3d-Metal Catalyzed N- and C-Alkylation Reactions via Borrowing Hydrogen or Hydrogen Autotransfer

Chemical Reviews, Год журнала: 2018, Номер 119(4), С. 2524 - 2549

Опубликована: Ноя. 20, 2018

The conservation of our element resources is a fundamental challenge mankind. development alcohol refunctionalization reactions possible fossil carbon strategy since alcohols can be obtained from indigestible and abundantly available biomass. rare noble metals, frequently used in key technologies such as catalysis, might feasible by replacing them with highly abundant metals. alkylation amines related C–C coupling are early examples reactions. These follow mostly the borrowing hydrogen or autotransfer catalysis concept, many 3d-metal catalysts have been disclosed recent years. In this review, we summarize progress made developing Cu, Ni, Co, Fe, Mn for C–N bond formation using concept. We expect that findings field will inspire others to develop new efficient selective earth-abundant metal applications novel mediated

Язык: Английский

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New Strategies for the Transition-Metal Catalyzed Synthesis of Aliphatic Amines

Chemical Reviews, Год журнала: 2020, Номер 120(5), С. 2613 - 2692

Опубликована: Фев. 17, 2020

Transition-metal catalyzed reactions that are able to construct complex aliphatic amines from simple, readily available feedstocks have become a cornerstone of modern synthetic organic chemistry. In light the ever-increasing importance across range chemical sciences, this review aims provide concise overview transition-metal approaches alkylamine synthesis and their functionalization. Selected examples amine bond forming include: (a) hydroamination hydroaminoalkylation, (b) C(sp3)–H functionalization, (c) visible-light-mediated photoredox catalysis.

Язык: Английский

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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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Strategies and mechanisms of metal–ligand cooperativity in first-row transition metal complex catalysts

Chemical Society Reviews, Год журнала: 2020, Номер 49(24), С. 8933 - 8987

Опубликована: Янв. 1, 2020

The use of metal–ligand cooperation (MLC) by transition metal bifunctional catalysts has emerged at the forefront homogeneous catalysis science.

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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Recent advances in sustainable synthesis of N-heterocycles following acceptorless dehydrogenative coupling protocol using alcohols

Organic Chemistry Frontiers, Год журнала: 2021, Номер 8(11), С. 2673 - 2709

Опубликована: Янв. 1, 2021

In this review, we have summarized various aspects of homogeneous and heterogeneously catalyzed recent advancements in the synthesis heterocycles following ADC approach.

Язык: Английский

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From Hydrogenation to Transfer Hydrogenation to Hydrogen Auto-Transfer in Enantioselective Metal-Catalyzed Carbonyl Reductive Coupling: Past, Present, and Future

ACS Catalysis, Год журнала: 2021, Номер 11(9), С. 5572 - 5585

Опубликована: Апрель 22, 2021

Atom-efficient processes that occur via addition, redistribution or removal of hydrogen underlie many large volume industrial and pervade all segments chemical industry. Although carbonyl addition is one the oldest most broadly utilized methods for C-C bond formation, delivery non-stabilized carbanions to compounds has relied on premetalated reagents metallic/organometallic reductants, which pose issues safety challenges vis-à-vis implementation. Catalytic reductive couplings promoted hydrogenation, transfer hydrogenation auto-transfer allow abundant unsaturated hydrocarbons serve as substitutes organometallic reagents, enabling formation in absence stoichiometric metals. This perspective (a) highlights past milestones catalytic auto-transfer, (b) summarizes current enantioselective couplings, (c) describes future opportunities based patterns reactivity animate transformations this type.

Язык: Английский

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Borrowing Hydrogen Amination Reactions: A Complex Analysis of Trends and Correlations of the Various Reaction Parameters

ACS Catalysis, Год журнала: 2022, Номер 12(12), С. 7142 - 7198

Опубликована: Июнь 1, 2022

Borrowing hydrogen or the autotransfer amination is a powerful approach to create single C–N bonds, starting from stable and readily available substrates: amines alcohols. It considered as one of most atom-efficient green methods synthesize complex amines. Herein, we attempted arrange array existing data in comprehensive structured manner determine correlations between experimental conditions catalysis outcome both within different groups catalysts defined using machine analysis. For each type N-nucleophiles (aromatic, aliphatic, heteroaromatic amines, amides), efficient working were suggested, including attributing optimal base temperature regime for metal.

Язык: Английский

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Enantioconvergent transformations of secondary alcohols through borrowing hydrogen catalysis

Chemical Society Reviews, Год журнала: 2023, Номер 52(16), С. 5541 - 5562

Опубликована: Янв. 1, 2023

Enantioconvergent transformations of racemic secondary alcohols to enantioenriched chiral amines, N-heterocycles, higher-order and ketones through borrowing hydrogen catalysis is covered in this review.

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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