Borrowing Hydrogen for Organic Synthesis

ACS Central Science, Год журнала: 2021, Номер 7(4), С. 570 - 585

Опубликована: Март 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.

Язык: Английский

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Homogeneous manganese-catalyzed hydrogenation and dehydrogenation reactions

Chem, Год журнала: 2020, Номер 7(5), С. 1180 - 1223

Опубликована: Дек. 9, 2020

Язык: Английский

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Manganese-catalyzed hydrogenation, dehydrogenation, and hydroelementation reactions

Chemical Society Reviews, Год журнала: 2022, Номер 51(11), С. 4386 - 4464

Опубликована: Янв. 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.

Язык: Английский

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

Chemical Reviews, Год журнала: 2024, Номер 124(9), С. 6078 - 6144

Опубликована: Апрель 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

Язык: Английский

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Manganese(I)‐Catalyzed β‐Methylation of Alcohols Using Methanol as C₁ Source

Angewandte Chemie International Edition, Год журнала: 2019, Номер 59(1), С. 215 - 220

Опубликована: Окт. 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)

Язык: Английский

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Manganese‐Catalyzed β‐Methylation of Alcohols by Methanol

Angewandte Chemie International Edition, Год журнала: 2019, Номер 59(4), С. 1485 - 1490

Опубликована: Ноя. 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.

Язык: Английский

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

ACS Catalysis, Год журнала: 2019, Номер 9(9), С. 8575 - 8580

Опубликована: Авг. 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).

Язык: Английский

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Direct Synthesis of Cycloalkanes from Diols and Secondary Alcohols or Ketones Using a Homogeneous Manganese Catalyst

Journal of the American Chemical Society, Год журнала: 2019, Номер 141(44), С. 17487 - 17492

Опубликована: Окт. 29, 2019

A method for the synthesis of substituted cycloalkanes was developed using diols and secondary alcohols or ketones via a cascade hydrogen borrowing sequence. non-noble air-stable manganese catalyst (2 mol %) used to perform this transformation. Various 1,5-pentanediols (3-4 equiv) (1 were investigated prepare collection cyclohexanes in diastereoselective fashion. Similarly, cyclopentane, cyclohexane, cycloheptane rings constructed from 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, sterically hindered following (4 + 1), (5 (6 1) strategy, respectively. This reaction provides an atom economic methodology construct two C-C bonds at single carbon center generating high-value readily available as feedstock earth-abundant metal catalyst.

Язык: Английский

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Recent advancement in oxidation or acceptorless dehydrogenation of alcohols to valorised products using manganese based catalysts

Coordination Chemistry Reviews, Год журнала: 2020, Номер 411, С. 213241 - 213241

Опубликована: Март 4, 2020

Язык: Английский

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Sustainable Alkylation of Nitriles with Alcohols by Manganese Catalysis

The Journal of Organic Chemistry, Год журнала: 2019, Номер 84(12), С. 7927 - 7935

Опубликована: Май 22, 2019

A general and chemoselective catalytic alkylation of nitriles using a homogeneous nonprecious manganese catalyst is presented. This reaction uses naturally abundant alcohols readily available as coupling partners. The tolerates wide range functional groups heterocyclic moieties, efficiently providing useful cyanoalkylated products with water the only side product. Importantly, methanol can be used C1 source C-methylation achieved. mechanistic investigations support multiple role metal-ligand catalyst, dehydrogenative activation alcohol, α-C-H nitrile, hydrogenation in-situ-formed unsaturated intermediate.

Язык: Английский

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