First-Row Transition Metal (De)Hydrogenation Catalysis Based On Functional Pincer Ligands

Chemical Reviews, Journal Year: 2018, Volume and Issue: 119(4), P. 2681 - 2751

Published: Dec. 31, 2018

The use of 3d metals in de/hydrogenation catalysis has emerged as a competitive field with respect to "traditional" precious metal catalyzed transformations. introduction functional pincer ligands that can store protons and/or electrons expressed by metal-ligand cooperativity and ligand redox-activity strongly stimulated this development conceptual starting point for rational catalyst design. This review aims at providing comprehensive picture the utilization first-row transition hydrogenation dehydrogenation related synthetic concepts relying on these such hydrogen borrowing methodology. Particular emphasis is put implementation relevance cooperating redox-active within mechanistic scenarios.

Language: Английский

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Homogeneous manganese-catalyzed hydrogenation and dehydrogenation reactions

Chem, Journal Year: 2020, Volume and Issue: 7(5), P. 1180 - 1223

Published: Dec. 9, 2020

Language: Английский

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Manganese-Catalyzed α-Alkylation of Ketones, Esters, and Amides Using Alcohols

ACS Catalysis, Journal Year: 2018, Volume and Issue: 8(11), P. 10300 - 10305

Published: Oct. 2, 2018

Herein we report the manganese-catalyzed C–C bond-forming reactions via α-alkylation of ketones, amides, and esters, using primary alcohols. β-Alkylation secondary alcohols by to obtain α-alkylated ketones is also reported. The are catalyzed a (iPr-PNP)Mn(H)(CO)2 pincer complex under mild conditions in presence (catalytic) base liberating water (and H2 case alcohol alkylation) as sole byproduct.

Language: Английский

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Manganese-catalyzed hydrogenation, dehydrogenation, and hydroelementation reactions

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(11), P. 4386 - 4464

Published: Jan. 1, 2022

The emerging field of organometallic catalysis has shifted towards research on Earth-abundant transition metals due to their ready availability, economic advantage, and novel properties. In this case, manganese, the third most abundant transition-metal in Earth's crust, emerged as one leading competitors. Accordingly, a large number molecularly-defined Mn-complexes been synthesized employed for hydrogenation, dehydrogenation, hydroelementation reactions. regard, catalyst design is based three pillars, namely, metal-ligand bifunctionality, ligand hemilability, redox activity. Indeed, developed catalysts not only differ chelating atoms they possess but also working principles, thereby different turnover numbers product molecules. Hence, critical assessment molecularly defined manganese terms atoms, reaction conditions, mechanistic pathway, significant. Herein, we analyze complexes catalytic activity, versatility allow multiple transformations routes convert substrates target This article will be helpful get significant insight into design, aiding design.

Language: Английский

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Alcohols as Substrates in Transition-Metal-Catalyzed Arylation, Alkylation, and Related Reactions

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(9), P. 6078 - 6144

Published: April 17, 2024

Alcohols are abundant and attractive feedstock molecules for organic synthesis. Many methods their functionalization require them to first be converted into a more activated derivative, while recent years have seen vast increase in the number of complexity-building transformations that directly harness unprotected alcohols. This Review discusses how transition metal catalysis can used toward this goal. These broadly classified three categories. Deoxygenative functionalizations, representing derivatization C–O bond, enable alcohol act as leaving group formation new C–C bonds. Etherifications, characterized by O–H represent classical reactivity has been modernized include mild reaction conditions, diverse partners, high selectivities. Lastly, chain reactions described, wherein acts mediator formal C–H alkyl backbone. Each these classes transformation will discussed context intermolecular arylation, alkylation, related reactions, illustrating alcohols harnessed

Language: Английский

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Manganese(I)‐Catalyzed β‐Methylation of Alcohols Using Methanol as C₁ Source

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 59(1), P. 215 - 220

Published: Oct. 25, 2019

Highly selective β-methylation of alcohols was achieved using an earth-abundant first row transition metal in the air stable molecular manganese complex [Mn(CO)

Language: Английский

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Manganese Catalyzed α-Alkylation of Nitriles with Primary Alcohols

ACS Catalysis, Journal Year: 2018, Volume and Issue: 8(10), P. 9226 - 9231

Published: Aug. 24, 2018

The manganese(I) complex bearing a bidentate hydrazone ligand efficiently catalyzes the α-alkylations of nitrile using primary alcohols as alkylating agents. α-Functionalized nitriles were selectively obtained in good to excellent yields. reaction is environmentally benign, producing water sole byproduct. Both benzylic and aliphatic could be used functional groups tolerated.

Language: Английский

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Nonbifunctional Outer-Sphere Strategy Achieved Highly Active α-Alkylation of Ketones with Alcohols by N-Heterocyclic Carbene Manganese (NHC-Mn)

Organic Letters, Journal Year: 2019, Volume and Issue: 21(19), P. 8065 - 8070

Published: Sept. 16, 2019

The unusual nonbifunctional outer-sphere strategy was successfully utilized in developing an easily accessible N-heterocyclic carbene manganese (NHC-Mn) system for highly active α-alkylation of ketones with alcohols. This efficient a wide range and alcohols under mild reaction conditions, also the green synthesis quinoline derivatives. direct mechanism high activity present demonstrate potential catalyst design acceptorless dehydrogenative transformations.

Language: Английский

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Recent Progress with Pincer Transition Metal Catalysts for Sustainability

Catalysts, Journal Year: 2020, Volume and Issue: 10(7), P. 773 - 773

Published: July 11, 2020

Our planet urgently needs sustainable solutions to alleviate the anthropogenic global warming and climate change. Homogeneous catalysis has potential play a fundamental role in this process, providing novel, efficient, at same time eco-friendly routes for both chemicals energy production. In particular, pincer-type ligation shows promising properties terms of long-term stability selectivity, as well allowing mild reaction conditions low catalyst loading. Indeed, pincer complexes have been applied plethora chemical processes, such hydrogen release, CO2 capture conversion, N2 fixation, biomass valorization synthesis high-value fuels. work, we show main advances last five years use transition metal key catalytic processes aiming more

Language: Английский

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Manganese Catalyzed Acceptorless Dehydrogenative Coupling Reactions

ChemCatChem, Journal Year: 2019, Volume and Issue: 12(7), P. 1891 - 1902

Published: Dec. 21, 2019

Abstract Acceptorless dehydrogenative coupling (ADC) has emerged as a powerful tool in the chemists’ arsenal for construction of various carbon‐carbon and carbon‐heteroatom bonds. These protocols are highly atom economical environmentally benign they do not require pre‐functionalized starting material produce only dihydrogen (and water) by‐product. This technique, coupled with Earths’ abundant less toxic manganese catalysis, can prove to be vital strategy generation molecular complexity from simple materials. Manganese catalyzed DHC been growing interest, low‐ high‐valent catalysts have developed. were demonstrated show excellent catalytic activity formation carbon‐carbon, bonds, cascade reactions. In this mini‐review, we would like highlight recent progress that made ADC

Language: Английский

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