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

Ivan Borkovic,

Zorana Ferjančić, Filip Bihelović

и другие.

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

C-to-N atom swapping and skeletal editing in indoles and benzofurans DOI Creative Commons
Zhe Wang, Pengwei Xu, Shu‐Min Guo

и другие.

Nature, Год журнала: 2025, Номер unknown

Опубликована: Май 21, 2025

Abstract Skeletal editing comprises the structural reorganization of compounds. Such can be achieved through atom swapping, insertion, deletion or compound’s backbone structure 1,2 . Conducted at a late stage in drug development campaigns, skeletal enables diversification an existing pharmacophore, enhancing efficiency development. Instead constructing heteroarene classically from basic building blocks, variants are readily accessible directly starting lead compound approved pharmacophore. Here we present C to N swapping indoles C2 position give indazoles oxidative cleavage indole core and subsequent ring closure. Reactions proceed ring-opened oximes as intermediates. These deconstructed intermediates also diverted into benzimidazoles resulting overall with concomitant reorganization. The same diverting strategies equally well applicable benzofurans leading either benzisoxazoles benzoxazoles. classes obtained these methods—indazoles 3,4 , 5 6,7 benzoxazoles 8 —are biologically relevant moieties found substructures natural products pharmaceuticals. procedures introduced substantially enlarge methods portfolio emerging field editing.

Язык: Английский

Процитировано

2

Transition Metal-Catalyzed Nitrogen Atom Insertion into Carbocycles DOI
Hong Lu, Jie Chang, Hao Wei

и другие.

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

Процитировано

1

Parametrization of κ2-N,O-Oxazoline Preligands for Enantioselective Cobaltaelectro-Catalyzed C–H Activations DOI Creative Commons
Suman Dana, Neeraj Kumar Pandit, Philipp Boos

и другие.

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 4450 - 4459

Опубликована: Фев. 28, 2025

Enantioselective electrocatalyzed C–H activations have emerged as a transformative platform for the assembly of value-added chiral organic molecules. Despite recent progress, construction multiple C(sp3)-stereogenic centers via C(sp3)–C(sp3) bond formation has thus far proven to be elusive. In contrast, we herein report an annulative activation strategy, generating Fsp3-rich molecules with high levels diastereo- and enantioselectivity. κ2-N,O-oxazoline preligands were effectively employed in enantioselective cobalt(III)-catalyzed reactions. Using DFT-derived descriptors regression statistical modeling, performed parametrization study on modularity preligands. The resulted model describing ligands' selectivity characterized by key steric, electronic, interaction behaviors.

Язык: Английский

Процитировано

1

Induced Circularly Polarized Luminescence From 0D Quantum Dots by 2D Chiral Nanosheets DOI
Yuqi Xiao,

Aiyan Shi,

Guojian Yang

и другие.

Small, Год журнала: 2024, Номер unknown

Опубликована: Сен. 5, 2024

Abstract Materials with circularly polarized luminescence (CPL) exhibit great application potential in biological scenes such as cell imaging, optical probes, etc. However, most developed materials are non‐aqueous and toxic, which seriously restricts their compatibility the life systems. Thus, it is necessary to explore a water‐based CPL system high biocompatibility so that promote biologic process. Herein, facile efficient route achieve properties of functional aqueous solution demonstrated by combination 0D quantum dots (QDs) 2D chiral nanosheets. Benefited specific absorption ability nanosheets for left/right‐handed CPL, QDs adsorbed onto surface through hydrogen bond interactions showed apparent features. In addition, this has good extensibility property can be effectively regulated changing kind emissive QDs. More importantly, nano‐composite fabrication process (one‐step mixing) suitable real applications, undoubtedly beneficial further progress materials.

Язык: Английский

Процитировано

1

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

Ivan Borkovic,

Zorana Ferjančić, Filip Bihelović

и другие.

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

Процитировано

1