Atroposelective Synthesis of Axially Chiral Styrenes by Platinum‐ Catalyzed Stereoselective Hydrosilylation of Internal Alkynes

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(30)

Опубликована: Май 25, 2023

Abstract Hydrofunctionalization of alkynes is one the most efficient ways to access axially chiral styrenes with open‐chained olefins. While great advances have been achieved for 1‐alkynylnaphthalen‐2‐ols and analogues, atroposelective hydrofunctionalization unactivated internal lags. Herein we reported a platinum‐catalyzed hydrosilylation first time. With monodentate TADDOL‐derived phosphonite L1 used as ligand, various were in excellent enantioselectivities high E ‐selectivities. Control experiments showed that N H‐arylamide groups significant effects on both yields could act directing groups. The potential utilities products shown by transformations amide motifs products.

Язык: Английский

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Directing Group Repositioning Strategy Enabled Site- and Enantioselective Addition of Heteroaromatic C–H Bonds to Acyclic Internal Alkenes

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(12), С. 6861 - 6870

Опубликована: Март 14, 2023

Despite the notable advances achieved in Murai-type hydroarylations, highly enantioselective catalytic addition of native (hetero)arenes to internal alkenes remains a prominent challenge. Herein, we report directing group repositioning strategy, which enables iridium-catalyzed heteroarenes including furan, benzofuran, and thiophene enamides. The C-H bond at C2 position heteroarene is site-selectively cleaved added regioselectively β-position an enamide, affording valuable β-heteroaryl amide with high enantioselectivity. Mechanistic studies indicate that rate enantioselectivity are determined by separate elementary steps.

Язык: Английский

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Reversal of Regioselectivity in Asymmetric C−H Bond Annulation with Bromoalkynes under Cobalt Catalysis**

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(6)

Опубликована: Дек. 14, 2023

Abstract Metal‐catalyzed asymmetric C−H bond annulation strategy offers a versatile platform, allowing the construction of complex P‐chiral molecules through atom‐ and step‐economical fashion. However, regioselective insertion π‐coupling partner between M−C with high enantio‐induction remain elusive. Using commercially available Co(II) salt chiral‐Salox ligands, we demonstrate an unusual protocol for regio‐reversal, enantioselective phosphinamide bromoalkyne desymmetrization. The reaction proceeds ligand‐assisted enantiodetermining cyclocobaltation followed by Co−C, subsequent reductive elimination, halogen exchange carboxylate resulted in P‐stereogenic compounds excellent ee (up to >99 %). isolation cobaltacycle involved catalytic cycle outcome control experiments provide support plausible mechanism.

Язык: Английский

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Iridium-Catalyzed Tandem Dehydrogenation/Hydroarylation Approach to Synthetically Versatile C2-Alkenyl N–H Indoles

ACS Catalysis, Год журнала: 2024, Номер 14(5), С. 2872 - 2882

Опубликована: Фев. 9, 2024

Readily available N-carbamoyl indolines can be converted into highly valuable 2-alkenyl and 2-alkyl indoles in a one-pot reaction, through an autotandem catalytic cascade promoted by iridium complex. The process entails dehydrogenation reaction initiated iridium-promoted C(sp3)–H activation, the addition of resulting indole to alkyne -or alkene-partner, spontaneous loss carbamoyl directing group. Interestingly, C2-alkenyl participate variety metal-catalyzed annulations C–H including formal [4 + 1] 2] cycloadditions, as well cross-dehydrogenative cyclizations, thus enabling divergent access collection functionally rich nitrogen-containing heterocycles.

Язык: Английский

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CoH-catalyzed asymmetric remote hydroalkylation of heterocyclic alkenes: a rapid approach to chiral five-membered S- and O-heterocycles

Chemical Science, Год журнала: 2024, Номер 15(23), С. 8888 - 8895

Опубликована: Янв. 1, 2024

A highly efficient method achieves precise construction of alkyl chiral centers at remote C3-positions in five-membered S/O-heterocycles via cobalt-catalyzed asymmetric hydroalkylation heterocyclic alkenes.

Язык: Английский

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Cobalt Hydride-Catalyzed Hydroalkynylation of Alkenes with Alkynyl Trifluoroborates

ACS Catalysis, Год журнала: 2024, Номер 14(12), С. 9294 - 9301

Опубликована: Июнь 4, 2024

A cobalt-catalyzed hydroalkynylation of alkenes with alkynyl trifluoroborates is described, proceeding through a cobalt hydride-mediated radical-polar crossover metal hydrogen-atom-transfer process. This method affords structurally diverse alkynyl-containing compounds in high yields under mild conditions and features wide substrate scope, good functional group tolerance, suitability for late-stage functionalization relatively complex natural products bioactive molecules. Expanding the scope to alkenyltrifluoroborate salts further increases utility developed methodology. approach paves an alternative route radical-involved alkynylation alkenylation reactions nucleophilic alkynyl/alkenyl reagents.

Язык: Английский

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Applications of Luminescent Cyclometalated Metal Complexes as Sensors and Switches

Synlett, Год журнала: 2025, Номер unknown

Опубликована: Март 19, 2025

Abstract Cyclometalated complexes, including those with pincer ligands and other chelating frameworks, such as porphyrin rings polyenes, have garnered significant attention due to their diverse applications in ion analyte detection across synthetic chemistry, environmental monitoring, medicine, electronics. These complexes exhibit fascinating chromic behaviors, mechanochromism, chemochromism, vapochromism, which are particularly useful sensing applications. Of particular interest photophysical properties, especially involving lanthanides, offer unique luminescent optical characteristics. Metals nickel (Ni), palladium (Pd), ruthenium (Ru), gold (Au), rhodium (Rh) been extensively studied order understand photochemical activity explore potential light-emitting devices, photo-induced electron transfer, technologies. Their vapochromic mechanochromic properties make them highly attractive for sensing, while photoluminescent capabilities enhance utility optoelectronic devices practical This review provides a comprehensive overview of applications, gas, cation, anion sensing. The discussion also highlights the need incorporate specific examples that demonstrate suitability these targeted tasks, further emphasizing promise advancing sensor device 1 Introduction 2 Strategies 3 Applications 4 Other Miscellaneous Examples 5 Drawbacks Limitations 6 Conclusion Perspectives 7 List Abbreviations Definitions

Язык: Английский

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Stereodivergent Construction of Enamides via a Radical-Mediated Isodesmic Reaction

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 6749 - 6759

Опубликована: Апрель 10, 2025

Язык: Английский

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Access to chiral sulfones with an all-carbon quaternary stereocenter from sulfur dioxide

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(15), С. 4275 - 4283

Опубликована: Янв. 1, 2024

A copper-catalyzed enantioselective four-component reaction via the insertion of sulfur dioxide toward synthesis chiral sulfones bearing an all-carbon quaternary stereocenter at β position is reported.

Язык: Английский

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Amide-Directed, Rhodium-Catalyzed Regio- and Enantioselective Hydroacylation of Internal Alkenes with Unfunctionalized Aldehydes

Journal of the American Chemical Society, Год журнала: 2023, Номер 146(1), С. 723 - 732

Опубликована: Дек. 20, 2023

Despite the current progress achieved in asymmetric hydroacylations, highly enantioselective catalytic addition of unfunctionalized aldehydes to internal alkenes remains an unsolved challenge. Here, using a coordination-assisted strategy, we developed rhodium-catalyzed regio- and such as enamides β,γ-unsaturated amides. Valuable α-amino ketones 1,4-dicarbonyl compounds were directly obtained with high enantioselectivity from readily available materials.

Язык: Английский

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