Hydrogenation or Dehydrogenation of N-Containing Heterocycles Catalyzed by a Single Manganese Complex DOI

Viktoriia Zubar,

Jannik C. Borghs,

Magnus Rueping

et al.

Organic Letters, Journal Year: 2020, Volume and Issue: 22(10), P. 3974 - 3978

Published: May 4, 2020

A highly chemoselective base-metal catalyzed hydrogenation and acceptorless dehydrogenation of N-heterocycles is presented. well-defined Mn complex operates at low catalyst loading (as as 2 mol %) under mild reaction conditions. The described catalytic system tolerates various functional groups, the corresponding reduced heterocycles can be obtained in high yields. Experimental studies indicate a metal-ligand cooperative catalysis mechanism.

Language: Английский

Transition-Metal-Catalyzed Reductive Amination Employing Hydrogen DOI
Τ. Irrgang, Rhett Kempe

Chemical Reviews, Journal Year: 2020, Volume and Issue: 120(17), P. 9583 - 9674

Published: Aug. 19, 2020

The reductive amination, the reaction of an aldehyde or a ketone with ammonia amine in presence reducing agent and often catalyst, is important synthesis has been intensively investigated academia industry for century. Besides aldehydes, ketones, amines, starting materials have used that can be converted into (for instance, carboxylic acids organic carbonate nitriles) nitro compound) same catalyst. Mechanistically, starts condensation step during which carbonyl compound reacts amine, forming corresponding imine followed by reduction to alkyl product. Many these steps require catalyst activate agent. amination impressive regard product scope since primary, secondary, tertiary amines are accessible hydrogen most attractive agent, especially if large-scale formation issue, inexpensive abundantly available. Alkyl produced use fine bulk chemicals. They key functional groups many pharmaceuticals, agro chemicals, materials. In this review, we summarize work published on employing as No comprehensive review focusing subject 1948, albeit interesting summaries dealing one other aspect appeared. Impressive progress using catalysts based earth-abundant metals, nanostructured heterogeneous catalysts, made early development field recent years.

Language: Английский

Citations

354
Homogeneous manganese-catalyzed hydrogenation and dehydrogenation reactions DOI Creative Commons
Yujie Wang, Mingyang Wang, Yibiao Li

et al.

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

Published: Dec. 9, 2020

Language: Английский

Citations

218
Reversible hydrogenation of carbon dioxide to formic acid using a Mn-pincer complex in the presence of lysine DOI Creative Commons
Duo Wei, Rui Sang, Peter Sponholz

et al.

Nature Energy, Journal Year: 2022, Volume and Issue: 7(5), P. 438 - 447

Published: May 19, 2022

Abstract Efficient hydrogen storage and release are essential for effective use of as an energy carrier. In principle, formic acid could be used a convenient medium via reversible CO 2 hydrogenation. However, noble metal-based catalysts currently needed to facilitate the (de)hydrogenation, produced during is generally released, resulting in undesirable emissions. Here we report α -amino acid-promoted system hydrogenation using Mn-pincer complex homogeneous catalyst. We observe good stability reusability catalyst lysine amino at high productivities (CO hydrogenation: total turnover number 2,000,000; dehydrogenation: 600,000). Employing potassium lysinate, achieve >80% H evolution efficiency >99.9% retention ten charge–discharge cycles, avoiding re-loading steps between each cycle. This process was scaled up by factor 18 without obvious drop productivity.

Language: Английский

Citations

178
Manganese-catalyzed hydrogenation, dehydrogenation, and hydroelementation reactions DOI
Kuhali Das, Satyadeep Waiba, Akash Jana

et al.

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

Citations

160
Development of a practical non-noble metal catalyst for hydrogenation of N-heteroarenes DOI
Veronica Papa, Yi-Xuan Cao,

Anke Spannenberg

et al.

Nature Catalysis, Journal Year: 2020, Volume and Issue: 3(2), P. 135 - 142

Published: Jan. 6, 2020

Language: Английский

Citations

155
Robust and efficient hydrogenation of carbonyl compounds catalysed by mixed donor Mn(I) pincer complexes DOI Creative Commons
Wenjun Yang, Ivan Yu. Chernyshov, Robin K. A. van Schendel

et al.

