Surmounting Alkoxide Trap Strategy: N-Heterocyclic Carbene Chromium(0)-Catalyzed C-Alkylation between Alcohols

ACS Catalysis, Год журнала: 2023, Номер 13(19), С. 12481 - 12493

Опубликована: Сен. 8, 2023

The crucial role of the alkoxide trap problem and impact oxidation state chromium center were demonstrated on catalytic activity due to d-wall issue. Through strategy surmounting trap, a Cr(0) catalyst was presented herein for efficient C-alkylation between alcohols via borrowing hydrogen/hydrogen autotransfer. synthesized bis-(N-heterocyclic carbene)-Cr(0) system shows an performance (40 examples, up 96% yield). Only loading cheap readily available base NaOH is effective enough reaction. Compared with Cr(III)/Cr(II), can well avoid d-p π interaction in key metal-alkoxide intermediate, thus overcoming thermodynamic sink problem. It plausible that Cr(III) systems need be reduced Cr(II) weakening effect enhancing by using reductive strong bases. This should helpful development nonprecious transition metal catalysts.

Язык: Английский

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Electronically tuneable orthometalated Ru^II–NHC complexes as efficient catalysts for C–C and C–N bond formations via borrowing hydrogen strategy

Catalysis Science & Technology, Год журнала: 2021, Номер 12(1), С. 67 - 74

Опубликована: Ноя. 10, 2021

A series of simple and electronically tuneable cyclometalated Ru II –NHC complexes have been explored as efficient catalysts for various C–C/N bond forming reactions via a BH methodology.

Язык: Английский

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Progressive study on ruthenium catalysis for de(hydrogenative) alkylation and alkenylation using alcohols as a sustainable source

Organic & Biomolecular Chemistry, Год журнала: 2022, Номер 20(41), С. 7998 - 8030

Опубликована: Янв. 1, 2022

This review focuses on the Ru-catalyzed de(hydrogenative) formation of C–C and CC bonds. The comparative reactivity different Ru-complexes to gain selectivity in product is presented, together with brief mechanistic insights.

Язык: Английский

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Selective cross-coupling of α,β-unsaturated nitriles with aldehydes or alcohols by hydrogen transfer catalysis towards β-ketonitriles and glutaronitriles

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(9), С. 2613 - 2623

Опубликована: Янв. 1, 2024

A Ru-catalyzed selective hydroacylation of acrylonitriles with aldehydes or alcohols towards β-ketonitriles is established. Glutaronitriles can be obtained through a one-step tandem and Michael addition acrylonitrile alcohols.

Язык: Английский

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Recent progress in transition metal complexes featuring silylene as ligands

Chemical Communications, Год журнала: 2024, Номер 60(71), С. 9483 - 9512

Опубликована: Янв. 1, 2024

This review highlights recent advances in transition metal complexes of silylene, showcasing their efficacy hydroboration, hydrosilylation, hydrogenation, hydrogen isotope exchange, and small molecule activation chemistry.

Язык: Английский

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Recent Developments of Transition‐Metal‐Catalyzed Cross‐Coupling of Nitriles and Alcohols

ChemistrySelect, Год журнала: 2024, Номер 9(32)

Опубликована: Авг. 22, 2024

Abstract Cross‐coupling of nitriles and alcohols offers an environmentally friendly atom‐economical method for the synthesis various valuable compounds. These compounds include α ‐alkylated ‐olefinated nitriles, primary amines, imines, N ‐alkylation amides, ‐heterocycles, δ ‐hydroxynitriles, olefins, etc . Herein, we have reviewed recent developments (from 2013–date) transition‐metal‐catalyzed cross‐coupling alcohols. A number transition metal complexes such as noble metals Ru Ir, well base Mn, Fe, Co, Ni are presented. Moreover, different product types, reaction conditions mechanisms discussed to understand catalyst development.

Язык: Английский

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Ru^II-Complexes of heteroditopic chelating NHC ligands: effective catalysts for the β-alkylation of secondary alcohols and the synthesis of 2-alkylaminoquinoline derivatives following the dehydrogenative protocol

Organic & Biomolecular Chemistry, Год журнала: 2022, Номер 20(9), С. 1945 - 1951

Опубликована: Янв. 1, 2022

Ru II -Complexes of a heteroditopic NHC ligand, featuring ImNHC and tzNHC donors, were noted to be very efficient catalysts (up 0.001 mol%) for β-alkylation secondary alcohols one pot synthesis diverse 2-alkylaminoquinoline derivatives.

Язык: Английский

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Ruthenium‐Catalyzed α‐Alkylation of Arylacetonitriles with Primary Alcohols: N‐heterocyclic Carbene‐Amine's Promotional Influence

ChemistrySelect, Год журнала: 2025, Номер 10(7)

Опубликована: Фев. 1, 2025

Abstract Transition‐metal‐catalyzed α‐alkylation of nitriles with alcohols is an environmentally benign reaction, and the development simple efficient catalysts for this transformation a growing area research. In study, we report serial bidentate N ‐heterocyclic carbene (NHC) ruthenium complexes different extra donors alcohols. Through adjusting backbone NHC ligands, catalytic activities these could be controlled. The complex ( Ru3 ) bearing amine donor benzimidazolium exhibited highest activity. A large variety α‐alkylated were obtained in 30%–88% yields, by using 1 mol% amount Cs 2 CO 3 (20 mol%). Detailed control experiments deuterium‐labeling suggested that reaction proceeds via borrowing hydrogen pathway.

Язык: Английский

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Gram-scale synthesis of carboxylic acids via catalytic acceptorless dehydrogenative coupling of alcohols and hydroxides at an ultralow Ru loading

Applied Catalysis A General, Год журнала: 2021, Номер 630, С. 118443 - 118443

Опубликована: Ноя. 27, 2021

Язык: Английский

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Ruthenium-Catalyzed Divergent Acceptorless Dehydrogenative Coupling of 1,3-Diols with Arylhydrazines: Synthesis of Pyrazoles and 2-Pyrazolines

Organic Letters, Год журнала: 2022, Номер 24(21), С. 3878 - 3883

Опубликована: Май 24, 2022

Herein, the divergent transformations of 1,3-diols with arylhydrazines via acceptorless dehydrogenative coupling reactions to selectively synthesize pyrazoles and 2-pyrazolines were reported, which based on Ru3(CO)12/NHC-phosphine-phosphine catalytic systems. The featured low catalyst loading, high selectivity, wide substrate scope, good yields, only water hydrogen gas (H2) as byproducts.

Язык: Английский

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