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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Exploration of Chemical Compound, Conformer, and Reaction Space with Meta-Dynamics Simulations Based on Tight-Binding Quantum Chemical Calculations

Journal of Chemical Theory and Computation, Год журнала: 2019, Номер 15(5), С. 2847 - 2862

Опубликована: Апрель 3, 2019

The semiempirical tight-binding based quantum chemistry method GFN2-xTB is used in the framework of meta-dynamics (MTD) to globally explore chemical compound, conformer, and reaction space. biasing potential given as a sum Gaussian functions expressed with root-mean-square-deviation (RMSD) Cartesian space metric for collective variables. This choice makes approach robust generally applicable three common problems (i.e., conformer search, exploration virtual nanoreactor, guessing paths). Because inherent locality atomic RMSD, functional group or fragment selective treatments are possible facilitating investigation catalytic processes where, example, only substrate thermally activated. Due approximate character method, resulting structure ensembles require further refinement more sophisticated, density wave function theory methods. However, extremely efficient running routinely on laptop computers minutes hours computation time even realistically sized molecules few hundred atoms. Furthermore, underlying energy surface containing almost all elements ( Z = 1-86) consistent including covalent dissociation process electronically complicated situations in, transition metal systems. As examples, thermal decomposition, ethyne oligomerization, oxidation hydrocarbons (by oxygen P450 enzyme model), Miller-Urey model system, forbidden dimerization, multistep intramolecular cyclization shown. For typical conformational search organic drug molecules, new MTD(RMSD) algorithm yields lower structures complete at reduced computational effort compared its already well performing predecessor.

Язык: Английский

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Transition‐Metal‐Mediated and ‐Catalyzed C−F Bond Activation by Fluorine Elimination

Angewandte Chemie International Edition, Год журнала: 2018, Номер 58(2), С. 390 - 402

Опубликована: Июнь 28, 2018

Abstract The activation of carbon–fluorine (C−F) bonds is an important topic in synthetic organic chemistry. Metal‐mediated and ‐catalyzed elimination β‐ or α‐fluorine proceeds under milder conditions than oxidative addition to C−F bonds. initiated from organometallic intermediates having fluorine substituents on carbon atoms β α metal centers, respectively. Transformations through these processes (C−F bond cleavage), which are typically preceded by carbon–carbon (or carbon–heteroatom) formation, have been increasingly developed the past five years as methods. In this Minireview, we summarize applications transition‐metal‐mediated chemistry a historical perspective with early studies systematic recent studies.

Язык: Английский

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Enantioselective Cobalt(III)‐Catalyzed C−H Activation Enabled by Chiral Carboxylic Acid Cooperation

Angewandte Chemie International Edition, Год журнала: 2018, Номер 57(47), С. 15425 - 15429

Опубликована: Окт. 6, 2018

The enantioselective cobalt(III)-catalyzed C-H alkylation was achieved through the design of a novel chiral acid. activation characterized by high position-, regio- and enantio-control under exceedingly mild reaction conditions. Thereby, robust cooperative cobalt(III) catalysis proved tolerant valuable electrophilic functional groups, including hydroxyl, bromo, iodo substituents. Mechanistic studies revealed considerable additive effect on kinetics negative non-linear-effect.

Язык: Английский

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Recent Advances in Alkenyl sp² C–H and C–F Bond Functionalizations: Scope, Mechanism, and Applications

Chemical Reviews, Год журнала: 2022, Номер 122(24), С. 17479 - 17646

Опубликована: Окт. 14, 2022

Alkenes and their derivatives are featured widely in a variety of natural products, pharmaceuticals, advanced materials. Significant efforts have been made toward the development new practical methods to access this important class compounds by selectively activating alkenyl C(sp2)–H bonds recent years. In comprehensive review, we describe state-of-the-art strategies for direct functionalization sp2 C–H C–F until June 2022. Moreover, metal-free, photoredox, electrochemical also covered. For clarity, review has divided into two parts; first part focuses on currently available using different alkene as starting materials, second describes bond easily accessible gem-difluoroalkenes material. This includes scope, limitations, mechanistic studies, stereoselective control (using directing groups well metal-migration strategies), applications complex molecule synthesis where appropriate. Overall, aims document considerable advancements, current status, emerging work critically summarizing contributions researchers working fascinating area is expected stimulate novel, innovative, broadly applicable functionalizations coming

Язык: Английский

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Metal-catalysed C–Het (F, O, S, N) and C–C bond arylation

Chemical Society Reviews, Год журнала: 2021, Номер 50(16), С. 8903 - 8953

Опубликована: Янв. 1, 2021

The formation of C–aryl bonds has been the focus intensive research over last decades for construction complex molecules from simple, readily available feedstocks.

Язык: Английский

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Heteromultimetallic catalysis for sustainable organic syntheses

Chemical Society Reviews, Год журнала: 2017, Номер 46(23), С. 7399 - 7420

Опубликована: Янв. 1, 2017

Fully complementary bimetallic catalysis has been identified as an increasingly powerful tool for molecular transformations, which was largely inspired by early examples of sequential catalytic transformations.

Язык: Английский

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Transition-metal-catalyzed C–H allylation reactions

Chem, Год журнала: 2020, Номер 7(3), С. 555 - 605

Опубликована: Ноя. 13, 2020

Язык: Английский

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Recent advances in three-component difunctionalization ofgem-difluoroalkenes

Chemical Communications, Год журнала: 2020, Номер 56(72), С. 10442 - 10452

Опубликована: Янв. 1, 2020

Three-component difunctionalization ofgem-difluoroalkenesviathe generation and transformation of a α-fluoroalkylated carbanion, carbon–metal species, radical, carbocation intermediate.

Язык: Английский

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