Borrowing Hydrogen Amination Reactions: A Complex Analysis of Trends and Correlations of the Various Reaction Parameters

ACS Catalysis, Год журнала: 2022, Номер 12(12), С. 7142 - 7198

Опубликована: Июнь 1, 2022

Borrowing hydrogen or the autotransfer amination is a powerful approach to create single C–N bonds, starting from stable and readily available substrates: amines alcohols. It considered as one of most atom-efficient green methods synthesize complex amines. Herein, we attempted arrange array existing data in comprehensive structured manner determine correlations between experimental conditions catalysis outcome both within different groups catalysts defined using machine analysis. For each type N-nucleophiles (aromatic, aliphatic, heteroaromatic amines, amides), efficient working were suggested, including attributing optimal base temperature regime for metal.

Язык: Английский

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Unleashing the potentiality of metals: synergistic catalysis with light and electricity

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(14), С. 4024 - 4040

Опубликована: Янв. 1, 2024

This review provides a comprehensive overview of metal catalysis in photo-electrochemical systems, discussing reaction mechanisms and offering prospects for this triadic catalytic mode.

Язык: Английский

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Enhanced Hydride Donation Achieved Molybdenum Catalyzed Direct N-Alkylation of Anilines or Nitroarenes with Alcohols: From Computational Design to Experiment

ACS Catalysis, Год журнала: 2021, Номер 11(16), С. 10377 - 10382

Опубликована: Авг. 5, 2021

An example of homogeneous Mo-catalyzed direct N-alkylation anilines or nitroarenes with alcohols is presented. The DFT aimed design suggested the easily accessible bis-NHC-Mo(0) complex features a strong hydride-donating ability, achieving effective challenging alcohols. enhanced strategy should be useful in designing highly active systems for borrowing hydrogen transformations.

Язык: Английский

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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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Half-Sandwich Iridium Complexes with Hydrazone Ligands: Synthesis and Catalytic Activity in N-Alkylation of Anilines or Nitroarenes with Alcohols via Hydrogen Autotransfer

Inorganic Chemistry, Год журнала: 2022, Номер 61(27), С. 10310 - 10320

Опубликована: Июнь 29, 2022

Here, we synthesize a series of hydrazone-based N,O-chelate half-sandwich iridium complexes through facile route. All air-stable show high catalytic activity in N-alkylation broad scope aniline derivatives and alcohols with liberating water as the sole byproduct. This reaction provides smooth route to diverse monoalkylated amines good excellent yields at moderate temperature low catalyst loading. Moreover, challenging process using nitroarene substrates coupling partners is also carried out this system. The mechanistic study shows that present catalysis proceeds hydrogen borrowing mechanism. iridium(III) 1-4 are characterized by infrared (IR) spectroscopy, nuclear magnetic resonance (NMR) elemental analysis.

Язык: Английский

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Low‐Temperature N‐Alkylation of Amines with Alcohols in Protic Solvents Catalyzed by Iridium Complexes Bearing N‐Heterocyclic Carbenes

European Journal of Organic Chemistry, Год журнала: 2024, Номер 27(6)

Опубликована: Янв. 1, 2024

Abstract Amines are important compounds found in natural products, pharmaceuticals, and fine chemicals. Therefore, the development of elegant, environmentally friendly, simple synthetic methods is desirable. Recently, borrowing‐hydrogen (BH) strategy has received considerable attention for C−N bond formations because its high atomic efficiency absence toxic waste generation. Researchers have recently reported that use N‐heterocyclic carbene (NHC) ligands with strong electron‐donating properties protic solvents can increase catalytic activity BH strategy. herein, we focused on versatility methods, such as a system allows synthesis, operates at low reaction temperatures, involves effective solvent simultaneously. The catalyzed N‐alkylation alcohols amines under mild conditions was investigated using NHC complexes developed by our group. We achieved synthesis various alkylamines conditions, 40–60 °C, iridium comprising structures 2,2,2‐trifluoroethanol 1,1,1,3,3,3‐hexafluoroisopropanol.

Язык: Английский

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Preparation of a novel cadmium-containing coordination polymer and catalytic application in the synthesis of N-alkylated aminoquinoline derivatives via the borrowing hydrogen approach

Dalton Transactions, Год журнала: 2024, Номер 53(11), С. 5064 - 5072

Опубликована: Янв. 1, 2024

Herein, we report an efficient and straightforward approach for the synthesis of

Язык: Английский

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A well-defined phosphine free metal-ligand cooperative route for N-alkylation of aromatic amines via activation of renewable alcohols catalyzed by a NNN pincer cobalt(II) complexes

Dalton Transactions, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Two cobalt( ii ) complexes C1 and C2, supported by an NNN pincer, were synthesized, characterized with various techniques. These utilized to study catalytic activity in the N -alkylation of amines via borrowing hydrogen strategy.

Язык: Английский

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Molybdenum‐Catalyzed Asymmetric Amination of α‐Hydroxy Esters: Synthesis of α‐Amino Acids

Advanced Science, Год журнала: 2025, Номер unknown

Опубликована: Март 10, 2025

Abstract Unnatural α‐amino acids are found in a wide variety of bioactive compounds ranging from proteins to pharmaceutical agents materials science. As result, the investigation efficient and simple methods for their synthesis is major purpose reaction development. In this study, it that catalyst based on molybdenum, an earth‐abundant transition metal, can facilitate amination readily accessible α‐hydroxy esters afford N ‐protected unnatural acid high yield. This process also enables enantioselective amination, which proceeds through cooperative catalysis chiral molybdenum complex with phosphoric (CPA), complements earlier procedures catalytic important class compounds. The obtained protected ester products directly useful or further utilized commercially available drugs analogs.

Язык: Английский

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Selective Monoalkylation or Dialkylation of Indenes with Alcohols by Bis-N-Heterocyclic Carbene Manganese

ACS Catalysis, Год журнала: 2024, Номер unknown, С. 18032 - 18044

Опубликована: Ноя. 22, 2024

Selective direct alkylation of indenes is important for the synthesis and decoration indene derivatives. In contrast to traditional methods, using unactivated alcohol as reagents via borrowing hydrogen or autotransfer highly attractive. However, nature high-lying lowest unoccupied molecular orbital condensation intermediate raises a big challenge development BH system alcohols. Through tuning stability reactivity metal-hydride species by theoretical prediction, herein, we succeeded in developing non-noble Mn-catalyzed selective monoalkylation dialkylation under mild conditions, producing corresponding versatile alkylated satisfactory yields. A broad scope substrates including primary benzylic, aliphatic, amino, hydroxyl, second alcohols well various are tolerated system. Additionally, this method could be used potential precatalyst complexes bioactive molecules. Mechanistic studies control experiments, kinetic investigations, isotope effect, deuterium labeling density functional theory calculations, reveal proper successful process.

Язык: Английский

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