Photoinduced Copper-Catalyzed Late-Stage Azidoarylation of Alkenes via Arylthianthrenium Salts

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(25), С. 13542 - 13548

Опубликована: Июнь 12, 2023

The arylethylamine pharmacophore is conserved across a range of biologically active natural products and pharmaceuticals, particularly in molecules that act on the central nervous system. Herein, we present photoinduced copper-catalyzed azidoarylation alkenes at late stage with arylthianthrenium salts, allowing access to highly functionalized acyclic (hetero)arylethylamine scaffolds are otherwise difficult access. A mechanistic study consistent rac-BINAP-CuI-azide (2) as photoactive catalytic species. We show utility new method by expedient synthesis racemic melphalan four steps through C-H functionalization.

Язык: Английский

---

Nickel Meets Aryl Thianthrenium Salts: Ni(I)-Catalyzed Halogenation of Arenes

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(18), С. 9988 - 9993

Опубликована: Май 1, 2023

Herein, a regioselective, late-stage two-step arene halogenation method is reported. We propose how unusual Ni(I)/(III) catalysis enabled by combination of aryl thianthrenium and Ni redox properties that hitherto unachieved with other (pseudo)halides. The catalyst accessed in situ from inexpensive NiCl2·6(H2O) zinc without the need supporting ligands.

Язык: Английский

---

Selective Fluorosulfonylation of Thianthrenium Salts Enabled by Electrochemistry

Organic Letters, Год журнала: 2023, Номер 25(4), С. 581 - 586

Опубликована: Янв. 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.

Язык: Английский

---

Transition-metal-free C–S bond cleavage and transformation of organosulfur compounds

Chemical Communications, Год журнала: 2023, Номер 59(36), С. 5343 - 5364

Опубликована: Янв. 1, 2023

The activation and transformation of organic chemical bonds is a fundamental scientific problem. In the past several decades, C-S bond cleavage for construction C-C C-heteroatom has received tremendous attention in chemistry. Although significant progress been made field transition metal strategies, variety novel transition-metal-free strategies have also developed using halogenated reagents, oxidants, acids, bases. Moreover, photochemical electrochemical methods to achieve organosulfur compounds. To date, however, no comprehensive review reported. Therefore, we herein provide major advances compounds, including thioethers, sulfoxides, sulfones, thioacetals, sulfonium salts, sulfur ylides.

Язык: Английский

---

Thianthrenium-Enabled Phosphorylation of Aryl C–H Bonds via Electron Donor–Acceptor Complex Photoactivation

Organic Letters, Год журнала: 2023, Номер 25(20), С. 3784 - 3789

Опубликована: Май 16, 2023

An efficient strategy for the preparation of aryl phosphonates via blue-light-promoted single electron transfer process an EDA complex between phosphites and thianthrenium salts has been demonstrated. The corresponding substituted were obtained in good to excellent yields, byproduct thianthrene can be recovered reused quantity. This developed method realizes construction through indirect C-H functionalization arenes, which potential application value drug discovery development.

Язык: Английский

---

Arylthianthrenium Salts as the Aryl Sources: Visible Light/Copper Catalysis-Enabled Intermolecular Azidosulfonylation of Alkenes

Organic Letters, Год журнала: 2024, Номер 26(9), С. 1845 - 1850

Опубликована: Фев. 26, 2024

The difunctionalization of alkenes using aryl thianthrenium salts as the sources has been reported sporadically. However, four-component on basis not thus far and still remains a challenge. Herein, visible light/copper catalysis-enabled reaction salts, DABCO·(SO

Язык: Английский

---

Unified metal-free intermolecular Heck-type sulfonylation, cyanation, amination, amidation of alkenes by thianthrenation

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Янв. 15, 2024

Abstract Direct and site-selective C-H functionalization of alkenes under environmentally benign conditions represents a useful attractive yet challenging transformation to access value-added molecules. Herein, unified protocol for variety intermolecular Heck-type functionalizations C sp2 -H bond has been developed by thianthrenation. The reaction features metal-free operationally simple exclusive cine -selective aliphatic aryl forge C-C, C-N, C-P, C-S bonds at room temperature, providing general with nucleophiles (Nu = sulfinates, cyanides, amines, amides). Alkenes undergo -sulfonylation, cyanation, amination afford alkenyl sulfones, nitriles enamines.

Язык: Английский

---

A Practical and Regioselective Strategy for Aromatic C–H Difunctionalization via Site-Selective C–H Thianthrenation

Organic Letters, Год журнала: 2024, Номер 26(9), С. 1813 - 1818

Опубликована: Фев. 22, 2024

Herein, we present a novel Catellani-type reaction that employed aryl-thianthrenium salts as aryl substrates to trigger the subsequent palladium/norbornene cooperatively catalyzed progress. This strategy can achieve site-selective C–H difunctionalization of compounds without directing groups or known initiating reagent. A series functionalized syntheses bioactive molecules further demonstrated potential this strategy.

Язык: Английский

---

Synthetic Applications of Sulfonium Salts as Aryl Radical Precursors

European Journal of Organic Chemistry, Год журнала: 2023, Номер 26(43)

Опубликована: Сен. 13, 2023

Abstract The utilization of aryl radicals as open‐shelled intermediates has become an essential tool for both conventional and state‐of‐the‐art synthetic chemistry. However, the current methods generating are still inefficient, greatly impeding their practical applications. Encouragingly, sulfonium salts have emerged appealing sources a wide range transformations aimed at creating novel chemical bonds driven by distinctive structural attributes tendencies. This review primarily focuses on specific reaction mechanisms underlying cleavage C−S in salts, leading to generation corresponding within diverse conditions.

Язык: Английский

---

Regiospecific Alkene Aminofunctionalization via an Electrogenerated Dielectrophile

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(15), С. 8299 - 8307

Опубликована: Апрель 6, 2023

Modular strategies to rapidly increase molecular complexity have proven immensely synthetically valuable. In principle, transformation of an alkene into a dielectrophile presents opportunity deliver two unique nucleophiles across alkene. Unfortunately, the selectivity profiles known dielectrophiles largely precluded this deceptively simple synthetic approach. Herein, we demonstrate that dicationic adducts generated through electrolysis alkenes and thianthrene possess profile relative more conventional dielectrophiles. Specifically, these species undergo single perfectly regioselective substitution reaction with phthalimide salts. This observation unlocks appealing new platform for aminofunctionalization reactions. As illustrative example, implement reactivity paradigm address longstanding challenge: diamination distinct nitrogen nucleophiles. Studies mechanism process reveal key alkenyl thianthrenium salt intermediate controls exquisite regioselectivity highlight importance proton sources in controlling sulfonium electrophiles.

Язык: Английский

---