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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A comprehensive overview of directing groups applied in metal-catalysed C–H functionalisation chemistry

Chemical Society Reviews, Год журнала: 2018, Номер 47(17), С. 6603 - 6743

Опубликована: Янв. 1, 2018

The present review is devoted to summarizing the recent advances (2015-2017) in field of metal-catalysed group-directed C-H functionalisation. In order clearly showcase molecular diversity that can now be accessed by means directed functionalisation, whole organized following directing groups installed on a substrate. Its aim comprehensive reference work, where specific group easily found, together with transformations which have been carried out it. Hence, primary format this schemes accompanied concise explanatory text, are ordered sections according their chemical structure. feature typical substrates used, products obtained as well required reaction conditions. Importantly, each example commented respect most important positive features and drawbacks, aspects such selectivity, substrate scope, conditions, removal, greenness. targeted readership both experts functionalisation chemistry (to provide overview progress made last years) and, even more so, all organic chemists who want introduce way thinking for design straightforward, efficient step-economic synthetic routes towards molecules interest them. Accordingly, should particular also scientists from industrial R&D sector. overall goal promote application reactions outside research dedicated method development establishing it valuable archetype contemporary R&D, comparable role cross-coupling play date.

Язык: Английский

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Catalytic Transformations of Functionalized Cyclic Organic Carbonates

Angewandte Chemie International Edition, Год журнала: 2018, Номер 57(42), С. 13735 - 13747

Опубликована: Июнь 6, 2018

Functionalized cyclic organic carbonates and related heterocycles have emerged as highly versatile heterocyclic substrates for ring-opening decarboxylative catalytic transformations allowing the development of new stereo- enantioselective C-N, C-O, C-C, C-S C-B bond formation reactions. Transition-metal-mediated conversions only recently been rejuvenated powerful approaches towards preparation more complex molecules. This minireview will highlight potential structurally with a focus on their synthetic value mechanistic manifolds that are involved upon conversion.

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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Thioamide‐Directed Cobalt(III)‐Catalyzed Selective Amidation of C(sp³)−H Bonds

Angewandte Chemie International Edition, Год журнала: 2017, Номер 56(52), С. 16550 - 16554

Опубликована: Окт. 28, 2017

A mild, oxidant-free, and selective Cp*CoIII -catalyzed amidation of thioamides with robust dioxazolone amidating agents via C(sp3 )-H bond activation to generate the desired amidated products is reported. The method efficient allows for C-H a wide range functionalized aryl-, heteroaryl-, alkyl-substituted dioxazolones under conditions. observed regioselectivity towards primary supported by computational studies cyclometalation proposed proceed means an external carboxylate-assisted concerted metalation/deprotonation mechanism. reported rare example use directing group other than commonly used pyridine quinolone classes functionalization first exploit thioamides.

Язык: Английский

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Rhodium(III)-Catalyzed Synthesis of Naphthols via C–H Activation of Sulfoxonium Ylides

Organic Letters, Год журнала: 2017, Номер 19(16), С. 4307 - 4310

Опубликована: Авг. 7, 2017

Direct and efficient synthesis of 1-naphthols has been realized via Rh(III)-catalyzed C-H activation sulfoxonium ylides subsequent annulation with alkynes, where the ylide functioned as a new traceless bifunctional directing group. This reaction occurred under redox-neutral conditions broad substrate scope.

Язык: Английский

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Recent advances using [Cp*Co(CO)I₂] catalysts as a powerful tool for C–H functionalisation

Dalton Transactions, Год журнала: 2017, Номер 46(30), С. 9721 - 9739

Опубликована: Янв. 1, 2017

This perspective highlights recent applications of Cp*Co^III catalysts in C–H functionalisation protocols, exemplifying both terminal couplings and heterocycle formation.

Язык: Английский

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Recent Progress on Cyclic Nitrenoid Precursors in Transition‐Metal‐Catalyzed Nitrene‐Transfer Reactions

Chemistry - A European Journal, Год журнала: 2018, Номер 25(13), С. 3156 - 3180

Опубликована: Сен. 5, 2018

Abstract Nitrene‐transfer reactions are powerful synthetic tools for the direct incorporation of nitrogen atoms into organic molecules. The discovery novel nitrene‐transfer has been dominantly supported not only by improvements in transition‐metal catalysts but also employment precursors nitrenoids. Since pioneering work involving use azides and iminoiodinanes as practical nitrogen‐containing compounds was reported, a new approach using various N‐heterocycles containing strain energy or weak bond emerged. In this review, we briefly summarize history chemistry from viewpoint its precursors. particular, such 2 H ‐azirines, 1,4,2‐dioxazol‐5‐ones, 1,2,4‐oxadiazol‐5‐ones, isoxazol‐5(4 )‐ones, isoxazoles is comprehensively described, showing recent remarkable progress chemistry.

Язык: Английский

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Non-C₂-Symmetric Chiral-at-Ruthenium Catalyst for Highly Efficient Enantioselective Intramolecular C(sp³)–H Amidation

Journal of the American Chemical Society, Год журнала: 2019, Номер 141(48), С. 19048 - 19057

Опубликована: Ноя. 21, 2019

A new class of chiral ruthenium catalysts is introduced in which cyclometalated by two 7-methyl-1,7-phenanthrolinium heterocycles, resulting chelating pyridylidene remote N-heterocyclic carbene ligands (rNHCs). The overall chirality results from a stereogenic metal center featuring either Λ or Δ absolute configuration. This work features the importance relative metal-centered stereochemistry. Only non-C2-symmetric chiral-at-ruthenium complexes display unprecedented catalytic activity for intramolecular C(sp3)–H amidation 1,4,2-dioxazol-5-ones to provide γ-lactams with up 99:1 er and catalyst loadings down 0.005 mol % (up 11 200 TON), while C2-symmetric diastereomer favors an undesired Curtius-type rearrangement. DFT calculations elucidate origins superior C–H reactivity displayed compared related counterparts.

Язык: Английский

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“Alkene-to-Alkene” Difunctionalization of Enaminones for the Synthesis of Polyfunctionalized Alkenes by Transition-Metal-Free C–H and C–N Bond Transformation

Organic Letters, Год журнала: 2023, Номер 25(47), С. 8451 - 8456

Опубликована: Ноя. 16, 2023

The three-component reactions of enaminones, disulfides, and alcohols for the synthesis polyfunctionalized alkenes have been realized via C-H C-N bond transformation on enaminones. proceed in a novel "alkene-to-alkene" difunctionalization mode without using any transition metal. application alkene products divergent sulfenyl heteroaryls, including sulfenylated pyrazoles, pyrimidines, isoxazoles, simple annulation has also verified.

Язык: Английский

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