Methanol as the Hydrogen Source in the Selective Transfer Hydrogenation of Alkynes Enabled by a Manganese Pincer Complex

Organic Letters, Journal Year: 2020, Volume and Issue: 22(15), P. 6067 - 6071

Published: July 28, 2020

The first base metal-catalyzed transfer hydrogenation of alkynes with methanol is described. An air and moisture stable manganese pincer complex catalyzes the reduction a variety different to corresponding (Z)-olefins in high yields. reaction stereo- chemoselective scalable.

Language: Английский

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The Deuterated “Magic Methyl” Group: A Guide to Site‐Selective Trideuteromethyl Incorporation and Labeling by Using CD₃Reagents

Chemistry - A European Journal, Journal Year: 2021, Volume and Issue: 27(46), P. 11751 - 11772

Published: June 2, 2021

Abstract In the field of medicinal chemistry, precise installation a trideuteromethyl group is gaining ever‐increasing attention. Site‐selective incorporation deuterated “magic methyl” can provide profound pharmacological benefits and be considered an important tool for drug optimization development. This review provides structured overview, according to trideuteromethylation reagent, currently established methods site‐selective carbon atoms. addition CD 3 , selective introduction 2 H CDH groups also considered. For all methods, corresponding mechanism scope are discussed whenever reported. As such, this starting point synthetic chemists further advance methodologies. At same time, aims guide chemists, offering them available C−CD formation strategies preparation new or modified drugs.

Language: Английский

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Broadening of horizons in the synthesis of CD₃-labeled molecules

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(19), P. 10806 - 10835

Published: Jan. 1, 2021

This review highlights the different approaches for preparation of CD 3 -labeling molecules.

Language: Английский

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Advancements in multifunctional manganese complexes for catalytic hydrogen transfer reactions

Chemical Communications, Journal Year: 2021, Volume and Issue: 57(69), P. 8534 - 8549

Published: Jan. 1, 2021

Manganese catalyzed hydrogen transfer reactions enabled net reductions and cascade CC- CN-bond formation reactions. The success is aided by multifunctional ligand design namely metal–ligand bifunctionality, hemilability, redox non-innocence.

Language: Английский

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Towards ligand simplification in manganese-catalyzed hydrogenation and hydrosilylation processes

Coordination Chemistry Reviews, Journal Year: 2022, Volume and Issue: 458, P. 214421 - 214421

Published: Jan. 31, 2022

Language: Английский

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Well-Defined Phosphine-Free Manganese(II)-Complex-Catalyzed Synthesis of Quinolines, Pyrroles, and Pyridines

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(13), P. 8351 - 8367

Published: June 21, 2022

Herein, we report a simple, phosphine-free, and inexpensive catalytic system based on manganese(II) complex for synthesizing different important N-heterocycles such as quinolines, pyrroles, pyridines from amino alcohols ketones. Several control experiments, kinetic studies, DFT calculations were carried out to support the plausible reaction mechanism. We also detected two potential intermediates in cycle using ESI-MS analysis. Based these metal-ligand cooperative mechanism was proposed.

Language: Английский

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Multi-Functionality of Methanol in Sustainable Catalysis: Beyond Methanol Economy

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(22), P. 15013 - 15053

Published: Nov. 6, 2023

Methanol is a fundamental feedstock and widely used in the chemical petroleum industries. It can serve as C1 source to make variety of C–C C–N bond formation dehydrogenative coupling products, which have important applications natural products drug discovery. A high hydrogen content (12.5 wt%) methanol makes it an effective H2 donor for transfer hydrogenation various reducible functional groups. plethora transition metal-based processes been developed using methanol. Notably, recent review articles focused on aspect However, more updated that examines challenges both C1-source H2-source organic transformations contributing concept economy has not presented yet. This Review summarizes (homogeneous, heterogeneous, photo-) catalyst system C-, N-, O-methylation ketones, alcohols, amides, nitriles, heterocyclic compounds, sulfones, amines, sulfonamides direct N-methylation nitro compounds under borrowing strategy N-formylation amines acceptorless dehydrogenation source. also covers insights into reaction mechanisms role carefully selected ligands metal catalysis activation incorporation -CD3, methylation molecules. Moreover, describes groups such aldehydes, alkynes, with detail.

Language: Английский

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Manganese‐Catalyzed Mono‐N‐Methylation of Aliphatic Primary Amines without the Requirement of External High‐Hydrogen Pressure

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(13)

Published: Feb. 1, 2024

Abstract The synthesis of mono‐ N ‐methylated aliphatic primary amines has traditionally been challenging, requiring noble metal catalysts and high‐pressure H 2 for achieving satisfactory yields selectivity. Herein, we developed an approach the selective coupling methanol amines, without hydrogen, using a manganese‐based catalyst. Remarkably, up to 98 % with broad substrate scope were achieved at low catalyst loadings. Notably, due weak base‐catalyzed alcoholysis formamide intermediates, our novel protocol not only obviates addition but also prevents side secondary ‐methylation, supported by control experiments density functional theory calculations.

Language: Английский

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A Phosphine-Free Manganese Catalyst Enables Stereoselective Synthesis of (1 + n)-Membered Cycloalkanes from Methyl Ketones and 1,n-Diols

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(4), P. 2615 - 2626

Published: Jan. 24, 2020

Herein, we report the stereoselective synthesis of (1 + n)-membered cycloalkane from methyl ketone and 1,n-diol. A manganese(I) complex bearing a phosphine-free ligand catalyzed reaction, which involved formation two C–C bonds via sequence intermolecular- intramolecular-borrowing hydrogenation reactions. It produces 2 mol water as sole byproduct, making process atom economical environmentally benign. Multisubstituted cycloalkanes were obtained in good to excellent yields with very high selectivities. thorough mechanistic analysis by high-level DFT computation rationalizes choice pincer establishes role hemilability for this efficient transformation.

Language: Английский

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Palladacycle-Phosphine Catalyzed Methylation of Amines and Ketones Using Methanol

The Journal of Organic Chemistry, Journal Year: 2019, Volume and Issue: 84(16), P. 10472 - 10480

Published: July 23, 2019

Methylation of amines and ketones with palladacycle precatalyst has been performed using methanol as an environmentally benign reagent. Various undergo methylation reaction to yield monomethylated or in moderate good isolated yields. Moreover, this protocol was tested for the chemoselective 4-aminobenzenesulfonamide. The scope further extended deuteromethylation ketones.

Language: Английский

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