Energy transfer-enabled unsymmetrical diamination using bifunctional nitrogen-radical precursors

Nature Catalysis, Год журнала: 2022, Номер 5(12), С. 1120 - 1130

Опубликована: Дек. 8, 2022

Язык: Английский

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Recent advances in aminative difunctionalization of alkenes

Organic & Biomolecular Chemistry, Год журнала: 2021, Номер 19(14), С. 3036 - 3054

Опубликована: Янв. 1, 2021

This review summarizes recent advances in transition metal-catalyzed or metal-free aminative difunctionalization of alkenes to construct nitrogen-containing compounds.

Язык: Английский

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Iron‐Catalyzed Radical Asymmetric Aminoazidation and Diazidation of Styrenes

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(22), С. 12455 - 12460

Опубликована: Март 22, 2021

Abstract Asymmetric aminoazidation and diazidation of alkenes are straightforward strategies to build value‐added chiral nitrogen‐containing compounds from feedstock chemicals. They provide direct access organoazides complement enantioselective diamination. Despite the advances in non‐asymmetric reactions, asymmetric or based on acyclic systems has not been previously reported. Here we describe iron‐catalyzed intermolecular styrenes. The method is practically useful requires relatively low loading catalyst ligand. With mild reaction conditions, can be completed a 20 mmol scale. Studies mechanism suggest that proceeds via radical pathway involves stereocontrol an free which probably takes place through group transfer mechanism.

Язык: Английский

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Insights into the Recent Synthetic Advances of Organoselenium Compounds

ChemistrySelect, Год журнала: 2021, Номер 6(4), С. 663 - 679

Опубликована: Янв. 25, 2021

Abstract The ever‐growing interest for organoselenium compounds amongst the chemists has made commendable impact in field of medicinal chemistry, material chemical biology and biochemistry. Researchers have progressively contributed development over years which been periodically reviewed. On similar note, this review attempts at providing an overview recent advances chemistry while covering their catalytic indulgence different transformational approaches, role asymmetric synthesis, synthetic approaches steering synthesis. These encompass selenofunctionalization and/or cyclization, electrochemical selenylation, bromolactonization, [2,3]‐ or [1,2]‐sigmatropic rearrangement reactions among others. Herein, we focused on developed past three that not covered previously reviewed scientific material. With knowledge progress covered, could contribute towards future along with improvement current status.

Язык: Английский

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Diastereodivergent Intermolecular 1,2-Diamination of Unactivated Alkenes Enabled by Iodine Catalysis

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(11), С. 4112 - 4118

Опубликована: Март 12, 2021

The stereospecific, substrate (nitrogen source)-controlled intermolecular anti- and syn-1,2-diaminations of unactivated alkenes using the same catalysis (an iodine catalyst) is reported. combined use two potential methods provides access to all disastereomeric forms 1,2-diamines in spite availability E- Z-alkenes, resulting products can be readily converted into free vicinal diamines.

Язык: Английский

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Palladium-Catalyzed Asymmetric Sequential Hydroamination of 1,3-Enynes: Enantioselective Syntheses of Chiral Imidazolidinones

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(25), С. 11364 - 11376

Опубликована: Июнь 10, 2022

Pd-catalyzed sequential hydroamination of readily available 1,3-enynes is reported. The redox-neutral process provides an efficient route to synthesize a broad scope imidazolidinones, thiadiazolidines, and imidazolidines. Asymmetric generates series synthetically valuable, enantioenriched imidazolidinones. Mechanistic studies revealed that the transformation occurred via intermolecular enyne pathway give allene intermediate. Subsequent intramolecular intermediate proceeded under Curtin-Hammett principle provide imidazolidinone products.

Язык: Английский

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Tuning Orbital Symmetry of Iridium Nitrenoid Enables Catalytic Diastereo- and Enantioselective Alkene Difunctionalizations

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(10), С. 3993 - 4004

Опубликована: Март 5, 2021

Among the central themes in synthetic chemistry is establishment of novel strategies that usher development more efficient and mild reactions also expand chemical space for asymmetric catalysis. Herein, we present an approach to revitalize Cp*Ir(κ2-LX) system as a catalyst toward alkene difunctionalizations via nitrenoid-mediated pathway. A key strategy tuning orbital symmetry Ir nitrenoid intermediates by ligand modification impart desired catalytic activity with suppression deactivation. On basis frontier molecular (FMO) analysis, systematically engineered new capable stepwise transfer allow nucleophile incorporation. Using protocol, range difunctionalized lactams can be produced diastereoselective manner various nucleophiles. Mechanistic investigations revealed plays crucial role both nitrenoid-delivery stereoselectivity-determining steps. The current mechanistic platform enabled methods introducing two-point chirality (oxy-alkyl)lactam products excellent enantioselectivity.

Язык: Английский

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Bifunctional sulfilimines enable synthesis of multiple N-heterocycles from alkenes

Nature Chemistry, Год журнала: 2022, Номер 14(8), С. 898 - 904

Опубликована: Июль 25, 2022

Abstract Intramolecular cyclization of nitrogen-containing molecules onto pendant alkenes is an efficient strategy for the construction N-heterocycles, which are paramount importance in, example, pharmaceuticals and materials. Similar intermolecular reactions, however, scarcer nitrogen building blocks, including N-centred radicals, divergent modular versions not established. Here we report use sulfilimines as bifunctional N-radical precursors reactions with to produce N-unprotected heterocycles in a single step through photoredox catalysis. Structurally diverse can be synthesized step, subsequently engage afford synthetically valuable five-, six- seven-membered heterocycles. The broad scope achievable by radical-polar crossover annulation enabled character reagents, distinguishes itself from all other N-centred-radical-based reactions. synthesis allows larger structural diversity N-heterocycle products than currently methods.

Язык: Английский

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Regiodivergent Electrophotocatalytic Aminooxygenation of Aryl Olefins

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(41), С. 18803 - 18809

Опубликована: Окт. 4, 2022

A method for the regiodivergent aminooxygenation of aryl olefins under electrophotocatalytic conditions is described. The procedure employs a trisaminocyclopropenium (TAC) ion catalyst with visible light irradiation controlled electrochemical potential to convert corresponding oxazolines high chemo- and diastereoselectivity. With judicious choice between two inexpensive abundant reagents, namely water urethane, either 2-amino-1-ol or 1-amino-2-ol derivatives could be prepared from same substrate. This amenable multigram synthesis oxazoline products low loadings.

Язык: Английский

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Electrophilic Selenium-Catalyzed Desymmetrizing Cyclization to Access P-Stereogenic Heterocycles

ACS Catalysis, Год журнала: 2023, Номер 13(20), С. 13301 - 13309

Опубликована: Окт. 2, 2023

The construction of phosphorus stereocenters under metal-free conditions remains a formidable challenge. Herein, we report mechanistically distinct chiral electrophilic selenium catalysis-enabled desymmetrizing cyclization to access valuable phosphorus-stereogenic heterocycles with high efficiency. This ambient temperature method affords broad range compounds that bear phenolic hydroxyl group as useful synthetic handle and, thus, enriches the toolbox for rapid generation molecular complexity. control experiments and DFT calculations indicate dual-hydrogen-bonding bridge formed between substrate TfO– anion plays crucial role in determining enantioselectivity transformation.

Язык: Английский

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