Bifunctional sulfilimines enable synthesis of multiple N-heterocycles from alkenes

Nature Chemistry, Journal Year: 2022, Volume and Issue: 14(8), P. 898 - 904

Published: July 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.

Language: Английский

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Regiodivergent Electrophotocatalytic Aminooxygenation of Aryl Olefins

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(41), P. 18803 - 18809

Published: Oct. 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.

Language: Английский

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Regiospecific Alkene Aminofunctionalization via an Electrogenerated Dielectrophile

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(15), P. 8299 - 8307

Published: April 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.

Language: Английский

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

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(20), P. 13301 - 13309

Published: Oct. 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.

Language: Английский

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Mechanochemical synthesis of organoselenium compounds

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Jan. 26, 2024

We disclose herein a strategy for the rapid synthesis of versatile organoselenium compounds under mild conditions. In this work, magnesium-based selenium nucleophiles are formed in situ from easily available organic halides, magnesium metal, and elemental via mechanical stimulation. This process occurs liquid-assisted grinding (LAG) conditions, requires no complicated pre-activation procedures, operates broadly across diverse range aryl, heteroaryl, alkyl substrates. symmetrical diselenides efficiently obtained after work-up air, while one-pot nucleophilic addition reactions with various electrophiles allow comprehensive unsymmetrical monoselenides high functional group tolerance. Notably, method is applied to regioselective selenylation diiodoarenes polyaromatic aryl halides that difficult operate solution approaches. Besides selenium, sulfur tellurium also competent process, which showcases potential methodology facile organochalcogen compounds.

Language: Английский

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Catalytic Enantioselective Aminative Difunctionalization of Alkenes

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(10), P. 7029 - 7038

Published: March 1, 2024

Enantioselective difunctionalization of alkenes offers a straightforward means for the rapid construction enantioenriched complex molecules. Despite tremendous efforts devoted to this field, enantioselective aminative remains challenge, particularly through an electrophilic addition fashion. Herein, we report unprecedented approach via copper-catalyzed with external azo compounds as nitrogen sources. A series valuable cyclic hydrazine derivatives either [3 + 2] cycloaddition or intramolecular cyclization have been achieved in high chemo-, regio-, enantio-, and diastereoselectivities. In transformation, wide range functional groups, such carboxylic acid, hydroxy, amide, sulfonamide, aryl could serve nucleophiles. Importantly, new cyano oxazoline chiral ligand was found play crucial role control enantioselectivity.

Language: Английский

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Asymmetric Synthesis with Organoselenium Compounds – The Past Twelve Years

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(21)

Published: Jan. 11, 2024

Abstract The discovery and synthetic applications of novel organoselenium compounds their reactions proceeded rapidly during the past fifty years such processes are now carried out routinely in many laboratories. At same time, growing demand for new enantioselective provided challenges. convergence selenium chemistry asymmetric synthesis led to key developments 1970s, although majority early work was based on stoichiometric processes. More recently, greater emphasis has been placed greener catalytic variations, along with a deeper understanding mechanisms. present review covers literature this field from 2010 2023 encompasses mediated by chiral selenium‐based reagents, auxiliaries, especially, catalysts. Protocols achiral conjunction other species catalysts, as well that controlled substrates, also included.

Language: Английский

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Electrochemical Organoselenium-Catalyzed Intermolecular Hydroazolylation of Alkenes with Low Catalyst Loadings

Organic Letters, Journal Year: 2022, Volume and Issue: 24(29), P. 5345 - 5350

Published: July 19, 2022

The organoselenium-catalyzed amination of alkenes is a promising way to construct functionalized amines. However, the use chemical oxidants and unavoidable formation allylic amine or enamine are two main limitations these methodologies. Against this background, we herein report an electro-selenocatalytic regime for hydroazolylation with azoles under external oxidant-free conditions low catalyst loadings. Moreover, protocol enables generation amines without vinyl substituents.

Language: Английский

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Selenylation Chemistry Suitable for On‐Plate Parallel and On‐DNA Library Synthesis Enabling High‐Throughput Medicinal Chemistry

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(35)

Published: May 17, 2022

Abstract Click chemistry is a concept wherein modular synthesis used for rapid functional discovery. To this end, continuous discovery of clickable chemical transformations the pillar to support development field. This report details C3‐H selenylation indole that suitable on‐plate parallel and DNA‐encoded library ( Se DEL) via bioinspired LUMO activation strategy. reaction modular, robust highly site‐selective, it features simple mild system (catalyzed by nonmetallic B(C 6 F 5 ) 3 at room temperature), high yields excellent group compatibility. Using method, 1350 indole‐selenides was synthesized in an efficient practical manner, enabling identification ai as promising compound with nanomolar antiproliferative activity cancer cells situ phenotypic screening. These results indicate great potential new high‐throughput medicinal biology.

Language: Английский

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Enantioselective Selenol-ene Using Rh-Hydride Catalysis

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(40), P. 18246 - 18250

Published: Sept. 26, 2022

This study showcases the first enantioselective hydroselenation of styrenes. Organoselenium building blocks are accessed with selectivity for branched isomer. Through a Rh-hydride pathway, C–Se bonds can be forged excellent regio- and enantiocontrol.

Language: Английский

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