Palladium‐Catalyzed Fluorinative Bifunctionalization of Aziridines and Azetidines with gem‐Difluorocyclopropanes

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(42)

Published: Aug. 12, 2023

Abstract An unprecedented Pd‐catalyzed fluorinative bifunctionalization of aziridines and azetidines was successfully developed via regioselective C−C C−F bond cleavage gem‐difluorocyclopropanes, leading to various β,β′‐bisfluorinated amines β,γ‐bisfluorinated amines. This reaction achieved by incorporating a 2‐fluorinated allyl group fluorine atom scissored from gem‐difluorocyclopropane in 100 % economy for the first time. The mechanistic investigations indicated that underwent amine attacking palladium complex generate η 2 ‐coordinated N‐allyl aziridine followed fluoride ligand transfer affording final β‐ γ‐fluorinated

Language: Английский

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Enantioselective merged gold/organocatalysis

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(27), P. 3607 - 3623

Published: Jan. 1, 2024

This highlight demonstrates the state of art in field enantioselective merged gold/organocatalysis by leveraging unique reactivity each catalyst.

Language: Английский

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Visible-Light-Mediated Ruthenium-Catalyzed para-Selective Alkylation of Unprotected Anilines

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(11), P. 7310 - 7321

Published: May 15, 2023

Anilines are important moieties in organic chemistry, pharmaceuticals, and materials science. Although para-selective functionalization of anilides tertiary anilines is well established, unprotected have posed a challenge. Herein, we report visible-light-mediated Ru(II)-catalyzed para-alkylation anilines. The distinct Ru(II)–aniline complex enabled the reaction to proceed with extremely high efficiency (2 h) under mild conditions. good functional group tolerance allowed late-stage even aggregation-induced emission luminogen labeling natural products drugs. A mechanistic investigation suggests that crucial for both triggering controlling para-selectivity.

Language: Английский

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Catalytic Asymmetric P–H Insertion Reactions

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(36), P. 20031 - 20040

Published: Aug. 29, 2023

Albeit notable endeavors in enantioselective carbene insertion into X–H bonds (X = C, O, N, S, Si, B), the catalytic asymmetric P–H reactions still stand for a long-lasting challenge. By merging transition-metal catalysis with organocatalysis, we achieve scalable transformation between diazo pyrazoleamides and H-phosphine oxides that upon subsequent reduction delivers wide variety of optically active β-hydroxyl phosphine good yields high enantioselectivity. The achiral copper catalyst fosters carbenoid bond, while chiral cinchona alkaloid-derived organocatalyst controls outcome. Density functional theory (DFT) calculations further reveal chelates to organocatalyst, enhances its acidity, accordingly promotes proton transfer. Our work showcases potential combining organocatalysis realize elusive reactions.

Language: Английский

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Efficient Synthesis of Diaryl Quaternary Centers by Rh(II)/Xantphos Catalyzed Relay C−H Functionalization and Allylic Alkylation

Chemistry - A European Journal, Journal Year: 2022, Volume and Issue: 29(3)

Published: Oct. 14, 2022

A three-component reaction of N, N-disubstituted aniline, α-diazo ester, and an allylic electrophile has been realized by [Rh(II)]2 /Xantphos catalysis, providing a direct access to various aniline derivatives bearing diaryl quaternary centers in good yields. The synthetic utility this protocol was demonstrated facile derivatization the products for preparation biologically relevant molecules structural scaffolds, which offers high potential increasing molecular diversity. Mechanistic studies identified α, α-diarylacetate species as active intermediate, thereby revealing presence C(sp2 )-H functionalization derivatives/allylic alkylation cascade attractive catalytic transformation.

Language: Английский

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Enantioconvergent and diastereoselective synthesis of atropisomeric hydrazides bearing a cyclic quaternary stereocenter through ternary catalysis

Chemical Science, Journal Year: 2024, Volume and Issue: 15(33), P. 13240 - 13249

Published: Jan. 1, 2024

The enantioselective and diastereoselective synthesis of atropisomeric hydrazides with defined vicinal central axial chirality via ternary catalysis in a one-pot process is reported.

Language: Английский

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Design Approaches That Utilize Ionic Interactions to Control Selectivity in Transition Metal Catalysis

Chemical Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 28, 2025

The attractive force between two oppositely charged ions can constitute a powerful design tool in selective catalysis. Enzymes make extensive use of ionic interactions alongside variety other noncovalent interactions; recent years have seen synthetic chemists begin to seriously explore these catalyst designs that also incorporate reactive transition metal. In isolation, single interaction exhibits low directionality, but many successful systems they exist additional which provide high degree organization at the selectivity-determining state. Even situations with key interaction, directionality is not always detrimental, and even be advantageous, conferring generality catalyst. This Review explores approaches utilize control selectivity metal It divided into halves: first, occurs outer sphere complex, using ligand or bound an anion; second, bears formal charge, associated counterion.

Language: Английский

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Multicomponent reactions to access S-aryl dithiocarbamates via an electron donor–acceptor complex under open-to-air conditions

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(7), P. 1378 - 1385

Published: Jan. 1, 2024

An efficient transition-metal/photocatalyst-free visible-light-driven one-pot three-component reaction between thianthrenium salts, carbon disulfide and amines under air atmosphere for the preparation of S -aryl dithiocarbamates is developed.

Language: Английский

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Chiral Osmium(II)/Salox Species Enabled Enantioselective γ‐C(sp³)−H Amidation: Integrated Experimental and Computational Validation For the Ligand Design and Reaction Development

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(20)

Published: March 19, 2024

Abstract Herein, multiple types of chiral Os(II) complexes have been designed to address the appealing yet challenging asymmetric C(sp 3 )−H functionalization, among which Os(II)/Salox species is found be most efficient for precise stereocontrol in realizing amidation. As exemplified by enantioenriched pyrrolidinone synthesis, such tailored catalyst efficiently enables an intramolecular site‐/enantioselective amidation γ‐position dioxazolone substrates, benzyl, propargyl and allyl groups bearing various substituted forms are well compatible, affording corresponding γ‐lactam products with good er values (up 99 : 1) diverse functionality (>35 examples). The unique performance advantage developed system terms catalytic energy profile induction has further clarified integrated experimental computational studies.

Language: Английский

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Synthesis of Cyclopenta[b]indoles via Rhodium‐Catalyzed Cascade Migration‐Annulation of 1‐Sulfonyl‐1,2,3‐triazoles and Indoles

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(10), P. 1623 - 1628

Published: May 5, 2023

Abstract A rhodium‐catalyzed cascade 1,3‐sulfinate migration, intermolecular [3+2] annulation of 1‐sulfonyl‐1,2,3‐triazoles and indoles was achieved. The one‐pot protocol provided a method to construct cyclopenta[ b ]indoles bearing four stereocenters in 45% 99% yields with 1.6:1 >20:1 diastereoselectivities. In addition, could be transformed into variety functionalized compounds, demonstrating the synthetic value this migration‐annulation strategy ring system synthesis. magnified image

Language: Английский

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