Phosphine-Free Well-Defined Mn(I) Complex-Catalyzed Synthesis of Amine, Imine, and 2,3-Dihydro-1H-perimidine via Hydrogen Autotransfer or Acceptorless Dehydrogenative Coupling of Amine and Alcohol DOI
Kalicharan Das, Avijit Mondal,

Debjyoti Pal

et al.

Organometallics, Journal Year: 2019, Volume and Issue: 38(8), P. 1815 - 1825

Published: April 12, 2019

The application of nontoxic, earth-abundant transition metals in place costly noble is a paramount goal catalysis and especially interesting if the air- moisture-stable ligand scaffold used. Herein, we report synthesis amines/imines directly from alcohol amines via hydrogen autotransfer or acceptorless dehydrogenation catalyzed by well-defined phosphine-free Mn complexes. Both imines can be obtained same set alcohols using catalyst, only tuning reaction conditions. amount nature base are found to highly important aspect for observed selectivity. primary secondary have been employed as substrates N-alkylation reaction. As highlight, showed chemoselective resveratrol derivatives. Furthermore, Mn-catalyzed dehydrogenative structurally 2,3-dihydro-1H-perimidines has also demonstrated. Density functional theory calculations were carried out model path calculate profile.

Language: Английский

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

Lukas Alig,

Maximilian Fritz,

Sven Schneider

et al.

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

Citations

764
Catalytic (de)hydrogenation promoted by non-precious metals – Co, Fe and Mn: recent advances in an emerging field DOI Creative Commons
Georgy A. Filonenko, Robbert van Putten, Emiel J. M. Hensen

et al.

Chemical Society Reviews, Journal Year: 2018, Volume and Issue: 47(4), P. 1459 - 1483

Published: Jan. 1, 2018

Catalytic hydrogenation and dehydrogenation reactions form the core of modern chemical industry. This vast class is found in any part synthesis starting from milligram-scale exploratory organic chemistry to multi-ton base chemicals production. Noble metal catalysis has long been key driving force enabling these transformations with carbonyl substrates their nitrogen-containing counterparts. review aimed at introducing reader remarkable progress made last three years development catalysts for hydrogenations dehydrogenative transformations.

Language: Английский

Citations

612
Manganese Complexes for (De)Hydrogenation Catalysis: A Comparison to Cobalt and Iron Catalysts DOI
Fabian Kallmeier, Rhett Kempe

Angewandte Chemie International Edition, Journal Year: 2017, Volume and Issue: 57(1), P. 46 - 60

Published: Oct. 24, 2017

The sustainable use of the resources on our planet is essential. Noble metals are very rare and diversely used in key technologies, such as catalysis. Manganese third most abundant transition metal Earth's crust based recently discovered impressive reactivity hydrogenation dehydrogenation reactions, a potentially useful noble-metal "replacement". hope novel selectivity profiles, not possible with noble metals, also an aim manganese complexes (de)hydrogenation reactions was demonstrated for first time 2016. Herein, we summarize work that has been published since then especially discuss importance homogeneous catalysts comparison to cobalt iron catalysts.

Language: Английский

Citations

525
Homogeneous Catalysis by Cobalt and Manganese Pincer Complexes DOI
Arup Mukherjee, David Milstein

ACS Catalysis, Journal Year: 2018, Volume and Issue: 8(12), P. 11435 - 11469

Published: Oct. 16, 2018

Homogeneous catalysis of organic transformations by metal complexes has been mostly based on noble metals. In recent years, tremendous progress made in the field base-metal catalysis, with pincer-type complexes, such as iron, cobalt, nickel, and manganese pincer systems. Particularly impressive is explosive growth Mn-based first being reported recently 2016. This review covers homogeneously catalyzed reactions using cobalt manganese. Various are described, including acceptorless dehydrogenation, hydrogenation, dehydrogenative coupling, hydrogen borrowing, transfer, H–X additions, C–C alkene polymerization N2 fixation, their scope brief mechanistic comments.

Language: Английский

Citations

494
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

217
Recent Advances in Catalysis with Transition‐Metal Pincer Compounds DOI
Hugo Valdés, Marco A. García‐Eleno, Daniel Canseco‐González

et al.

ChemCatChem, Journal Year: 2018, Volume and Issue: 10(15), P. 3136 - 3172

Published: March 24, 2018

Abstract Pincer complexes are useful tools for organic synthesis. Their high stability and easy functionalization have allowed the development of novel catalytic systems that had a tremendous impact in different areas chemistry. Thus, reactions nowadays fundamental part several synthetic routes, as they allow “greener” procedures with atom efficiency. In this context, pincer contributed to establishment efficient reactions. herein we summarize most recent relevant advances involving catalysts.

Language: Английский

Citations

216
Manganese-Catalyzed α-Alkylation of Ketones, Esters, and Amides Using Alcohols DOI Creative Commons
Subrata Chakraborty, Prosenjit Daw,

Yehoshoa Ben David

et al.

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

Citations

187
Direct Synthesis of Benzimidazoles by Dehydrogenative Coupling of Aromatic Diamines and Alcohols Catalyzed by Cobalt DOI
Prosenjit Daw,

Yehoshoa Ben‐David,

David Milstein

et al.

ACS Catalysis, Journal Year: 2017, Volume and Issue: 7(11), P. 7456 - 7460

Published: Sept. 27, 2017

Herein, we present the base-metal-catalyzed dehydrogenative coupling of primary alcohols and aromatic diamines to selectively form functionalized 2-substituted benzimidazoles, liberating water hydrogen gas as sole byproducts. The reaction is catalyzed by pincer complexes Earth-abundant cobalt under base-free conditions.

Language: Английский

Citations

182
Manganese-Catalyzed and Base-Switchable Synthesis of Amines or Imines via Borrowing Hydrogen or Dehydrogenative Condensation DOI
Robin Fertig, Τ. Irrgang,

Frederik Freitag

et al.

ACS Catalysis, Journal Year: 2018, Volume and Issue: 8(9), P. 8525 - 8530

Published: Aug. 8, 2018

The use of earth-abundant transition metals as a noble metal replacement in catalysis is especially interesting if different catalytic reactivity observed. We report, here, on the selective manganese-catalyzed base-switchable synthesis N-alkylated amines or imines. In both reactions, borrowing hydrogen/hydrogen autotransfer (N-alkyl amine formation) dehydrogenative condensation (imine formation), we start from same and alcohols Mn precatalyst. key presence potassium base to prefer N-alkylation sodium permit imine formation. Both bases react with manganese hydride via deprotonation. manganate reacts about 40 times faster an give corresponding than hydride. selectivity seems unique for complexes. observe broad scope complete product overlap, all alcohol combinations can be converted into N-alkyl imine, good functional group tolerance.

Language: Английский

Citations

180
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

158