DFT-Enabled Development of Hemilabile (P^∧N) Ligands for Gold(I/III) RedOx Catalysis: Application to the Thiotosylation of Aryl Iodides

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(6), С. 3660 - 3674

Опубликована: Фев. 5, 2024

Ligand-enabled oxidative addition of Csp2-X bonds to Au(I) centers has recently appeared as a valuable strategy for the development catalytic RedOx processes. Several cross-coupling reactions that were previously considered difficult achieve reported lately, thus expanding synthetic potential gold(I) complexes beyond traditional nucleophilic functionalization π-systems. MeDalPhos played an important role in this and, despite several studies on alternative structures, remains, so far, only general ligand such process. We report herein discovery and DFT-enabled structural optimization new family hemilabile (P∧N) ligands can promote aryl iodides gold(I). These flexible ligands, which possess common 2-methylamino heteroaromatic N-donor motif, are structurally electronically tunable, being easily accessible affordable. The corresponding shown outperform reactivity (MeDalPhos)Au(I) series alkoxy- amidoarylations alkenes. Their comparatively higher further highlighted thiotosylation iodides, challenging unreported C–S reaction could not be achieved under classical Pd(0/II) catalysis allows divergent access sulfur derivatives.

Язык: Английский

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L‐Shaped Heterobidentate Imidazo[1,5‐a]pyridin‐3‐ylidene (N,C)‐Ligands for Oxidant‐Free Au^I/Au^III Catalysis

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(12)

Опубликована: Янв. 25, 2023

In the last decade, major advances have been made in homogeneous gold catalysis. However, Au

Язык: Английский

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Enantioselective merged gold/organocatalysis

Chemical Communications, Год журнала: 2024, Номер 60(27), С. 3607 - 3623

Опубликована: Янв. 1, 2024

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

Язык: Английский

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Gold-based enantioselective bimetallic catalysis

Chemical Communications, Год журнала: 2023, Номер 59(52), С. 8007 - 8016

Опубликована: Янв. 1, 2023

Multimetallic catalysis is a powerful strategy to access complex molecular scaffolds efficiently from easily available starting materials.

Язык: Английский

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Fluorinated Biphenyl Phosphine Ligands for Accelerated [Au(I)]-Catalysis

ACS Catalysis, Год журнала: 2024, Номер 14(8), С. 6128 - 6136

Опубликована: Апрель 8, 2024

Fluorinated JohnPhos-type ligands are proposed as accelerating tools in homogeneous gold(I) catalysis, with PedroPhosAuCl (Cat1) the most efficient one. The well corresponding gold complexes were synthesized high yields and fully characterized also via single-crystal X-ray diffraction. A secondary interaction between distal phenyl ring of phosphane ligand metal center is identified key for fine-tuning overall catalytic performance complexes. In particular, kinetic computational analysis revealed that by accommodating F atoms on biphenyl pendant ligand, more reactive organo-gold intermediates realized toward subsequent nucleophilic condensations. gold-catalyzed indole-hydroarylation 1,6-enynes intramolecular hydroindolynation alkynes have been adopted benchmark reactions to exemplify these effects.

Язык: Английский

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Au(I)‐Catalyzed Regiodivergent Hydroarylation of Allenes for the Synthesis of Tetrahydrodiazepines or Tetrahydrodiazonines

Advanced Synthesis & Catalysis, Год журнала: 2025, Номер unknown

Опубликована: Янв. 15, 2025

Abstract Allenes tethered to pyrroles undergo Au(I)‐catalyzed hydroarylation leading tetrahydrodiazepines or tetrahydrodiazonines. The regioselectivity of the reaction is governed by both substitution pattern allene and nature Au(I) ligand. Hence, alkyl‐gem‐disubstituted allenes preferentially lead via 7‐ exo ‐cyclizations, while aryl‐substituted tetrahydrodiazonines 9‐ endo ‐cyclization when a phosphite ligand used. Enantioselective reactions have been developed with SEGPHOS chiral ligand, heterocycles high enantioselectivity (up 96% ee). In addition, DFT calculations streamlined (7‐ vs ) these gold(I)‐catalyzed cyclizations.

Язык: Английский

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Gold‐Catalyzed Alkyne‐Amine Cascade Annulations: A Modern Strategy for Azaheterocycle Construction

The Chemical Record, Год журнала: 2025, Номер unknown

Опубликована: Апрель 7, 2025

Abstract Gold catalysis has experienced remarkable progress over the past two decades, particularly in transformations involving alkynes. While numerous aspects of gold‐catalyzed reactions have been extensively reviewed, specific area cascade annulations between functionalized amines and alkynes represents a distinct rapidly developing direction that warrants focused attention. This survey collects systematically analyzes these transformations, which emerged as convenient synthetic strategies to diverse nitrogen heterocycles. The relevant are classified firstly by chemical nature amine functional substituent, secondly size formed ring. field under consideration bridges several fundamental practical branches chemistry, including catalysis, organic synthesis, medicinal materials science.

Язык: Английский

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C−S Cross‐Coupling of Aryldiazonium Salts with Thiols Mediated by Gold

European Journal of Organic Chemistry, Год журнала: 2023, Номер 26(30)

Опубликована: Июль 11, 2023

Abstract In this work, the coupling of aryldiazonium salts with thiols mediated by readily accessible gold complex Me 2 SAuCl is described. reported protocol, addition 2,2′‐bipyridine as a ligand leads to higher yields than phosphines. The reaction proceeds at room temperature under soft mildconditions and has broad scope in both salt thiol. Notably, works containing two additional substituents.

Язык: Английский

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Gold-catalyzed highly enantioselective cycloadditions of 1,6-enynes and 1,6-diynes assisted by remote hydrogen bonding interaction

iScience, Год журнала: 2024, Номер 27(10), С. 110876 - 110876

Опубликована: Сен. 2, 2024

Язык: Английский

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Au(III) π‐Allyl Complexes: Synthesis, Structure, Reactivity, and Catalytic Applications

ChemCatChem, Год журнала: 2023, Номер 15(20)

Опубликована: Июль 21, 2023

Abstract π‐Allyl complexes of transition metals are key species in organometallic chemistry and homogeneous catalysis. Palladium(II) π‐allyl particular, have gained a lot attention, but their isoelectronic gold(III) counterparts long remained elusive. However, this situation changed during the last few years. This concept article describes preparative routes, characterization, structure reactivity such species, together with catalytic applications. The influence ancillary ligand at gold, either (P,C)/(N,C)‐cyclometalated or (P,N)‐hemilabile, is analysed detail. Au(III) Pd(II) also compared to highlight similarities differences.

Язык: Английский

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