Radical approaches to C–S bonds

Nature Reviews Chemistry, Journal Year: 2023, Volume and Issue: 7(8), P. 573 - 589

Published: June 21, 2023

Language: Английский

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Aminoselenation and Dehydroaromatization of Cyclohexanones with Anilines and Diselenides

Organic Letters, Journal Year: 2024, Volume and Issue: 26(22), P. 4835 - 4839

Published: May 29, 2024

A three-component cascade reaction involving cyclohexanones, anilines, and diaryl diselenides under metal-free conditions is reported. The ortho-selenation of cyclohexanones with diselenides, followed by sequential dehydroaromatization enables the preparation a variety o-selanyl anilines in moderate to excellent yields. This innovative transformation notable for its tolerance functional groups suitable late-stage modification complex pharmaceuticals.

Language: Английский

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Photochemical Organocatalytic Synthesis of Thioethers from Aryl Chlorides and Alcohols

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(5), P. 2907 - 2912

Published: Jan. 24, 2024

Thioethers, often found in pharmaceuticals and natural compounds, typically involve metal cross-coupling reactions, high temperatures, the use of disagreeable thiols for their synthesis. Here we present a straightforward, thiol-free organocatalytic protocol that uses mild conditions to stitch together inexpensive alcohols aryl chlorides, yielding diverse array alkyl thioethers. Central this approach was discovery tetramethylthiourea can serve as simple sulfur source upon intercepting photochemically generated radicals. To form radicals, used readily available indole thiolate organocatalyst that, when excited with 405 nm light, gained strongly reducing power, enabling activation unreactive chlorides via single-electron transfer. Radical trapping by thiourea, followed an alcohol attack polar path, resulted formation thioether products.

Language: Английский

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DFT-Enabled Development of Hemilabile (P^∧N) Ligands for Gold(I/III) RedOx Catalysis: Application to the Thiotosylation of Aryl Iodides

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(6), P. 3660 - 3674

Published: Feb. 5, 2024

Ligand-enabled oxidative addition of Csp2-X bonds to Au(I) centers has recently appeared as a valuable strategy for the development catalytic RedOx processes. Several cross-coupling reactions that were previously considered difficult achieve reported lately, thus expanding synthetic potential gold(I) complexes beyond traditional nucleophilic functionalization π-systems. MeDalPhos played an important role in this and, despite several studies on alternative structures, remains, so far, only general ligand such process. We report herein discovery and DFT-enabled structural optimization new family hemilabile (P∧N) ligands can promote aryl iodides gold(I). These flexible ligands, which possess common 2-methylamino heteroaromatic N-donor motif, are structurally electronically tunable, being easily accessible affordable. The corresponding shown outperform reactivity (MeDalPhos)Au(I) series alkoxy- amidoarylations alkenes. Their comparatively higher further highlighted thiotosylation iodides, challenging unreported C–S reaction could not be achieved under classical Pd(0/II) catalysis allows divergent access sulfur derivatives.

Language: Английский

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The green chemistry paradigm in modern organic synthesis

Russian Chemical Reviews, Journal Year: 2023, Volume and Issue: 92(12), P. RCR5104 - RCR5104

Published: Dec. 1, 2023

After the appearance of green chemistry concept, which was introduced in vocabulary early 1990s, its main statements have been continuously developed and modified. Currently, there are 10–12 cornerstones that should form basis for an ideal chemical process. This review analyzes accumulated experience achievements towards design products processes reduce or eliminate use generation hazardous substances. The presents views leading Russian scientists specializing various fields this subject, including homogeneous heterogeneous catalysis, fine basic organic synthesis, electrochemistry, polymer chemistry, based on bio-renewable feedstocks energetic compounds materials. A new approach to quantitative evaluation environmental friendliness by authors is described. <br> bibliography includes 1761.

Language: Английский

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Reaction of Diaryliodonium Salts with Potassium Alkyl Xanthates as an Entry Point to Accessing Organosulfur Compounds

Organic Letters, Journal Year: 2023, Volume and Issue: 25(1), P. 272 - 276

Published: Jan. 3, 2023

Preparation of S-aryl xanthates via transition-metal-catalyzed or SNAr reactions is complicated by their further transformations under the utilized conditions. In contrast, S-arylation potassium O-alkyl with diaryliodonium salts proceeds mild conditions, enabling access to substituted xanthates. The method exhibits good functional group tolerance and can be applied late-stage C–H functionalization drug molecules. Divergent resulting provide rapid a range medicinal chemistry-relevant organosulfur compounds.

Language: Английский

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A general electron donor–acceptor complex enabled cascade cyclization of alkynes to access sulfur-containing heterocycles

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(8), P. 3111 - 3116

Published: Jan. 1, 2023

A general visible light-promoted and electron–donor–acceptor complex-enabled cascade reaction of alkynes to produce functionalized sulfur-containing heterocycles under photocatalyst-, base-, oxidant- metal-free conditions was developed.

Language: Английский

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Gold-catalyzed alkenylation and arylation of phosphorothioates

Chemical Science, Journal Year: 2023, Volume and Issue: 14(45), P. 13134 - 13139

Published: Jan. 1, 2023

Reported herein is the ligand-enabled gold-catalyzed alkenylation and arylation of phosphorothioates using alkenyl aryl iodides. Mechanistic studies revealed a crucial role in situ generated Ag-sulfur complex, which undergoes facile transmetalation with Au(iii) intermediate, thereby leading to successful realization present reaction. Moreover, for first time, phosphoroselenoates under gold redox catalysis has been presented.

Language: Английский

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Generation and Application of Aryl Radicals Under Photoinduced Conditions

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(31)

Published: March 28, 2024

Abstract Photoinduced aryl radical generation is a powerful strategy in organic synthesis that facilitates the formation of diverse carbon‐carbon and carbon‐heteroatom bonds. The synthetic applications photoinduced complex compounds, including natural products, physiologically significant molecules, functional materials, have received immense attention. An overview current developments production methods their uses given this article. A generalized idea how to choose reagents approach for radicals described, along with techniques associated mechanistic insights. Overall, article offers critical assessment results as well selection reaction parameters specific context cascades, cross‐coupling reactions, functionalization, selective C−H functionalization substrates.

Language: Английский

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Enantioselective Arylation of Sulfenamides to Access Sulfilimines Enabled by Palladium Catalysis

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(37)

Published: June 27, 2024

Abstract Sulfur‐containing functional groups have garnered considerable attention due to their common occurrence in ligands, pharmaceuticals, and insecticides. Nevertheless, enantioselective synthesis of sulfilimines, particularly diaryl sulfilimines remains a challenging persistent goal. Herein we report highly enantio‐ chemoselective cross–coupling sulfenamides with aryl diazonium salt construct diverse S(IV) stereocenters by Pd catalysis. Bisphosphine ligands bearing sulfinamide play crucial role achieving high reactivity selectivity. This approach provides general, modular divergent framework for quickly synthesizing chiral sulfoximines that are otherwise access. In addition, the origins chemoselectivity enantioselectivity were extensively investigated using density theory calculations.

Language: Английский

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