Aluminum-Containing Heterobimetallic Complexes as Versatile Platforms for Homogeneous Catalysis

ACS Catalysis, Год журнала: 2023, Номер 13(19), С. 12519 - 12542

Опубликована: Сен. 11, 2023

Within the broader area of heterobimetallic catalysis, Al/M compounds (M = any metal) are promising for design and execution catalytic manifolds. This Perspective reviews recent advances in focusing on their applications. Topics include polymerization, epoxide activation carbonylation, C–H functionalization, other important transformations mediated by catalysts. In each case, mechanistic role aluminum site is highlighted. A broad range Al-containing metalloligands combinations included to construct this comprehensive perspective.

Язык: Английский

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Nickel-Catalyzed Atroposelective C–H Alkylation Enabled by Bimetallic Catalysis with Air-Stable Heteroatom-Substituted Secondary Phosphine Oxide Preligands

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(13), С. 9172 - 9180

Опубликована: Март 21, 2024

The catalytic asymmetric construction of axially chiral C–N atropisomers remains a formidable challenge due to their low rotational barriers and is largely reliant on toxic, cost-intensive, precious metal catalysts. In sharp contrast, we herein describe the first nickel-catalyzed atroposelective C–H alkylation for compounds with aid heteroatom-substituted secondary phosphine oxide (HASPO)-ligated Ni–Al bimetallic catalyst. A wide range alkenes, including terminal internal were well compatible reaction, providing variety benzimidazole derivatives in high yields enantioselectivities (up 97:3 e.r.). key success was identification novel HASPOs as highly effective preligands. Mechanistic studies revealed catalyst mode action, in-depth data science analysis elucidated features responsible preligands controlling enantioselectivity.

Язык: Английский

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Pd/Chiral Phosphoric Acid-Enabled Asymmetric Intramolecular Double C–H Activation Reaction for the Synthesis of P-Stereogenic Benzophosphole Oxides

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Фев. 2, 2025

A Pd-catalyzed intramolecular asymmetric double C-H activation reaction was reported, and a BINOL skeleton-based chiral phosphoric acid (CPA) identified as suitable ligand for this transformation. broad range of P-stereogenic benzophosphole oxides were synthesized in moderate to excellent yield with high levels enantioselectivity (≤96% ee).

Язык: Английский

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Enantioselective C–H annulations enabled by either nickel- or cobalt-electrocatalysed C–H activation for catalyst-controlled chemodivergence

Nature Catalysis, Год журнала: 2025, Номер unknown

Опубликована: Март 7, 2025

Язык: Английский

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Ni‐SPO‐Al Catalyzed Stereoselective C–H Alkenylation of Quinazolinones with Alkynes to Prepare trans‐Isomers

European Journal of Organic Chemistry, Год журнала: 2025, Номер 28(5)

Опубликована: Янв. 4, 2025

Abstract A stereoselective Ni−Al bimetal‐catalyzed C−H alkenylation of quinazolinones with alkynes has been successfully developed. Good selectivity Z‐type quinazolinone products was obtained using readily available substrates, which exhibits a trans‐configuration opposite to the conventional alkynylation reactions and improves diversity compounds. In addition, reaction process further explored through KIE other control experiments, possible mechanism proposed.

Язык: Английский

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New reactivity of late 3d transition metal complexes in catalytic reactions of alkynes

Chemical Society Reviews, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

This review summarizes seven types of new reactivities found in late 3d metal complexes and catalytic examples recent years.

Язык: Английский

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Photocatalytic Pyridyl-carbamoylation of Alkenes for Accessing β-Pyridyl Amides

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 7, 2025

The β-pyridyl amide is a critical scaffold in medical discovery yet lacks efficient synthetic methods. Here, we describe, for the first time, visible-light-induced, redox-neutral radical cross-coupling reaction involving alkenes, oxamic acids, and cyanopyridines that offers versatile assembly of β-pyridylamides. This approach features mild conditions, high step efficiency, substrate breadth, providing green strategy alkene pyridyl-carbamoylation. Achieving this transformation relies on catalytic system, which adeptly avoids competing nucleophilic carbamoyl with electrophilic pyridyl radical, enabling three-component tandem process chemoselectivity.

Язык: Английский

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Intermolecular Carbophosphination of Alkynes with Phosphole Oxides via Ni−Al Bimetal‐Catalyzed C−P Bond Activation

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(49)

Опубликована: Окт. 17, 2023

Intermolecular carbophosphination reaction of alkynes or alkenes with unreactive C-P bonds remains an elusive challenge. Herein, we used a Ni-Al bimetallic catalyst to realize intermolecular 5-membered phosphole oxides, providing series 7-membered phosphepines in up 94 % yield.

Язык: Английский

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Computational Exploration of 1,2-Carboamine Carbonylation Catalyzed by Nickel

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(7), С. 4484 - 4495

Опубликована: Март 12, 2024

Nickel-catalyzed carbonylation of alkenes is a stereoselective and regioselective method for the synthesis amide compounds. Theoretical predictions with density functional theory calculations revealed mechanism origin stereoselectivity regioselectivity nickel-catalyzed norbornene. The reaction proceeds through oxidative addition, migration insertion alkenes, subsequent reduction elimination to afford cis-carbonylation product. C–N bond activation amides unfavorable because addition ability C–C stronger than that bond. determining step migratory strained olefin. structural analysis shows steroselectivity controlled by steric hindrance methyl groups olefins substituents IMes in ligands.

Язык: Английский

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Palladium(II)-Catalyzed Site-Selective C(sp³)–H Alkenylation of Oligopeptides

Organic Letters, Год журнала: 2024, Номер 26(44), С. 9455 - 9459

Опубликована: Окт. 24, 2024

An innovative palladium-catalyzed alkenylation of peptides and vinyl iodides has been developed. This method does not require the introduction a directing group uses carboxylic acid groups as endogenous groups. It is noteworthy that two key building blocks for ilamycins CXCR7 modulators were prepared using our methodology. In addition, free residue can be linked to variety other compounds, providing novel approach synthesis peptide drugs in future.

Язык: Английский

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