Synthesis and Transformations of NH‐Sulfoximines

Chemistry - A European Journal, Год журнала: 2021, Номер 27(69), С. 17293 - 17321

Опубликована: Сен. 14, 2021

Recent years have seen a marked increase in the occurrence of sulfoximines chemical sciences, often presented as valuable motifs for medicinal chemistry. This has been prompted by both pioneering works taking sulfoximine containing compounds into clinical trials and concurrent development powerful synthetic methods. review covers recent developments synthesis concentrating on since 2015. includes extensive S-N S-C bond formations. Flow chemistry processes are also covered. Finally, subsequent transformations sulfoximines, particularly N-functionalization reviewed, including N-S, N-P, N-C forming cyclization reactions.

Язык: Английский

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Synthesis of chiral sulfinate esters by asymmetric condensation

Nature, Год журнала: 2022, Номер 604(7905), С. 298 - 303

Опубликована: Фев. 14, 2022

Язык: Английский

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Catalytic Enantioselective Sulfur Alkylation of Sulfenamides for the Asymmetric Synthesis of Sulfoximines

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(39), С. 17808 - 17814

Опубликована: Сен. 26, 2022

Sulfoximines are increasingly incorporated in agrochemicals and pharmaceuticals, with the two enantiomers of chiral sulfoximines often having profoundly different binding interactions biomolecules. Therefore, their application to drug discovery development requires challenging preparation single rather than racemic mixtures. Here, we report a general fundamentally new asymmetric synthesis sulfoximines. The first S-alkylation sulfenamides, which readily accessible sulfur compounds one carbon nitrogen substituent, represents key step. A broad scope for was achieved by rhodium-catalyzed coupling diazo under mild conditions. When rhodium catalyst utilized loadings as low 0.1 mol %, products were obtained high yields enantiomeric ratios up 98:2 at newly generated center. efficiently converted variety complete retention stereochemistry. utility this approach further demonstrated complex sulfoximine agrochemical.

Язык: Английский

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Cobalt(III)/Chiral Carboxylic Acid‐Catalyzed Enantioselective Synthesis of Benzothiadiazine‐1‐oxides via C−H Activation

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(28)

Опубликована: Май 2, 2022

Abstract Among sulfoximine derivatives containing a chiral sulfur center, benzothiadiazine‐1‐oxides are important for applications in medicinal chemistry. Here, we report that the combination of an achiral cobalt(III) catalyst and pseudo‐ C 2 ‐symmetric H 8 ‐binaphthyl carboxylic acid enables asymmetric synthesis from sulfoximines dioxazolones via enantioselective C−H bond cleavage. With optimized protocol, with several functional groups can be accessed high enantioselectivity.

Язык: Английский

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Synthesis of Chiral Sulfonimidoyl Chloride via Desymmetrizing Enantioselective Hydrolysis

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(9), С. 5439 - 5446

Опубликована: Фев. 22, 2023

Direct construction of chiral S(VI) from prochiral S(II) is a formidable challenge due to the inevitable formation stable S(IV). Previous synthetic strategies rely on conversion S(IV) or enantioselective desymmetrization preformed symmetrical substrates. Here, we report desymmetrizing hydrolysis in situ-generated symmetric aza-dichlorosulfonium sulfenamides for preparation sulfonimidoyl chlorides, which could be used as general synthon obtaining series derivatives.

Язык: Английский

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Asymmetric Synthesis of S(IV) and S(VI) Stereogenic Centers

JACS Au, Год журнала: 2023, Номер 3(3), С. 700 - 714

Опубликована: Фев. 28, 2023

Sulfur can form diverse S(IV) and S(VI) stereogenic centers, of which some have gained significant attention recently due to their increasing use as pharmacophores in drug discovery programs. The preparation these sulfur centers enantiopure has been challenging, progress made will be discussed this Perspective. This Perspective summarizes different strategies, with selected works, for asymmetric synthesis moieties, including diastereoselective transformations using chiral auxiliaries, enantiospecific compounds, catalytic enantioselective synthesis. We discuss the advantages limitations strategies provide our views on how field develop.

