3d Transition Metals for C–H Activation

Chemical Reviews, Год журнала: 2018, Номер 119(4), С. 2192 - 2452

Опубликована: Ноя. 27, 2018

C–H activation has surfaced as an increasingly powerful tool for molecular sciences, with notable applications to material crop protection, drug discovery, and pharmaceutical industries, among others. Despite major advances, the vast majority of these functionalizations required precious 4d or 5d transition metal catalysts. Given cost-effective sustainable nature earth-abundant first row metals, development less toxic, inexpensive 3d catalysts gained considerable recent momentum a significantly more environmentally-benign economically-attractive alternative. Herein, we provide comprehensive overview on until summer 2018.

Язык: Английский

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Toolbox for Distal C–H Bond Functionalizations in Organic Molecules

Chemical Reviews, Год журнала: 2021, Номер 122(6), С. 5682 - 5841

Опубликована: Окт. 18, 2021

Transition-metal-catalyzed C–H activation has developed a contemporary approach to the omnipresent area of retrosynthetic disconnection. Scientific researchers have been tempted take help this methodology plan their synthetic discourses. This paradigm shift helped in development industrial units as well, making synthesis natural products and pharmaceutical drugs step-economical. In vast zone bond activation, functionalization proximal bonds gained utmost popularity. Unlike bonds, distal is more strenuous requires distinctly specialized techniques. review, we compiled various methods adopted functionalize mechanistic insights within each these procedures, scope methodology. With give complete overview expeditious progress made field organic chemistry while also highlighting its pitfalls, thus leaving open for further modifications.

Язык: Английский

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Transition Metal‐Catalyzed Enantioselective C−H Functionalization via Chiral Transient Directing Group Strategies

Angewandte Chemie International Edition, Год журнала: 2020, Номер 59(45), С. 19773 - 19786

Опубликована: Июль 20, 2020

Abstract Transition metal‐catalyzed enantioselective functionalization of C−H bond, the most abundant functionality in organic molecules, has emerged as an expedient synthetic approach to streamline synthesis complex chiral molecules. Despite significant progress, traditional directing group‐enabled strategies require additional steps for installation and removal groups from target molecule. The recently developed asymmetric using transient ( c TDGs) offers a promising alternative that can circumvent this obstacle therefore simplify process. In Minireview, we briefly discuss advent recent advances emerging concept, with emphasis on discussing creation various stereogenic centers developments TDGs. Applications natural product ligand derivatizations are also discussed. We hope Minireview will highlight great potential strategy help inspire further endeavors.

Язык: Английский

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Recent Advances in Catalytic C(sp²)–H Allylation Reactions

ACS Catalysis, Год журнала: 2017, Номер 7(4), С. 2821 - 2847

Опубликована: Март 14, 2017

The linear or branched allyl moieties on aromatic rings are well-known as ubiquitous structural motifs found in a range of natural products and medicinally relevant molecules. They also represent an important class organic intermediates for the transformation olefin group into many useful functional groups. Established methods installation allylic groups rely primarily nucleophilic substitution transmetalation aryl metal complexes to electrophiles, Lewis acid-mediated Friedel–Crafts allylation electron-rich arenes, Tsuji–Trost reactions with π-allyl species. Complementing previous protocols, transition metal-catalyzed via C–H activation strategy using various surrogates like acetates, carbonates, phosphonates, halides, alcohols, vinyl oxiranes, allenes, 1,3-dienes, others have recently emerged powerful tool creating corresponding allyl, crotyl prenyl moieties. This review, which includes all reported literature until beginning 2017, focuses recent progress direct vinylic C(sp2)–H bonds sources catalysts.

Язык: Английский

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Increasing Catalyst Efficiency in C−H Activation Catalysis

Angewandte Chemie International Edition, Год журнала: 2017, Номер 57(9), С. 2296 - 2306

Опубликована: Дек. 5, 2017

Abstract C−H activation reactions with high catalyst turnover numbers are still very rare in the literature and 10 mol % is a common loading this field. We offer representative overview of efficient catalysis to highlight neglected aspect development inspire future effort towards more activation. Examples ranging from palladium catalysis, Cp*Rh III ‐ Cp*Co ‐catalysis, borylation silylation methane presented. In these reactions, up tens thousands turnovers have been observed.

Язык: Английский

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Sulfoxonium Ylides as a Carbene Precursor in Rh(III)-Catalyzed C–H Acylmethylation of Arenes

Organic Letters, Год журнала: 2017, Номер 19(19), С. 5256 - 5259

Опубликована: Сен. 13, 2017

Sulfoxonium ylides act as an efficient carbene precursor in rhodium(III)-catalyzed C-H acylmethlyation of a variety arenes assisted by different chelating groups, and both aryl- alkyl-substituted β-carbonyl sulfoxonium are applicable. The system proceeded under redox-neutral conditions with broad scope, high efficiency, functional group tolerance.

Язык: Английский

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Recent advances in the sulfonylation of C–H bonds with the insertion of sulfur dioxide

Chemical Communications, Год журнала: 2018, Номер 54(89), С. 12561 - 12569

Опубликована: Янв. 1, 2018

Recent advances in the sulfonylation of C-H bonds with insertion sulfur dioxide are summarized. Usually, a surrogate, DABCO·(SO2)2, is used, which avoids utilization gaseous transformation. Inorganic sulfites such as sodium metabisulfite also effective C(sp3)-H bond sulfonylation. under transition metal catalysis or through radical process has been developed. In some cases, can be performed catalyst- and additive-free conditions, facilitated by visible light irradiation. The efficiency investigated merging catalysis.

Язык: Английский

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3d metallaelectrocatalysis for resource economical syntheses

Chemical Society Reviews, Год журнала: 2020, Номер 49(13), С. 4254 - 4272

Опубликована: Янв. 1, 2020

This review summarizes key developments in 3d metallaelectrocatalysis the context of resource economy molecular syntheses.

Язык: Английский

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C–H deuteration of organic compounds and potential drug candidates

Chemical Society Reviews, Год журнала: 2022, Номер 51(8), С. 3123 - 3163

Опубликована: Янв. 1, 2022

This review summarises deuteration methods of various organic motifs containing C(sp 2 )−H and 3 bonds utilizing C−H bond functionalisation as a key step along with variety catalysts, exemplifies their biological relevance.

Язык: Английский

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Weak-Coordination in C–H Bond Functionalizations Catalyzed by 3d Metals

ACS Catalysis, Год журнала: 2022, Номер 12(6), С. 3452 - 3506

Опубликована: Март 3, 2022

Transition-metal-catalyzed C–H bond functionalizations have had an enormous influence on organic synthesis in recent times. However, the use of low-abundance 4d and 5d metals is almost inevitable, they are high demand. This will be a cause concern, hence, it important to develop methods based 3d metals, which widely present Earth's crust. In this regard, metal catalysts or their precursors for catalysis, general, functionalizations, particular, has gained significant momentum The major development catalytic with been achieved predominantly strongly coordinating directing groups such as pyridyl, pyrimidinyl, pyrazolyl, 8-amino-quinolinyl groups. Thus, prefunctionalization substrates these necessary, contradicts step- atom-economy activation. commonly available functional aldehyde, ketone, carboxylic acid, amide, hydroxy, N-oxides loosely bind through weak-coordination. These weakly orient activate regioselectively without need preinstalled Although challenging, contemporary topic actively pursued by many researchers Through article, we provide comprehensive overview metal-catalyzed, coordinating, directing-group-enabled reported until March 2021.

Язык: Английский

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