Ni-catalyzed C–S bond construction and cleavage

Chemical Society Reviews, Год журнала: 2022, Номер 51(19), С. 8351 - 8377

Опубликована: Янв. 1, 2022

This review focuses on nickel-catalyzed construction and transformation of various sulfide-containing compounds, such as sulfides, disulfides, hypervalent sulfur-containing compounds.

Язык: Английский

---

Acetate Facilitated Nickel Catalyzed Coupling of Aryl Chlorides and Alkyl Thiols

ACS Catalysis, Год журнала: 2022, Номер 12(4), С. 2233 - 2243

Опубликована: Янв. 31, 2022

We report a mild, fast, and convenient catalytic system for the coupling of aryl chlorides with primary, secondary, as well previously challenging tertiary alkyl thiols using an air-stable nickel(II) precatayst in combination low-cost base potassium acetate at room temperature. This tolerates variety functional groups enables generation thioethers wide range substrates, including pharmaceutical compounds excellent yields. Chemoselective functionalization disubstituted substrates was demonstrated. Kinetic NMR studies, DFT computations support Ni(0)/Ni(II) cycle identify oxidative addition product resting state. Acetate coordination subsequent facilitated formation thiolate complex via internal deprotonation play key role cycle.

Язык: Английский

---

Construction of diverse C–S/C–Se bonds via nickel catalyzed reductive coupling employing thiosulfonates and a selenosulfonate under mild conditions

Organic Chemistry Frontiers, Год журнала: 2022, Номер 9(5), С. 1375 - 1382

Опубликована: Янв. 1, 2022

A nickel-catalyzed reductive cross coupling between organic iodides and thiosulfonates a selenosulfonate under mild conditions is disclosed.

Язык: Английский

---

Mechanistic Investigation of the Nickel-Catalyzed Metathesis between Aryl Thioethers and Aryl Nitriles

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(29), С. 13096 - 13108

Опубликована: Июль 14, 2022

Functional group metathesis is an emerging field in organic chemistry with promising synthetic applications. However, no complete mechanistic studies of these reactions have been reported to date, particularly regarding the nature key functional transfer mechanism. Unraveling mechanism transformations would not only allow for their further improvement but also lead design novel reactions. Herein, we describe our detailed nickel-catalyzed reaction between aryl methyl sulfides and nitriles, combining experimental computational results. These did support a proceeding through reversible migratory insertion nitrile into Ni–Ar bond provided strong alternative involving transmetalation step two independently generated oxidative addition complexes. Extensive kinetic analysis, including rate law determination Eyring indicated complex as resting state catalytic reaction. Depending on concentration sulfide, either reductive elimination or C(sp2)–S sulfide turnover-limiting NMR studies, unusual 31P–2H HMBC experiment using deuterium-labeled complexes, unambiguously demonstrated that cyanide groups exchange during step, rather than moieties. In addition, Hammett analyses Ni(II) complexes revealed this central proceeds via associative Organometallic synthesis, isolation, characterization all putative intermediates possible deactivation shed light mechanism, identification pathway, which has led improved protocol.

Язык: Английский

---

Nickel-catalyzed cross-electrophile coupling of aryl thiols with aryl bromides via C–S bond activation

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(20), С. 5171 - 5179

Опубликована: Янв. 1, 2023

We report a cross-electrophile coupling of aryl thiols with bromides via C–S bond activation instead S–H cleavage. The reaction proceeded effectively in the presence nickel catalyst, magnesium, and lithium chloride to afford various biaryls moderate good yields.

Язык: Английский

---

Light-Controlled Switch for Divergent Coupling of Thiols to Disulfides/Thioethers over CdS Quantum Dots

ACS Materials Letters, Год журнала: 2025, Номер unknown, С. 1533 - 1539

Опубликована: Март 24, 2025

Язык: Английский

---

Transition‐Metal‐Free Difunctionalization of Sulfur Nucleophiles**

Angewandte Chemie International Edition, Год журнала: 2022, Номер 62(8)

Опубликована: Дек. 22, 2022

Efficient protocols for accessing iodo-substituted diaryl and aryl(vinyl) sulfides have been developed using iodonium salts as reactive electrophilic arylation vinylation reagents. The reactions take place under transition-metal-free conditions, employing odorless convenient sulfur A wide variety of functional groups are tolerated in the S-diarylation, enabling regioselective late-stage application several heterocycles drug molecules mild reaction conditions. novel S-difunctionalization pathway was discovered vinyliodonium salts, which proceeds additive-free conditions grants excellent stereoselectivity synthesis sulfides. one-pot strategy combining diarylation subsequent reduction provided facile access to electron-rich thioanilines a direct potential candidate derivative. retained iodo group allows array further synthetic transformations. Mechanistic insights were elucidated by isolating key intermediate, relevant energy profile substantiated DFT calculations.

Язык: Английский

---

Ring Expansion toward Disila‐carbocycles via Highly Selective C−Si/C−Si Bond Cross‐Exchange

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(16)

Опубликована: Фев. 23, 2024

Herein, we successfully inhibited the preferential homodimerization and C-Si/Si-H bond cross-exchange of benzosilacyclobutenes monohydro-silacyclobutanes achieved first highly selective C-Si/C-Si reaction by deliberately tuning Ni-catalytic system, which constitutes a powerful atom-economical ring expansion method for preparing medium-sized cyclic compounds bearing two silicon atoms at junction, are otherwise inaccessible. The DFT calculation explicitly elucidated pivotal role Si-H silacyclobutanes high strain substrates in realizing C-Si bonds cleavage reformation catalytic cycle.

Язык: Английский

---

Nickel-free cross-electrophile coupling of unactivated alkyl bromides with thiosulfonates and sulfinyl sulfones

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(9), С. 2518 - 2527

Опубликована: Янв. 1, 2024

An unusual zinc-promoted reductive coupling between alkyl bromides and thiosulfonates under nickel-free conditions is described.

Язык: Английский

---

Synthesis of Thioethers via Nickel-Catalyzed Cross-Coupling of Aryl Halides with Ketene Dithioacetal

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Фев. 9, 2025

Herein, we present a nickel-catalyzed C–S cross-coupling between aryl halides and ketene dithioacetals under "base-free" conditions without an exogenous ligand. By employing easily available as sulfide donors, this reaction affords broad range of unsymmetrical alkyl-aryl sulfides using odorous toxic thiols. The newly developed catalytic methodology features excellent functional group tolerance, wide substrate scope, diverse downstream synthesis. Preliminary mechanism investigations reveal that Ni(I)/Ni(III) cycle might be involved.

Язык: Английский

---