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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Copper-Catalyzed Borylative Difunctionalization of π-Systems

ACS Catalysis, Год журнала: 2020, Номер 10(19), С. 11578 - 11622

Опубликована: Авг. 25, 2020

Organoboronates represent a cornerstone functional group in modern synthesis owing to their unique reactivity and divergent synthetic capability. Copper catalysis has become one of the most powerful methods stereoselectively install boron across diverse π-systems. Additionally, this method affords tremendous versatility enabled by difunctionalization π-system addition an electrophile. This review covers known electrophiles intercept catalytic intermediates borylative strategies that have been reported up end May 2020.

Язык: Английский

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Recent progress on selective deconstructive modes of halodifluoromethyl and trifluoromethyl-containing reagents

Chemical Society Reviews, Год журнала: 2020, Номер 49(24), С. 9197 - 9219

Опубликована: Янв. 1, 2020

Halodifluoromethyl and trifluoromethyl-containing compounds can act various rolesviaselective cleavage modes to access more valuable fluorinated or nonfluorinated molecules.

Язык: Английский

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Nickel-catalyzed allylic defluorinative alkylation of trifluoromethyl alkenes with reductive decarboxylation of redox-active esters

Chemical Science, Год журнала: 2018, Номер 10(3), С. 809 - 814

Опубликована: Ноя. 7, 2018

Synthesis of functionalized gem-difluoroalkenes was achieved through nickel-catalyzed allylic defluorinative alkylation trifluoromethyl alkenes with reductive decarboxylation redox-active esters.

Язык: Английский

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Visible‐Light‐Induced Selective Defluoroborylation of Polyfluoroarenes, gem‐Difluoroalkenes, and Trifluoromethylalkenes

Angewandte Chemie International Edition, Год журнала: 2019, Номер 59(10), С. 4009 - 4016

Опубликована: Дек. 18, 2019

Fluorinated organoboranes serve as versatile synthetic precursors for the preparation of value-added fluorinated organic compounds. Recent progress has been mainly focused on transition-metal catalyzed defluoroborylation. Herein, we report a photocatalytic defluoroborylation platform through direct B-H activation N-heterocyclic carbene boranes, synergistic merger photoredox catalyst and hydrogen atom transfer catalyst. This atom-economic operationally simple protocol enabled an extremely broad scope multifluorinated substrates including polyfluoroarenes, gem-difluoroalkenes, trifluoromethylalkenes in highly selective fashion. Intriguingly, can be free, regioselectivity obtained is complementary to reported transition-metal-catalysis many cases.

Язык: Английский

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Selective C−N Borylation of Alkyl Amines Promoted by Lewis Base

Angewandte Chemie International Edition, Год журнала: 2018, Номер 57(46), С. 15227 - 15231

Опубликована: Сен. 25, 2018

An efficient method for the metal-free deaminative borylation of alkylamines, using bis(catecholato)diboron as boron source, to directly synthesize various alkyl potassium trifluoroborate salts is introduced. The key this high reactivity utilization pyridinium salt activated with a catalytic amount bipyridine-type Lewis base promoter. This transformation shows good functional-group compatibility (e.g., it unimpeded by presence ketone, indole, internal alkene, or unactivated chloride) and can serve powerful synthetic tool amine groups in complex compounds. Mechanistic experiments computations suggest mechanism which B2 cat2 unit intercepts an radical generated single-electron transfer (SET) from boron-based reductant.

Язык: Английский

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Recent advances in asymmetric borylation by transition metal catalysis

Chemical Society Reviews, Год журнала: 2021, Номер 50(23), С. 13129 - 13188

Опубликована: Янв. 1, 2021

We provide a comprehensive overview of transition metal-catalysed asymmetric borylation processes to construct C–B, C–C, and other C–heteroatom bonds with considerable attention devoted the reaction modes mechanisms involved.

Язык: Английский

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Recent advances in the synthesis and applications of α-(trifluoromethyl)styrenes in organic synthesis

Chemical Communications, Год журнала: 2019, Номер 55(90), С. 13486 - 13505

Опубликована: Янв. 1, 2019

α-Trifluoromethylstyrene derivatives are versatile synthetic intermediates for the preparation of more complex fluorinated compounds. Much attention has been paid to these compounds by organic chemistry community, because they have successfully utilized in C-F bond activation a CF3 group, mainly including anionic SN2'-type substitution, cationic SN1'-type ipso-substitution and defluorinative functionalization with transition metals or photoredox catalysts. In addition, metal-catalyzed cycloaddition reactions α-trifluoromethylstyrenes developed construction cycloalkanes cycloalkenes containing fluoro trifluoromethyl groups. this review, we systematically summarized synthesis their applications chemistry, mechanisms were also discussed.

Язык: Английский

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