Borrowing Hydrogen for Organic Synthesis

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

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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 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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Manganese‐Catalyzed β‐Methylation of Alcohols by Methanol

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

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Control of Absolute Stereochemistry in Transition‐Metal‐Catalysed Hydrogen‐Borrowing Reactions

Chemistry - A European Journal, Journal Year: 2020, Volume and Issue: 26(57), P. 12912 - 12926

Published: April 16, 2020

Abstract Hydrogen‐borrowing catalysis represents a powerful method for the alkylation of amine or enolate nucleophiles with non‐activated alcohols. This approach relies upon catalyst that can mediate strategic series redox events, enabling formation C−C and C−N bonds producing water as sole by‐product. In majority cases these reactions have been employed to target achiral racemic products. contrast, focus this Minireview is hydrogen‐borrowing‐catalysed in which absolute stereochemical outcome process be controlled. Asymmetric hydrogen‐borrowing rapidly emerging synthesis enantioenriched carbonyl containing products examples involving both bond are presented. A variety different approaches discussed including use chiral auxiliaries, asymmetric enantiospecific processes.

Language: Английский

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Implementation of Cooperative Designs in Polarized Transition Metal Systems—Significance for Bond Activation and Catalysis

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(23), P. 14024 - 14055

Published: Nov. 17, 2020

Bond activation and catalysis are central to the development of a sustainable energy system. Frustrated Lewis Pairs have conceptually revolutionized inert chemical bonds. Far less developed hybrid systems containing at least one transition metal as part electron-donating/accepting composition. These cooperative architectures present advantages over traditional systems. For instance, they incorporate, concept FLPs, movement electron pairs typically encountered in elementary steps organometallic catalysis. This Perspective presents arguably most relevant recent progress vivid field research that aspires implement designs polarized Moreover, it provides tools for future developments shows molecular control bond-making -breaking processes can be achieved.

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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Nickel-Catalyzed Guerbet Type Reaction: C-Alkylation of Secondary Alcohols via Double (de)Hydrogenation

Organic Letters, Journal Year: 2021, Volume and Issue: 23(9), P. 3320 - 3325

Published: April 21, 2021

Acceptorless double dehydrogenative cross-coupling of secondary and primary alcohols under nickel catalysis is reported. This Guerbet type reaction provides an atom- a step-economical method for the C-alkylation mild, benign conditions. A broad range substrates including aromatic, cyclic, acyclic, aliphatic was well tolerated. Interestingly, cholesterol derivatives cyclopentanol with various were also demonstrated.

Language: Английский

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Preorganized Nitrogen Sites for Au₁₁ Amidation: A Generalizable Strategy toward Precision Functionalization of Metal Nanoclusters

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(22), P. 12164 - 12172

Published: May 26, 2023

Atomically precise metal nanoclusters have received tremendous attention due to their unique structures and properties. Although synthetic approaches this kind of nanomaterial been well developed, methods toward precision functionalization the as-synthesized are extremely limited, hindering interfacial modification related performance improvement. Herein, an amidation strategy has developed for Au11 nanocluster based on preorganized nitrogen sites. The did not change number gold atoms in kernel bonding mode surface ligands but slightly modified arrangement with introduction functionality chirality, thus representing a relatively mild method nanoclusters. stability oxidation barrier also improved accordingly. here would be generalizable

Language: Английский

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Three-Component Photochemical 1,2,5-Trifunctionalizations of Alkenes toward Densely Functionalized Lynchpins

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(43), P. 23814 - 23823

Published: Oct. 18, 2023

Radical remote 1,n-difunctionalization reactions (n > 2) of alkenes are powerful tools to efficiently introduce functional groups with selected distances into target molecules. Among these reactions, 1,5-difunctionalizations an important subclass, leading sought-after scaffolds, but typically suffer from tailored starting materials and strict limitations for the formed group in 2-position. Seeking address issues make radical more applicable, we report a novel three-component 1,2,5-trifunctionalization reaction between imine-based bifunctional reagents two distinct alkenes, driven by visible light energy transfer-catalysis. Key achieving this selective one-step installation three different via choreographed formation four bonds was utilization 1,2-boron shift rigorous capitalization polarities stabilities. Thorough mechanistic studies were carried out, synthetic utility obtained products demonstrated various downstream modifications. Notably, addition functionalization individual groups, their interplay gave rise unique array cyclic products.

Language: Английский

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