Dibenzothiophenium Salts: Practical Alternatives to Hypervalent I(III)-Based Reagents

Accounts of Chemical Research, Год журнала: 2025, Номер unknown

Опубликована: Фев. 2, 2025

ConspectusDuring the past few years, interest among organic synthesis practitioners in use of sulfonium salts has exponentially growth. This can arguably be attributed to a series specific factors: (a) The recent development more direct and efficient protocols for these species, which make reagents wide structural variety easily available multigram scale. (b) recognition that reactivity resembles hypervalent iodine compounds, therefore, they used as effective replacement such species most their applications. (c) Their intrinsic thermal stability tolerance air moisture, clearly surpass I(III)-reagents analogue reactivity, facilitate purification, isolation well-defined storage, safely handling on larger (d) Finally, possibility further functionalize once sulfur-containing platform been incorporated. Specifically, this last synthetic approach is not trivial when working with I(III)-species facilitates access no counterpart I(III) realm.This renewed led improvement already existing transformations well discovery unprecedented ones; particular, by incorporate partners traditional cross-coupling C–H activation steps or combine them modern technologies photocatalysis electrosynthesis. In Account, originally prepared our laboratory will outlined compared I(III)-counterparts. Some are now commercially available, started spread widely across chemistry community, helping speed process identification potentially bioactive products new functionaliced materials. However, challenges still remain. characterized an optimal balance between site-selectivity, showing broader compatibility toward sensitive functional groups need. addition, often makes necessary (sophisticated) catalysts activate latent hidden structures. Although priori one see fact disadvantage, it might actually decisive harvest full potential because surely preparation operational context I(III)-chemistry. If becomes true, may contribute expediting retrosynthetic disconnections that, date, impossible.

Язык: Английский

---

Transition Metal-Catalyzed Nitrogen Atom Insertion into Carbocycles

Accounts of Chemical Research, Год журнала: 2025, Номер unknown

Опубликована: Фев. 26, 2025

ConspectusN-Heterocycles are essential in pharmaceutical engineering, materials science, and synthetic chemistry. Recently, skeletal editing, which involves making specific point changes to the core of a molecule through single-atom insertion, deletion, or transmutation, has gained attention for its potential modify complex substrates. In this context, insertion nitrogen atoms into carbocycles form N-heterocycles emerged as significant research focus modern chemistry owing novel logic. This distinctive retrosynthetic approach enables late-stage modification molecular skeletons provides different pathway synthesizing multiply substituted N-heterocycles. Nevertheless, atom proven challenging because inherent inertness carbon-based difficulty cleaving C-C bonds. Therefore, selective editing remains growing field Account primarily highlights contributions our laboratory active acknowledges key from other researchers. It is organized two sections based on type carbocycle. The first section explores cycloalkenes. Recent Co-catalyzed oxidative azidation strategies have enabled cyclobutenes, cyclopentenes, cyclohexenes, facilitating synthesis polysubstituted pyridines, been conventionally pyridine cross-coupling. subsequent discovery realm arenes. site-selective stable arenes We developed method intramolecular benzene rings 2-amino biaryls by suppressing competing C-H process using paddlewheel dirhodium catalyst. addition, address issues we employed arenols substrates, could act controlling elements editing. reported Cu-catalyzed arenols, proceeds dearomative azidation/aryl migration process, enabling incorporation Inspired result, recently extended reaction model Fe-catalyst facilitate ring contraction nitrogen-inserted product, achieving carbon-to-nitrogen transmutation arenols. Various polyaromatic effectively undergo desired atom's presenting considerable various applications Account, present an overview achievements reactions, with scopes, mechanistic features, applications. anticipate that will provide valuable insights propel development innovative methodologies both N-heterocycle synthesis.

Язык: Английский

---

Molecular Ring Remodeling through C–C Bond Cleavage

Accounts of Chemical Research, Год журнала: 2025, Номер unknown

Опубликована: Фев. 27, 2025

ConspectusStable and inert C-C bonds form the fundamental framework of organic compounds. Consequently, direct transformations involving bond cleavage present an innovative approach for rapid modification remodeling molecular skeletons. In recent years, concept skeletal editing has garnered widespread attention been significantly developed, providing new opportunities late-stage bioactive molecules, high-value transformation bulk chemicals, a revolution in traditional fragment coupling strategies chemical synthesis. Notable advancements this field have focused on cyclic including ring expansion, contraction, ring-opening reactions, thereby enriching synthetic toolbox available to chemists. However, selective remains formidable challenge, especially complex due high dissociation energy difficulty achieving precise selectivity control. Over past few our group made efforts address these challenges. We demonstrated potential molecule reactions as efficient strategy synthesis molecules.Herein, we two major thematic achieved by group, utilizing cascade activation entropy-driven reconstruction via cleavage. These are characterized mild conditions, accessibility catalysts reagents, exceptional functional compatibility, emerging novel approaches through atom-incorporation mainly nitrogenation, oxygenation, halogenation synthesize pharmaceuticals, natural products, material molecules. (1) Ring expansion reactions: developed that enable insertion C-, N-, O-containing units into rings. methodologies offer practical routes synthesizing amides, amines, lactones, nitrogen-containing heterocycles. (2) Ring-opening enables construction distally difunctionalized frameworks. By transition metal catalysis radical-mediated process, successfully both single C═C double within Furthermore, tackled highly challenging arene (ARO) reaction, enabling stereoselective conjugated systems unsaturation liberation aromatic systems. Mechanistic studies DFT calculations provided critical insights processes. also identified key intermediates involved cleavage, benzyl azide, O-acetyl hydroxylamine, β-azido peroxyl radical, copper bisnitrene, 2-nitrene indazole. findings deepened understanding mechanisms strategy, which further promoted discovery related acyclic substrates.

Язык: Английский

---

Metal-Free Aziridination of Unactivated Olefins via Transient N-Pyridinium Iminoiodinanes

JACS Au, Год журнала: 2024, Номер 4(11), С. 4187 - 4193

Опубликована: Окт. 10, 2024

We describe a metal-free aziridination of unactivated olefins to generate

Язык: Английский

---

A Formal 1,2-Stevens Rearrangement of Thioester Ylides as a Single-Atom Molecular Editing Tool

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Дек. 23, 2024

A rhodium-catalyzed reaction of thioesters with diazo reagents was recognized as a powerful and unprecedented tool for single-atom molecular editing by the insertion single carbon atom into C(O)─S thioester bond, thereby leading to various α-thioketones possessing quaternary atom. selective precise defunctionalization polyfunctionalized products further demonstrated synthetic utility synthesis more common structural classes compounds.

Язык: Английский

---