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

Angewandte Chemie, Год журнала: 2023, Номер 135(12)

Опубликована: Янв. 25, 2023

Abstract In the last decade, major advances have been made in homogeneous gold catalysis. However, Au I /Au III catalytic cycle remains much less explored due to reluctance of undergo oxidative addition and stability intermediate. Herein, we report activation aryl halides at gold(I) enabled by NHC (NHC=N‐heterocyclic carbene) ligands through development a new class L‐shaped heterobidentate ImPy (ImPy=imidazo[1,5‐a]pyridin‐3‐ylidene) N,C that feature hemilabile character amino group combination with strong σ‐donation carbene center rigid conformation, imposed ligand architecture. Detailed characterization control studies reveal key features for redox cycle, wherein nitrogen is placed coordinating position framework. Given tremendous significance catalysis, anticipate this platform will find widespread application.

Язык: Английский

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

Опубликована: Авг. 16, 2023

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 pi-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-guided 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- amidoarylation 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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Ag/Au-Catalyzed Functionalization of Heterocycles Through C–H Activation

Topics in heterocyclic chemistry, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

Язык: Английский

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Consecutive Chirality Transfer: Efficient Synthesis of Chiral C,O-Chelated BINOL/Gold(III) Complexes for Asymmetric Catalysis and Chiral Resolution of Disubstituted BINOLs

Chemical Science, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

Diastereomeric resolution of C,O-chelated BINOL/gold( iii ) complexes was demonstrated, in which the recovered gold( dichloride could resolve BINOL derivatives. This new class achieved asymmetric catalysis with up to 99% ee.

Язык: Английский

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A Class of Chiral‐Bridged Biphenyl Monophosphine Ligands with Benzofuran Moiety and The Application in Diastereo‐ and Enantioselective Au(I)‐Catalyzed Cycloaddition

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(14), С. 3105 - 3110

Опубликована: Май 24, 2024

Abstract A class of novel chiral‐bridged biphenyl monophosphine ligands with a benzofuran moiety ( He‐phos ) has been successfully synthesized and reported. These exhibited good performance in the gold‐catalyzed enantioselective cycloaddition reaction 2‐(1‐alkynyl)‐2‐en‐1‐ones nitrones, resulting successful preparation series polyaryl‐substituted heterocyclic compounds high enantioselectivities (up to 99% yield, 98% ee). The wide substrate adaptability (53 examples) mild conditions demonstrate practicability this reaction.

Язык: Английский

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Gold(III) Catalyzed Overman Rearrangements: Controlling Steric Interactions using Pincer‐Type Ligands

ChemCatChem, Год журнала: 2022, Номер 14(24)

Опубликована: Окт. 26, 2022

Abstract Spatial control of reactivity is intrinsically difficult in gold catalysis due to the linear coordination mode Au(I) and commonly flat ligands employed for Au(III) complexes. Our recent report a novel sterically encumbered (NNN) diiPr Au−OH complex ( Eur. J. Inorg. Chem . 2021 , 3561–3564.) suggested that ligand framework capable interacting with substrates through its conveniently oriented aryl groups. We have now examined these steric properties more detail by varying ortho ‐substituent group x Au−Cl With just small modifications we were able vary buried volume around Cl atom correlate this yields obtained Au‐catalyzed Overman rearrangement. Computationally further elucidate stark difference originates from shift binding substrate Au catalyst rate limiting step reaction. thus conclude delicate spatial can be exercised propose an attractive platform efficient design complexes stereoselective catalysis.

Язык: Английский

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Gold-based multicatalytic systems for enantioselective C–C bond forming reactions

Advances in catalysis, Год журнала: 2023, Номер unknown, С. 245 - 275

Опубликована: Янв. 1, 2023

Язык: Английский

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