Sustainable Manganese-Catalyzed Solvent-Free Synthesis of Pyrroles from 1,4-Diols and Primary Amines DOI

Jannik C. Borghs,

Yury Lebedev, Magnus Rueping

et al.

Organic Letters, Journal Year: 2018, Volume and Issue: 21(1), P. 70 - 74

Published: Dec. 24, 2018

A general and selective metal-catalyzed conversion of biomass-derived primary diols amines to the highly valuable 2,5-unsubstituted pyrroles has been developed. The reaction is catalyzed by a stable nonprecious manganese complex (1 mol %) in absence organic solvents whereby water molecular hydrogen are only side products. catalyst shows unprecedented selectivity, avoiding formation pyrrolidines, cyclic imides, lactones.

Language: Английский

Recent Developments for the Deuterium and Tritium Labeling of Organic Molecules DOI Creative Commons
Sara Kopf, Florian Bourriquen, Wu Li

et al.

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(6), P. 6634 - 6718

Published: Feb. 18, 2022

Organic compounds labeled with hydrogen isotopes play a crucial role in numerous areas, from materials science to medicinal chemistry. Indeed, while the replacement of by deuterium gives rise improved absorption, distribution, metabolism, and excretion (ADME) properties drugs enables preparation internal standards for analytical mass spectrometry, use tritium-labeled is key technique all along drug discovery development pharmaceutical industry. For these reasons, interest new methodologies isotopic enrichment organic molecules extent their applications are equally rising. In this regard, Review intends comprehensively discuss developments area over last years (2017–2021). Notably, besides fundamental isotope exchange (HIE) reactions isotopically analogues common reagents, plethora reductive dehalogenative deuteration techniques other transformations incorporation emerging now part labeling toolkit.

Language: Английский

Citations

392

Borrowing Hydrogen for Organic Synthesis DOI Creative Commons

Benjamin G. Reed‐Berendt,

Daniel E. Latham,

Mubarak B. Dambatta

et al.

ACS Central Science, Journal Year: 2021, Volume and Issue: 7(4), P. 570 - 585

Published: March 25, 2021

Borrowing hydrogen is a process that used to diversify the synthetic utility of commodity alcohols. A catalyst first oxidizes an alcohol by removing form reactive carbonyl compound. This intermediate can undergo diverse range subsequent transformations before returns "borrowed" liberate product and regenerate catalyst. In this way, alcohols may be as alkylating agents whereby sole byproduct one-pot reaction water. recent decades, significant advances have been made in area, demonstrating many effective methods access valuable products. outlook highlights diversity metal biocatalysts are available for approach, well various performed, focusing on selection most advances. By succinctly describing conveying versatility borrowing chemistry, we anticipate its uptake will increase across wider scientific audience, expanding opportunities further development.

Language: Английский

Citations

321

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

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

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

Adam Cook,

Stephen G. Newman

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

Citations

39

Manganese(I)‐Catalyzed β‐Methylation of Alcohols Using Methanol as C1 Source DOI Creative Commons
Akash Kaithal, Pit van Bonn, Markus Hölscher

et al.

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

Citations

111

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

Iron-Catalyzed Borrowing Hydrogen β-C(sp3)-Methylation of Alcohols DOI Creative Commons

Kurt Polidano,

Jonathan M. J. Williams,

Louis C. Morrill

et al.

ACS Catalysis, Journal Year: 2019, Volume and Issue: 9(9), P. 8575 - 8580

Published: Aug. 21, 2019

Herein we report the iron-catalyzed β-C(sp3)-methylation of primary alcohols using methanol as a C1 building block. This borrowing hydrogen approach employs well-defined bench-stable (cyclopentadienone)iron(0) carbonyl complex precatalyst (5 mol %) and enables diverse selection substituted 2-arylethanols to undergo in good isolated yields (24 examples, 65% average yield).

Language: Английский

Citations

93

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

Citations

91

Commercial Pd/C-Catalyzed N-Methylation of Nitroarenes and Amines Using Methanol as Both C1 and H2 Source DOI
Vishakha Goyal,

Jyoti Gahtori,

N. ANAND

et al.

The Journal of Organic Chemistry, Journal Year: 2019, Volume and Issue: 84(23), P. 15389 - 15398

Published: Nov. 8, 2019

Herein, we report commercially available carbon-supported-palladium (Pd/C)-catalyzed N-methylation of nitroarenes and amines using MeOH as both a C1 H2 source. This transformation proceeds with high atom-economy in an environmentally friendly way via borrowing hydrogen mechanism. A total >30 structurally diverse N-methylamines, including bioactive compounds, were selectively synthesized isolated yields up to 95%. Furthermore, selective deuteration nimesulide, nonsteroidal anti-inflammatory drug, realized through the late-stage functionalization.

Language: Английский

Citations

80