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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Ruthenium(ii)-catalyzed synthesis of CF₃-isoquinolinones via C–H activation/annulation of benzoic acids and CF₃-imidoyl sulfoxonium ylides

Organic Chemistry Frontiers, Год журнала: 2022, Номер 9(16), С. 4388 - 4393

Опубликована: Янв. 1, 2022

The synthesis of 3-trifluoromethylisoquinolinones by a ruthenium( ii )-catalyzed C–H activation/annulation reaction benzoic acids and CF 3 -imidoyl sulfoxonium ylides has been achieved.

Язык: Английский

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Sigma-Bond Metathesis as an Unusual Asymmetric Induction Step in Rhodium-Catalyzed Enantiodivergent Synthesis of C–N Axially Chiral Biaryls

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(15), С. 8417 - 8429

Опубликована: Март 23, 2023

Mechanistic understanding of asymmetric induction plays a crucial role in designing new catalytic reactions. Reported herein is atroposelective access to C-N axially chiral isoquinolones via rhodium-catalyzed C-H activation N-alkoxy benzamides and annulation with imidoyl sulfoxonium ylides. The coupling system proceeded excellent functional group tolerance, different conditions were identified afford one or the other enantiomeric product each enantioselectivity for representative class ylide reagent, thus making both enantiomers readily available using same catalyst. Experimental computational studies revealed pathway alkylation enantio-determining formal nucleophilic substitution-C-N cyclization that mediated by rhodium catalyst σ-bond metathesis as mechanism. Computational indicated solvent-dependent enatiodivergence originated from levels neutral versus cationic species.

Язык: Английский

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Additive-free synthesis of β-keto phosphorodithioates via geminal hydro-phosphorodithiolation of sulfoxonium ylides with P4S10 and alcohols

Chinese Chemical Letters, Год журнала: 2024, Номер 35(9), С. 109513 - 109513

Опубликована: Янв. 21, 2024

Язык: Английский

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Chameleonic Reactivity of Imidoyl Sulfoxonium Ylides: Access to Functionalized Pyrroles and Dihydro-pyridines

Organic Letters, Год журнала: 2024, Номер 26(1), С. 62 - 67

Опубликована: Янв. 3, 2024

We have found a chameleonic reactivity of imidoyl sulfoxonium ylides. On the one hand, ylides react with electron-deficient reagents, such as alkynyl esters, to lead formation 1,2-dihydro-pyridines. The methyl group attached sulfur atom acts methylene donor. other pyridinium 1,4-zwitterionic thiolates, which leads functionalized pyrroles. Both transformations feature mild reaction conditions and good functional tolerance.

Язык: Английский

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Ruthenium-Catalyzed Chemoselective N–H Bond Insertion Reactions of 2-Pyridones/7-Azaindoles with Sulfoxonium Ylides

Organic Letters, Год журнала: 2021, Номер 23(3), С. 1038 - 1043

Опубликована: Янв. 21, 2021

A ruthenium-catalyzed highly chemoselective N-alkylation of 2-pyridones has been developed, affording N-alkylated 2-pyridone derivatives in good yields and excellent N-selectivity. The key to achieve this unprecedented N–H rather than O–H insertion reaction is the use CpRu(PPh3)2Cl as catalyst sulfoxonium ylides alkylation reagents. Moreover, protocol also amenable 7-azaindoles by slightly varying conditions. Furthermore, sulfonium are suitable reagents, providing selectivity.

Язык: Английский

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Transition-Metal-, Additive-, and Solvent-Free [3 + 3] Annulation of RCF₂-Imidoyl Sulfoxonium Ylides with Cyclopropenones to Give Multifunctionalized CF₃-Pyridones

The Journal of Organic Chemistry, Год журнала: 2021, Номер 87(2), С. 1124 - 1132

Опубликована: Дек. 29, 2021

An efficient and practical strategy was developed to synthesize 1,3,4-triaryl-6-trifluoromethylpyridones from CF3-imidoyl sulfoxonium ylides cyclopropenones in good excellent yields. This stepwise [3 + 3] annulation reaction carried out under transition-metal-, additive-, solvent-free conditions, generating 1 equiv of dimethyl sulfoxide as byproduct tolerating a series functional groups.

Язык: Английский

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Ruthenium-Catalyzed Hydroxyl-Directed peri-Selective C–H Activation and Annulation of 1-Naphthols with CF₃–Imidoyl Sulfoxonium Ylides for the Synthesis of 2-(Trifluoromethyl)-2,3-dihydrobenzo[de]chromen-2-amines

Organic Letters, Год журнала: 2022, Номер 24(40), С. 7288 - 7293

Опубликована: Окт. 4, 2022

A ruthenium-catalyzed peri-selective C-H activation and annulation of 1-naphthols with CF3-substituted imidoyl sulfoxonium ylides that uses hydroxyl as a weakly coordinating directing group is disclosed. The strategy provides facile practical route to diverse trifluoromethyl-containing 2,3-dihydrobenzo[de]chromen-2-amines high efficiency. Notable advantages this protocol include readily available materials, excellent regioselectivity, good functional compatibility, scalability.

Язык: Английский

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Rh(III)-Catalyzed Dual C–H Activation/Cascade Annulation of Benzimidates and CF₃-Imidoyl Sulfoxonium Ylides for the Synthesis of Trifluoromethyl-Decorated Benzo[de][1,8]naphthyridines

Organic Letters, Год журнала: 2022, Номер 24(48), С. 8864 - 8869

Опубликована: Дек. 1, 2022

An efficient and straightforward approach for the synthesis of trifluoromethyl-decorated benzo[de][1,8]naphthyridines has been achieved via Rh(III)-catalyzed dual C-H activation cascade annulation benzimidates CF3-imidoyl sulfoxonium ylides. The novel transformation involves formation four new chemical bonds along with release two molecules dimethyl sulfoxide (DMSO) one molecule each ethanol amine. optoelectronic properties obtained fused aromatic products have investigated by recording UV-vis absorption emission spectra.

Язык: Английский

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Formal [4+1] Annulation of Azoalkenes with CF₃-Imidoyl Sulfoxonium Ylides and Dual Double Bond Isomerization Cascade: Synthesis of Trifluoromethyl-Containing Pyrazole Derivatives

Organic Letters, Год журнала: 2022, Номер 24(37), С. 6822 - 6827

Опубликована: Сен. 9, 2022

A straightforward strategy for the metal-free construction of trifluoromethyl-containing pyrazole derivatives has been achieved from readily available α-halo hydrazones and CF3-imidoyl sulfoxonium ylides. The cascade transformation proceeds through formal [4+1] cycloaddition followed by an unexpected dual double bond isomerization. protocol features mild conditions, easy operation, excellent substrate compatibility, good regioselectivity. synthetic utility is demonstrated scale-up reaction further elaboration obtained products.

Язык: Английский

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