Язык: Английский

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Enantioselective sulfur(VI) fluoride exchange reaction of iminosulfur oxydifluorides

Nature Chemistry, Год журнала: 2024, Номер 16(3), С. 353 - 362

Опубликована: Фев. 14, 2024

Язык: Английский

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Electrooxidative Rhodium(III)/Chiral Carboxylic Acid‐Catalyzed Enantioselective C−H Annulation of Sulfoximines with Alkynes

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(15)

Опубликована: Янв. 30, 2024

Abstract The combination of achiral Cp*Rh(III) with chiral carboxylic acids (CCAs) represents an efficient catalytic system in transition metal‐catalyzed enantioselective C−H activation. However, this hybrid catalysis is limited to redox‐neutral activation reactions and the adopt oxidative remains elusive pose a significant challenge. Herein, we describe development electrochemical Cp*Rh(III)‐catalyzed annulation sulfoximines alkynes enabled by acid (CCA) operationally friendly undivided cell at room temperature. A broad range enantioenriched 1,2‐benzothiazines are obtained high yields excellent enantioselectivities (up 99 % yield 98 : 2 er). practicality method demonstrated scale‐up reaction batch reactor external circulation. crucial intermediate isolated, characterized, transformed, providing rational support for Rh(III)/Rh(I) electrocatalytic cycle.

Язык: Английский

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Cobalt(III)-Catalyzed Enantioselective C–H Functionalization: Ligand Innovation and Reaction Development

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

Опубликована: Фев. 26, 2025

ConspectusIn contrast to precious transition metals, such as palladium and rhodium, the development of novel chiral ligands for enantioselective C-H functionalizations catalyzed by earth-abundant, cost-effective, environmentally friendly 3d metals poses substantial challenges, primarily due variable oxidation states, intricate coordination patterns, limited mechanistic insights. In this Account, we summarize our research endeavors in three types Co(III) catalysis: pseudotetrahedral achiral Cp*Co(III)/chiral carbonyl acid (CCA) catalysis, situ-generated octahedral cobalt(III) via cobalt/salicyloxazoline (Salox) Co(II)/chiral phosphoric (CPA) cooperative achieved through strategic ligand design. Our initial objective was achieve functionalization Cp*Co(III) catalysts with external ligands, aiming circumvent laborious preparation CpxCo(III) complexes. To end, developed several CCA incorporating non-covalent interactions (NCIs) a crucial design element. Next, address limitations associated lengthy synthesis Cp-ligated complexes difficulties modification, explored concept situ generation catalysis using commercially available cobalt(II) salts tailor-made ligands. This exploration led two innovative catalytic systems, namely, Co(II)/Salox Co(II)/CCA sequential catalysis. The emerged versatile strategy, demonstrating excellent enantioselectivities across range asymmetric reactions construct various molecules central, axial, planar, inherent chirality. facile single step, along ease further enhances versatility applicability approach. Moreover, successfully applied cobalt/Salox electro- photochemical-catalyzed functionalization, electrons or oxygen traceless oxidant, thereby eliminating need stoichiometric chemical oxidants. Through studies reaction developments, elucidated detailed structure-enantioselectivity relationships which are expected inform future endeavors. Finally, Co(II)/CPA enabled spiro-γ-lactams olefination/asymmetric [4 + 1] spirocyclization. Mechanistically, establishment stereochemistry occurs during cyclization where CPA serves both neutral Brønsted acid, stereoinduction independent cleavage step. We anticipate that insights advancements Account will inspire innovations drive progress metal-catalyzed reactions.

Язык: Английский

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Asymmetric transformations from sulfoxonium ylides

Chemical Science, Год журнала: 2021, Номер 13(5), С. 1192 - 1209

Опубликована: Дек. 8, 2021

Sulfoxonium ylides are important surrogates for diazo compounds, and their use in industry as safer alternatives has been evaluated during recent years. Beyond the known classical transformations, these have also used a surprising plethora of novel intrinsic chemical reactions, especially Bench stability handling an advantage this class organosulfur molecules. Despite this, efficient asymmetric specifically catalytic enantioselective versions, only recently reported, there specific reasons this. This perspective article covers topic from first studies up to latest advances, giving personal perspectives showing main challenges area coming

Язык: Английский

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