective methods to access this class of compounds. Radical flurosulfonylation is recently emerging as promising approach the synthesis sulfonyl fluorides. However, scope applicable substrate reaction types are severely restricted by limited known radical reagents. Here, we introduce solid state, redox-active type fluorosulfonyl reagents, 1-fluorosulfonyl 2-aryl benzoimidazolium triflate (FABI) salts, enable fluorosulfonylation olefins under photoredox conditions. In comparison with precursor, gaseous FSO 2 Cl, FABI salts bench-stable, easy handle, affording yields in before challenging substrates. The advantage FABIs further demonstrated development an alkoxyl-fluorosulfonyl difunctionalization olefins, forges facile useful β-alkoxyl related compounds, would thus benefit study context chemical biology drug discovery future.

Language: Английский

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(Hetero)aryl‐S^VI Fluorides: Synthetic Development and Opportunities

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(23)

Published: March 18, 2022

(Hetero)arylsulfur compounds where the S atom is in oxidation state VI represent a large percentage of molecular functionalities present organic chemistry. More specifically, (hetero)aryl-S

Language: Английский

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Scalable, Chemoselective Nickel Electrocatalytic Sulfinylation of Aryl Halides with SO₂

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(37)

Published: July 12, 2022

Abstract Simple access to aryl sulfinates from iodides and bromides is reported using an inexpensive Ni‐electrocatalytic protocol. The reaction exhibits a broad scope, uses stock solution of simple SO 2 as sulfur source, can be scaled up in batch recycle flow settings. limitations this are clearly shown put into context by benchmarking with state‐of‐the‐art Pd‐based methods.

Language: Английский

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Catalytic Decarboxylative Fluorosulfonylation Enabled by Energy-Transfer-Mediated Photocatalysis

Organic Letters, Journal Year: 2022, Volume and Issue: 24(13), P. 2474 - 2478

Published: March 9, 2022

Sulfonyl fluorides are useful building blocks in a wide array of fields. Herein, we report catalytic decarboxylative fluorosulfonylation approach for converting abundant aliphatic carboxylic acids to the corresponding sulfonyl fluorides. This transformation is enabled by simple preactivation as aldoxime esters and energy-transfer-mediated photocatalysis. operationally method proceeds with high functional-group tolerance under mild redox-neutral conditions.

Language: Английский

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One-Pot Synthesis of Sulfonamides from Unactivated Acids and Amines via Aromatic Decarboxylative Halosulfonylation

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(39), P. 21189 - 21196

Published: Sept. 20, 2023

The coupling of carboxylic acids and amines to form amide linkages is the most commonly performed reaction in pharmaceutical industry. Herein, we report a new strategy that merges these traditional partners generate sulfonamides, important bioisosteres. This method leverages copper ligand-to-metal charge transfer (LMCT) convert aromatic sulfonyl chlorides, followed by one-pot amination corresponding sulfonamide. process requires no prefunctionalization native acid or amine extends diverse set aryl, heteroaryl, s-rich aliphatic substrates. Further, extend this synthesis (hetero)aryl fluorides, which have found utility as "click" handles chemical probes programmable bifunctional reagents. Finally, demonstrate protocols analogue synthesis.

Language: Английский

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