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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Catalytic Enantioselective Transformations Involving C–H Bond Cleavage by Transition-Metal Complexes

Chemical Reviews, Journal Year: 2017, Volume and Issue: 117(13), P. 8908 - 8976

Published: Feb. 17, 2017

The development of new methods for the direct functionalization unactivated C-H bonds is ushering in a paradigm shift field retrosynthetic analysis. In particular, catalytic enantioselective represents highly atom- and step-economic approach toward generation structural complexity. However, as result their ubiquity low reactivity, controlling both chemo- stereoselectivity such processes constitutes significant challenge. Herein we comprehensively review all asymmetric transition-metal-catalyzed methodologies that are believed to proceed via an inner-sphere-type mechanism, with emphasis on nature stereochemistry generation. Our analysis serves document considerable rapid progress within field, while also highlighting limitations current methods.

Language: Английский

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Access to P‐ and Axially Chiral Biaryl Phosphine Oxides by Enantioselective Cp^xIr^III‐Catalyzed C−H Arylations

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 57(39), P. 12901 - 12905

Published: July 25, 2018

An enantioselective C-H arylation of phosphine oxides with o-quinone diazides catalyzed by an iridium(III) complex bearing atropchiral cyclopentadienyl (Cpx ) ligand and phthaloyl tert-leucine as co-catalyst is reported. The method allows access to a) P-chiral biaryl oxides, b) atropo-enantioselective construction sterically demanding backbones, also c) selective assembly axial compounds in excellent yields diastereo- enantioselectivities. Enantiospecific reductions provide monodentate chiral phosphorus(III) having structures backbones proven importance ligands asymmetric catalysis.

Language: Английский

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General Enantioselective C−H Activation with Efficiently Tunable Cyclopentadienyl Ligands

Angewandte Chemie International Edition, Journal Year: 2017, Volume and Issue: 56(9), P. 2429 - 2434

Published: Jan. 26, 2017

Abstract Cyclopentadienyl (Cp) ligands enable efficient steering of various transition‐metal‐catalyzed transformations, in particular enantioselective C−H activation. Currently only few chiral Cp are available. Therefore, a conceptually general approach to ligand discovery would be invaluable as it the applicable and efficiently rapidly vary tune their structures. Herein, we describe three‐step gram‐scale synthesis structurally diverse widely collection (JasCp ligands) with highly variable adjustable Their modular nature amenability rapid structure variation enabled for three Rh III ‐catalyzed activation reactions, including one unprecedented transformation. This novel should further transformations.

Language: Английский

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Enantioselective C(sp³)–H Amidation of Thioamides Catalyzed by a Cobalt^III/Chiral Carboxylic Acid Hybrid System

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 58(4), P. 1153 - 1157

Published: Nov. 27, 2018

Abstract Recent advances in Cp x M III catalysis (M=Co, Rh, Ir) have enabled a variety of enantioselective C(sp 2 )−H functionalization reactions, but 3 is still largely unexplored. We describe an asymmetric amidation thioamides using achiral Co /chiral carboxylic acid hybrid catalytic system, which provides easy and straightforward access to chiral β‐amino thiocarbonyl carbonyl building blocks with quaternary carbon stereocenter.

Language: Английский

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Enantioselective remote meta-C–H arylation and alkylation via a chiral transient mediator

Nature, Journal Year: 2018, Volume and Issue: 558(7711), P. 581 - 585

Published: June 1, 2018

Language: Английский

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Enantioselective remote C–H activation directed by a chiral cation

Science, Journal Year: 2020, Volume and Issue: 367(6483), P. 1246 - 1251

Published: March 12, 2020

Chiral cations have been used extensively as organocatalysts, but their application to rendering transition metal-catalyzed processes enantioselective remains rare. This is despite the success of analogous charge-inverted strategy in which cationic metal complexes are paired with chiral anions. We report here a render common bipyridine ligand anionic and pair its iridium cation derived from quinine. applied these ion-paired long-range asymmetric induction desymmetrization geminal diaryl motif, located on carbon or phosphorus center, by C-H borylation. In principle, numerous classes could likewise be amenable this approach.

Language: Английский

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Chiral Cyclopentadienyl Ligands: Design, Syntheses, and Applications in Asymmetric Catalysis

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 60(24), P. 13198 - 13224

Published: July 16, 2020

The creation of new chiral ligands capable providing high stereocontrol in metal-catalyzed reactions is crucial modern organic synthesis. production bioactive molecules as single enantiomers increasingly required, and asymmetric catalysis with metal complexes constitutes one the most efficient synthetic strategies to access optically active compounds. Herein we offer a historical overview on development derivatives ubiquitous cyclopentadienyl ligand (CpX ), detail their successful application broad range transformations. Those include functionalization challenging C-H bonds beyond, giving an extensive catalogue valuable molecules. A critical comparison existing families, design, synthesis, complexation different metals also provided. In addition, future research directions are discussed further enhance performance CpX enantioselective catalysis.

Language: Английский

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Diverse Approaches for Enantioselective C−H Functionalization Reactions Using Group 9 Cp^xM^III Catalysts

Chemistry - A European Journal, Journal Year: 2020, Volume and Issue: 26(33), P. 7346 - 7357

Published: Jan. 29, 2020

Transition-metal-catalyzed C-H functionalization reactions with Cp*MIII catalysts (M=Co, Rh, Ir) have found a wide variety of applications in organic synthesis. Albeit the intrinsic difficulties achieving catalytic stereocontrol using these due to their lack additional coordination sites for external chiral ligands and conformational flexibility Cp ligand, enantioselective Group 9 metal triad Cp-type been intensively studied since 2012. In this minireview, progress according type catalyst used are summarized discussed. The development Cpx complexes thereof, artificial metalloenzymes, carboxylate-assisted activations, alkylations assisted by carboxylic acids or sulfonates, transient directing groups

Language: Английский

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New Approaches for Biaryl-Based Phosphine Ligand Synthesis via P═O Directed C–H Functionalizations

Accounts of Chemical Research, Journal Year: 2017, Volume and Issue: 50(6), P. 1480 - 1492

Published: May 9, 2017

Given the important influence of phosphine ligands in transition metal-catalyzed reactions, chemists have searched for straightforward and efficient methodologies synthesis diverse ligands. Although significant progress has been made this aspect over past decades, development new phosphorus-containing with properties superior to their predecessors remains a central task chemists. Recently, researchers demonstrated that biphenyl monophosphine function as highly transition-metal-catalyzed organic transformations, especially reactions where chelating bisphosphine cannot be used. In 1998, Buchwald introduced class air-stable based on dialkylbiaryl backbone. These successfully used wide variety palladium-catalyzed carbon-carbon, carbon-nitrogen, carbon-oxygen construction processes well serving supporting number other reactions. At same time, use often allows proceed short reaction times low catalyst loadings under mild conditions. However, chiral ligands, those chirality which is due biaryl axial chirality, very limited. Account, we summarize our kind including P═O directed C-H functionalization, diastereoselective enantioselective metal-free radical oxidative amination With these methods, series ligand precursors containing achiral or axially centers possessing both chirogenic phosphorus center different electronic steric effect obtained For preparation not only possess but many cases also at phosphorus, primary means introducing through menthyl phenylphosphinate. As auxiliary group, phenylphosphinate some unique features: (i) it easy prepare; (ii) products contain atom; (iii) group could easily transformed into functional groups, crucial diversity corresponding reaction, acts directing facilitates addition, application asymmetric catalysis studied good results The further underway laboratory, hope kinds will achieved

Language: Английский

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