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: Jan. 4, 2021

Abstract Any catalyst should be efficient and stable to implemented in practice. This requirement is particularly valid for manganese hydrogenation catalysts. While representing a more sustainable alternative conventional noble metal-based systems, catalysts are prone degrade under catalytic conditions once operation temperatures high. Herein, we report highly Mn(I)-CNP pre-catalyst which gives rise the excellent productivity (TOF° up 41 000 h −1 ) stability (TON 200 000) catalysis. system enables near-quantitative of ketones, imines, aldehydes formate esters at loadings as low 5–200 p.p.m. Our analysis points crucial role activation step performance system. employing alkoxide bases can ultimately provide catalytically competent species hydrogen atmosphere, Mn(I) with hydride donor promoters, e.g. KHBEt 3 , dramatically improves eliminates induction times associated slow activation.

Language: Английский

Citations

152
Asymmetric hydrogenation of ketimines with minimally different alkyl groups DOI
Mingyang Wang, Shihan Liu, Hao Liu

et al.

Nature, Journal Year: 2024, Volume and Issue: 631(8021), P. 556 - 562

Published: May 28, 2024

Language: Английский

Citations

30
Manganese‐Catalyzed Asymmetric Hydrogenation of Quinolines Enabled by π–π Interaction** DOI
Chenguang Liu, Mingyang Wang, Shihan Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 60(10), P. 5108 - 5113

Published: Nov. 26, 2020

Abstract The non‐noble metal‐catalyzed asymmetric hydrogenation of N‐heteroaromatics, quinolines, is reported. A new chiral pincer manganese catalyst showed outstanding catalytic activity in the affording high yields and enantioselectivities (up to 97 % ee). turnover number 3840 was reached at a low loading (S/C=4000), which competitive with most effective noble metal catalysts for this reaction. precise regulation enantioselectivity were ensured by π–π interaction.

Language: Английский

Citations

137
Unmasking the Ligand Effect in Manganese-Catalyzed Hydrogenation: Mechanistic Insight and Catalytic Application DOI
Yujie Wang, Lei Zhu, Zhihui Shao

et al.

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(43), P. 17337 - 17349

Published: Oct. 21, 2019

Manganese-catalyzed hydrogenation reactions have attracted broad interest since the first report in 2016. Among reported catalytic systems, Mn catalysts supported by tridentate PNP- and NNP-pincer ligands most commonly been used. For example, a number of PNP-Mn pincer for aldehydes, aldimines, ketones, nitriles, esters. Furthermore, various NNP-Mn shown to be active less-reactive substrates such as amides, carbonates, carbamates, urea derivations. These observations indicated that exhibit higher reactivity than their PNP counterparts. Such ligand effect Mn-catalyzed has yet confirmed. Herein, we investigated origin applicability this effect. A combination experimental theoretical investigations showed on complexes were more electron-rich less sterically hindered counterparts, leading series reactions. Inspired hydrogenations, developed N-heterocycles. Specifically, hydrogenated N-heterocycles (32 examples) with up 99% yields, corresponding afforded low under same conditions. This verified is generally applicable both carbonyl noncarbonyl based catalysis.

Language: Английский

Citations

129
Manganese‐Catalyzed β‐Methylation of Alcohols by Methanol DOI Creative Commons

Martin Schlagbauer,

Fabian Kallmeier, Τ. Irrgang

et al.

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 59(4), P. 1485 - 1490

Published: Nov. 19, 2019

Abstract We report an earth‐abundant‐metal‐catalyzed double and single methylation of alcohols. A manganese catalyst, which operates at low catalyst loadings short reaction times, mediates these reactions efficiently. broad scope primary secondary alcohols, including purely aliphatic examples, 1,2‐aminoalcohols can be methylated. Furthermore, alcohol for the synthesis pharmaceuticals has been demonstrated. The system tolerates many functional groups among them hydrogenation‐sensitive examples upscaling is easily achieved. Mechanistic investigations are indicative a borrowing hydrogen or autotransfer mechanism involving bimetallic K‐Mn catalyst. accepts as proton hydride from alcohols efficiently reacts with chalcone via transfer.

Language: Английский

Citations

106