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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Methodologies and Strategies for Selective Borylation of C–Het and C–C Bonds

Chemical Reviews, Год журнала: 2020, Номер 120(15), С. 7348 - 7398

Опубликована: Июнь 29, 2020

Organoborons have emerged as versatile building blocks in organic synthesis to achieve molecular diversity and carboxylic acid bioisosteres with broad applicability drug discovery. Traditionally, these compounds are prepared by the substitution of Grignard/lithium reagents electrophilic boron species Brown hydroboration. Recent developments provided new routes for efficient preparation organoborons applying reactions using chemical feedstocks leaving groups. As compared previous methods that used halides (I, Br, Cl), direct borylation less reactive C–Het C–C bonds has become highly important get efficiency functional-group compatibility. This Review aims provide a comprehensive overview this topic, including (1) C–F bond borylation, (2) C–O (3) C–S (4) C–N (5) borylation. Considerable attention is given strategies mechanisms involved. We expect will inspire chemists discover more transformations expand field.

Язык: Английский

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First-Row d-Block Element-Catalyzed Carbon–Boron Bond Formation and Related Processes

Chemical Reviews, Год журнала: 2021, Номер 121(21), С. 13238 - 13341

Опубликована: Окт. 7, 2021

Organoboron reagents represent a unique class of compounds because their utility in modern synthetic organic chemistry, often affording unprecedented reactivity. The transformation the carbon–boron bond into carbon–X (X = C, N, and O) stereocontrolled fashion has become invaluable medicinal agrochemistry, natural products chemistry as well materials science. Over past decade, first-row d-block transition metals have increasingly widely used catalysts for formation bond, traditionally catalyzed by expensive precious metals. This recent focus on alternative enabled growth fundamental methods organoboron chemistry. review surveys current state-of-the-art use element-based bonds.

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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A Copper(I)‐Catalyzed Enantioselective γ‐Boryl Substitution of Trifluoromethyl‐Substituted Alkenes: Synthesis of Enantioenriched γ,γ‐gem‐Difluoroallylboronates

Angewandte Chemie International Edition, Год журнала: 2018, Номер 57(24), С. 7196 - 7199

Опубликована: Апрель 27, 2018

Abstract The first catalytic enantioselective γ‐boryl substitution of CF 3 ‐substituted alkenes is reported. A series was treated with a diboron reagent in the presence copper(I)/Josiphos catalyst to afford corresponding optically active γ,γ‐ gem ‐difluoroallylboronates high enantioselectivity. thus obtained products could be readily converted into difluoromethylene‐containing homoallylic alcohols using highly stereospecific allylation reactions.

Язык: Английский

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Nickel-Catalyzed Enantioselective Reductive Aryl Fluoroalkenylation of Alkenes

ACS Catalysis, Год журнала: 2019, Номер 9(10), С. 9127 - 9133

Опубликована: Сен. 4, 2019

Enantioselective Ni-catalyzed reductive aryl monofluoroalkenylation of alkenes between bromides and gem-difluoroalkenes has been developed. The reaction proceeding under room temperature base-free conditions tolerates a wide range functional groups on both coupling partners. Various synthetically useful oxindoles containing monofluoroalkenyl substituent are obtained in good yields with 85%–95% enantiomeric excess. In addition, the synthetic method can be further applied to late-stage complex biologically active compounds.

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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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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Copper-Catalyzed Carboxylation of C–F Bonds with CO₂

ACS Catalysis, Год журнала: 2019, Номер 9(8), С. 6987 - 6992

Опубликована: Июль 5, 2019

An effective Cu-catalyzed selective formal carboxylation of C–F bonds with an atmospheric pressure CO2 is reported. A variety gem-difluoroalkenes, gem-difluorodienes, and α-trifluoro-methyl alkenes show high reactivity selectivity for this ipso monocarboxylation. Under mild conditions, diverse important α-fluoroacrylic acids α,α-difluorocarboxylates are obtained in good-to-high yields. Moreover, operationally simple protocol features good functional group tolerance, readily scalable, the resulting products converted into bioactive α-fluorinated carbonyl compounds, indicating potential application biochemistry drug discovery. Mechanistic studies reveal that fluorinated boronate esters might be vital intermediates transformation.

Язык: Английский

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Activation of the Si–B interelement bond related to catalysis

Chemical Society Reviews, Год журнала: 2020, Номер 50(3), С. 2010 - 2073

Опубликована: Дек. 16, 2020

Covering the past seven years, this review comprehensively summarises latest progress in preparation and application of Si–B reagents, including discussion relevant reaction mechanisms.

Язык: Английский

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