Progress in organocatalysis with hypervalent iodine catalysts

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(18), P. 8102 - 8139

Published: Jan. 1, 2022

Hypervalent iodine compounds as environmentally friendly and relatively inexpensive reagents have properties similar to transition metals. They are employed alternatives metal catalysts in organic synthesis mild, nontoxic, selective recyclable catalytic reagents. Formation of C-N, C-O, C-S, C-F C-C bonds can be seamlessly accomplished by hypervalent catalysed oxidative functionalisations. The aim this review is highlight recent developments the utilisation iodine(III) iodine(V) a wide range including chiral for stereoselective synthesis. Polymer-, magnetic nanoparticle- framework-supported also described.

Language: Английский

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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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Catalytic, Enantioselective Syn-Oxyamination of Alkenes

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(33), P. 13408 - 13417

Published: Aug. 10, 2021

The chemo-, regio-, diastereo-, and enantioselective 1,2-oxyamination of alkenes using selenium(II/IV) catalysis with a chiral diselenide catalyst is reported. This method uses N-tosylamides to generate oxazoline products that are useful both as protected 1,2-amino alcohol motifs ligands. reaction proceeds in good yields excellent enantio- diastereoselectivity for variety pendant functional groups such sulfonamides, alkyl halides, glycol-protected ketones. Furthermore, the rapid generation demonstrated expeditious assembly PHOX ligands well diversely amino alcohols.

Language: Английский

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Catalytic stereoselective synthesis involving hypervalent iodine-based chiral auxiliaries

Organic & Biomolecular Chemistry, Journal Year: 2023, Volume and Issue: 21(20), P. 4163 - 4180

Published: Jan. 1, 2023

A number of organic transformations have been achieved using hypervalent iodine reagents under mild reaction conditions. The use these as chiral organocatalyst exhibited highly selective asymmetric reactions.

Language: Английский

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Palladium-Catalyzed γ,γ′-Diarylation of Free Alkenyl Amines

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(27), P. 10352 - 10360

Published: June 23, 2021

The direct difunctionalization of alkenes is an effective way to construct multiple C-C bonds in one-pot using a single functional group. regioselective dicarbofunctionalization therefore important area research rapidly obtain complex organic molecules. Herein, we report palladium-catalyzed γ,γ'-diarylation free alkenyl amines through interrupted chain walking for the synthesis Z-selective amines. Notably, while 1,3-dicarbofunctionalization allyl groups well precedented, present disclosure allows highly substituted allylamines give trisubsubstituted olefin products. This cascade reaction operates via unprotected amine-directed Mizoroki-Heck (MH) pathway featuring β-hydride elimination selectively walk furnish new terminal which then generates cis-selective around sterically crowded moiety. operationally simple protocol applicable variety cyclic, branched, and linear secondary tertiary alkenylamines, has broad substrate scope with regard arene coupling partner as well. Mechanistic studies have been performed help elucidate mechanism, including presence likely unproductive side C-H activation pathway.

Language: Английский

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Olefin Difunctionalization for the Synthesis of Tetrahydroisoquinoline, Morpholine, Piperazine, and Azepane

Organic Letters, Journal Year: 2024, Volume and Issue: 26(1), P. 84 - 88

Published: Jan. 3, 2024

This report outlines a versatile strategy for synthesizing diverse array of N-heterocycles. By the utilization common olefins, this simple protocol facilitates their coupling with various bifunctional reagents. Furthermore, it can be integrated C–H amination techniques to directly produce N-heterocycles in multicomponent cascade process. The unique bond disconnection logic employed process underscores its efficiency achieving rapid simplification through couplings.

Language: Английский

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Imidazole-mediated Defluorosulfonylation of N-(Fluorosulfonyl)oxazolidinones Accessed by an Organoiodine(I/III)-catalyzed Oxyamination

Tetrahedron, Journal Year: 2025, Volume and Issue: unknown, P. 134611 - 134611

Published: March 1, 2025

Language: Английский

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Asymmetric oxidative rearrangement of indoles enabled by dual catalysis with in situ generated acyl hypoiodite and chiral phosphoric acid

Organic Chemistry Frontiers, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A dual catalytic asymmetric oxidative rearrangement of indoles via traceless halonium intermediates. This halide-catalyzed method features excellent enantioselectivity and broad functional group tolerance, including late-stage complex targets.

Language: Английский

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