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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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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Transition-Metal-Catalyzed, Coordination-Assisted Functionalization of Nonactivated C(sp³)–H Bonds

Chemical Reviews, Год журнала: 2021, Номер 121(24), С. 14957 - 15074

Опубликована: Окт. 29, 2021

Transition-metal-catalyzed, coordination-assisted C(sp3)–H functionalization has revolutionized synthetic planning over the past few decades as use of these directing groups allowed for increased access to many strategic positions in organic molecules. Nonetheless, several challenges remain preeminent, such requirement high temperatures, difficulty removing or converting groups, and, although metals provide some reactivity, employing outside palladium. This review aims give a comprehensive overview coordination-assisted, transition-metal-catalyzed, direct nonactivated bonds by covering literature since 2004 order demonstrate current state-of-the-art methods well limitations. For clarity, this been divided into nine sections transition metal catalyst with subdivisions type bond formation. Synthetic applications and reaction mechanism are discussed where appropriate.

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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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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Synthesis of Monofluoroalkenes: A Leap Forward

Synthesis, Год журнала: 2018, Номер 50(05), С. 881 - 955

Опубликована: Янв. 11, 2018

Monofluoroalkenes have found wide application in organic chemistry, medicinal and materials science. This review summarizes the most recent advances made regarding preparation of monofluoroalkenes, covering period between October 2010 September 2017. is divided three main parts, one for each possible substitution pattern, namely di-, tri-, tetrasubstituted. Then, class, further subclassification according to reaction type. 1 Introduction 2 Disubstituted 2.1 α-Monofluoroalkenes 2.2 β-Monofluoroalkenes 3 Trisubstituted 4 Tetrasubstituted 5 Conclusions

Язык: Английский

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Recent Advances in Transition Metal‐Catalyzed Functionalization of gem‐Difluoroalkenes

Israel Journal of Chemistry, Год журнала: 2020, Номер 60(3-4), С. 313 - 339

Опубликована: Март 1, 2020

gem-Difluorinated alkenes are readily accessible building blocks that can undergo functionalization to provide a broad spectrum of fluorinated and non-fluorinated products. Herein, we review recent (since 2017) transition metal-catalyzed transformations these specialized summarize general reactivity patterns reactions. Many reactions net C-F bond deliver monofluorinated These typically proceed through β-fluoro alkylmetal intermediates eliminate β-fluoride monofluoroalkene A second series exploit coinage metal fluorides add F- the gem-difluorinated alkene, further delivers trifluoromethyl-containing In stark contrast, few in "fluorine-retentive processes" difluoromethylene-based

Язык: Английский

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Synthesis of Alkylated Monofluoroalkenes via Fe-Catalyzed Defluorinative Cross-Coupling of Donor Alkenes with gem-Difluoroalkenes

Organic Letters, Год журнала: 2018, Номер 20(7), С. 1924 - 1927

Опубликована: Март 19, 2018

A reductive cross-coupling of gem-difluoroalkenes with diverse unactivated and heteroatom substituted olefins through a Fe-catalyzed hydrogen atom transfer (HAT) strategy is reported. Different from the previous HAT-type olefin reactions, presence fluorine in molecule results stereoselective β-F cleavage, leading to C(sp2)–C(sp3) bond formation. wide variety alkylated monofluoroalkenes were obtained good efficiency excellent Z selectivity under air- water-tolerant reaction conditions. similar defluorinative coupling was also realized.

Язык: Английский

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Visible Light‐Mediated Trifluoromethylation of Fluorinated Alkenes via C−F Bond Cleavage

Advanced Synthesis & Catalysis, Год журнала: 2018, Номер 360(20), С. 3894 - 3899

Опубликована: Авг. 9, 2018

Abstract A convenient photoredox‐catalyzed defluorinative trifluoromethylation of α ‐trifluoromethyl alkenes and gem ‐difluoroalkenes is developed. The reactions proceeded efficiently via trifluoromethyl radical addition followed by β ‐fluorine elimination process, providing a new entry to multifluorinated in moderate good yields with excellent stereoselectivity. magnified image

Язык: Английский

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Stereoselective Palladium‐Catalyzed C−F Bond Alkynylation of Tetrasubstituted gem‐Difluoroalkenes

Angewandte Chemie International Edition, Год журнала: 2020, Номер 59(28), С. 11293 - 11297

Опубликована: Апрель 18, 2020

A stereoselective Pd(PPh3 )4 -catalyzed C-F bond alkynylation of tetrasubstituted gem-difluoroalkenes with terminal alkynes has been developed. This method gives access to a great variety conjugated monofluoroenynes bearing alkene moiety well-defined stereochemistry. Chelation-assisted oxidative addition Pd the is proposed account for high level stereocontrol. An X-ray crystal structure key monofluorovinyl PdII intermediate obtained first time as evidence mechanism.

Язык: Английский

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