3d Transition Metals for C–H Activation

Chemical Reviews, Journal Year: 2018, Volume and Issue: 119(4), P. 2192 - 2452

Published: Nov. 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.

Language: Английский

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

Chemical Society Reviews, Journal Year: 2018, Volume and Issue: 47(17), P. 6603 - 6743

Published: Jan. 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.

Language: Английский

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Residue-Specific Peptide Modification: A Chemist’s Guide

Biochemistry, Journal Year: 2017, Volume and Issue: 56(30), P. 3863 - 3873

Published: June 27, 2017

Advances in bioconjugation and native protein modification are appearing at a blistering pace, making it increasingly time consuming for practitioners to identify the best chemical method modifying specific amino acid residue complex setting. The purpose of this perspective is provide an informative, graphically rich manual highlighting significant advances field over past decade. This guide will help triage candidate methods peptide alteration serve as starting point those seeking solve long-standing challenges.

Language: Английский

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C–H activation

Nature Reviews Methods Primers, Journal Year: 2021, Volume and Issue: 1(1)

Published: June 17, 2021

Language: Английский

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Late‐Stage Peptide Diversification by Position‐Selective C−H Activation

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 57(45), P. 14700 - 14717

Published: July 3, 2018

The late-stage modification of structurally complex peptides bears great potential for drug discovery, crop protection, and the pharmaceutical industry, among others. Whereas traditional approaches largely rely on prefunctionalizations, C-H activation catalysis has in recent years emerged as an increasingly powerful tool post-translational peptide modifications a step-economic manner. Herein, we summarize progress organometallic until June 2018, including position- chemoselective palladium-, ruthenium-, manganese-catalyzed processes.

Language: Английский

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Inert C–H Bond Transformations Enabled by Organometallic Manganese Catalysis

Accounts of Chemical Research, Journal Year: 2018, Volume and Issue: 51(3), P. 816 - 827

Published: Feb. 14, 2018

ConspectusTraditional organic synthesis relies heavily on the transformations of various preinstalled functional groups, such as cross-coupling reactions using organohalides and organometallic reagents. The strategy C–H activation enables direct formation C–C/C–X (X = heteroatom) bonds from inert bonds, which can enhance atom- step-economy synthesis. To date, precious metals have overwhelmingly dominated field; however, rarity high cost these necessitate development more sustainable catalysts. In this regard, catalysts based manganese are highly desirable owing to abundant reserve in earth's crust its economic benefits, low toxicity, potentially unique reactivity. Although first stoichiometric manganese-mediated reaction was reported early 1970, manganese-catalyzed largely underdeveloped. How construct an efficient catalytic cycle for remains a key issue be addressed.In Account, we summarize our recent advances bonds. overcome challenges associated with building manganese-based cycles, developed two novel strategies, namely, synergy between bases (with or w/o bases) acids. By implementing former strategy, cooperative manganese/base systems that facilitate new mode bond by via redox-neutral base-assisted deprotonation mechanism. As such, requirement tedious preparation MnR(CO)5 complexes (R Me, Bn, Ph) eliminated, series arenes partners having C≡C C═C were achieved. Through latter acids, disclosed "dual activation" performing transformations, is, merging C–X multiple Lewis Consequently, scope substrates could expanded include challenging ketones olefinic compounds. Additionally, range significantly broadened those bearing polarized C═O, C═N, C≡N aldehydes, imines, nitriles. Remarkably, innate reactivity different reversed catalysis, even carried out at room temperature. Our findings provide guiding information future beyond. Related important contributions other groups mentioned, remaining perspective emerging area also presented.

Language: Английский

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Transition-Metal-Catalyzed C–H Bond Activation for the Formation of C–C Bonds in Complex Molecules

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(12), P. 7692 - 7760

Published: May 10, 2023

Site-predictable and chemoselective C–H bond functionalization reactions offer synthetically powerful strategies for the step-economic diversification of both feedstock fine chemicals. Many transition-metal-catalyzed methods have emerged selective activation bonds. However, challenges regio- chemoselectivity with application to highly complex molecules bearing significant functional group density diversity. As molecular complexity increases within structures risks catalyst intolerance limited applicability grow number groups potentially Lewis basic heteroatoms. Given abundance bonds already diversified such as pharmaceuticals, natural products, materials, design selection reaction conditions tolerant catalysts has proved critical successful direct functionalization. such, innovations formation carbon–carbon been discovered developed overcome these limitations. This review highlights progress made metal-catalyzed C–C forming including alkylation, methylation, arylation, olefination targets.

Language: Английский

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C–F/C–H Functionalization by Manganese(I) Catalysis: Expedient (Per)Fluoro-Allylations and Alkenylations

ACS Catalysis, Journal Year: 2017, Volume and Issue: 7(6), P. 4209 - 4213

Published: May 11, 2017

C–F/C–H functionalizations proved to be viable within a versatile manganese(I) catalysis manifold. Thus, wealth of fluorinated alkenes were employed in through facile C–H activation. The robust nature the regime was among others reflected by first activation with perfluoroalkenes as well racemization-free on imines, amino acids, and peptides.

Language: Английский

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Photocatalytic Modification of Amino Acids, Peptides, and Proteins

Chemistry - A European Journal, Journal Year: 2018, Volume and Issue: 25(1), P. 26 - 42

Published: July 31, 2018

Abstract In the last decade, visible‐light photoredox catalysis has emerged as a powerful strategy to enable novel transformations in organic synthesis. Owing mild reaction conditions (i.e., room temperature, use of visible light) and high functional‐group tolerance, could represent an ideal for chemoselective biomolecule modification. Indeed, recent trend is its application development methodologies amino acid Herein, up‐to‐date overview photocatalytic modification single acids, peptides, proteins provided. The advantages offered by suitability biocompatible are described. addition, brief consideration current limitations approaches, well future challenges be addressed, discussed.

Language: Английский

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Redox‐Neutral Manganese(I)‐Catalyzed C−H Activation: Traceless Directing Group Enabled Regioselective Annulation

Angewandte Chemie International Edition, Journal Year: 2017, Volume and Issue: 56(41), P. 12778 - 12782

Published: Aug. 15, 2017

Abstract A strategy is reported in which traceless directing groups (TDGs) are used to promote the redox‐neutral Mn I ‐catalyzed regioselective synthesis of N‐heterocycles. Alkyne coupling partners bearing a group, serves as both chelator and internal oxidant, were control regioselectivity annulation reactions. This operationally simple approach highly effective with previously challenging unsymmetrical alkyne systems, including unbiased dialkyl alkynes, perfect regioselectivity. The conditions ability carry out on gram scale underscore usefulness this method. application concise bioactive compound PK11209 pharmaceutical moxaverine also described.

Language: Английский

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