Electrochemical strategies for C–H functionalization and C–N bond formation

Chemical Society Reviews, Год журнала: 2018, Номер 47(15), С. 5786 - 5865

Опубликована: Янв. 1, 2018

This review provides an overview of the use electrochemistry as appealing platform for expediting carbon–hydrogen functionalization and carbon–nitrogen bond formation.

Язык: Английский

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New Strategies for the Transition-Metal Catalyzed Synthesis of Aliphatic Amines

Chemical Reviews, Год журнала: 2020, Номер 120(5), С. 2613 - 2692

Опубликована: Фев. 17, 2020

Transition-metal catalyzed reactions that are able to construct complex aliphatic amines from simple, readily available feedstocks have become a cornerstone of modern synthetic organic chemistry. In light the ever-increasing importance across range chemical sciences, this review aims provide concise overview transition-metal approaches alkylamine synthesis and their functionalization. Selected examples amine bond forming include: (a) hydroamination hydroaminoalkylation, (b) C(sp3)–H functionalization, (c) visible-light-mediated photoredox catalysis.

Язык: Английский

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Efficient and selective N-alkylation of amines with alcohols catalysed by manganese pincer complexes

Nature Communications, Год журнала: 2016, Номер 7(1)

Опубликована: Окт. 6, 2016

Abstract Borrowing hydrogen (or autotransfer) reactions represent straightforward and sustainable C–N bond-forming processes. In general, precious metal-based catalysts are employed for this effective transformation. recent years, the use of earth abundant cheap non-noble metal process attracted considerable attention in scientific community. Here we show that selective N -alkylation amines with alcohols can be catalysed by defined PNP manganese pincer complexes. A variety substituted anilines monoalkylated different (hetero)aromatic aliphatic even presence other sensitive reducible functional groups. As a special highlight, report chemoselective monomethylation primary using methanol under mild conditions.

Язык: Английский

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Copper Hydride Catalyzed Hydroamination of Alkenes and Alkynes

Angewandte Chemie International Edition, Год журнала: 2015, Номер 55(1), С. 48 - 57

Опубликована: Дек. 10, 2015

Abstract Over the past few years, CuH‐catalyzed hydroamination has been discovered and developed as a robust conceptually novel approach for synthesis of enantioenriched secondary tertiary amines. The success in this area research was made possible through large body precedent copper(I) hydride catalysis well‐explored use hydroxylamine esters electrophilic amine sources related copper‐catalyzed processes. This Minireview details background, advances, mechanistic investigations hydroamination.

Язык: Английский

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Homogeneous Catalysis by Cobalt and Manganese Pincer Complexes

ACS Catalysis, Год журнала: 2018, Номер 8(12), С. 11435 - 11469

Опубликована: Окт. 16, 2018

Homogeneous catalysis of organic transformations by metal complexes has been mostly based on noble metals. In recent years, tremendous progress made in the field base-metal catalysis, with pincer-type complexes, such as iron, cobalt, nickel, and manganese pincer systems. Particularly impressive is explosive growth Mn-based first being reported recently 2016. This review covers homogeneously catalyzed reactions using cobalt manganese. Various are described, including acceptorless dehydrogenation, hydrogenation, dehydrogenative coupling, hydrogen borrowing, transfer, H–X additions, C–C alkene polymerization N2 fixation, their scope brief mechanistic comments.

Язык: Английский

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Recent Advances in Hydrometallation of Alkenes and Alkynes via the First Row Transition Metal Catalysis

Chinese Journal of Chemistry, Год журнала: 2018, Номер 36(11), С. 1075 - 1109

Опубликована: Авг. 20, 2018

Abstract Hydrometallation of alkenes and alkynes provides a straightforward route to access alkyl‐ or alkenyl‐metal reagents, which have wide range applications in organic transformations. In recent years, the first row transition metals (such as copper, nickel, cobalt, iron, etc .) emerged high activity selectivity this area with aid variety ligands. This review covers advances hydrometallation minimally functionalized unsaturated C—C bonds (including alkenes, alkynes, dienes, allenes, enynes, .), well transformations involving catalytic process via metal catalysis.

Язык: Английский

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Decarboxylative sp3 C–N coupling via dual copper and photoredox catalysis

Nature, Год журнала: 2018, Номер 559(7712), С. 83 - 88

Опубликована: Июнь 18, 2018

Язык: Английский

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Photochemical Generation of Nitrogen-Centered Amidyl, Hydrazonyl, and Imidyl Radicals: Methodology Developments and Catalytic Applications

ACS Catalysis, Год журнала: 2017, Номер 7(8), С. 4999 - 5022

Опубликована: Июнь 19, 2017

During the past decade, visible light photocatalysis has become a powerful synthetic platform for promoting challenging bond constructions under mild reaction conditions. These photocatalytic systems rely on harnessing energy purposes through generation of reactive but controllable free radical species. Recent progress in area established it as an enabling catalytic strategy and selective nitrogen-centered radicals. The application activation amides, hydrazones, imides represents valuable approach facilitating formation Within span only couple years, significant been made expediting amidyl, hydrazonyl, imidyl radicals from variety precursors. This Perspective highlights recent advances light-mediated these A particular emphasis is placed unique ability accessing elusive manifolds construction diversely functionalized nitrogen-containing motifs nontraditional disconnections contemporary chemistry.

Язык: Английский

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CuH-Catalyzed Olefin Functionalization: From Hydroamination to Carbonyl Addition

Accounts of Chemical Research, Год журнала: 2020, Номер 53(6), С. 1229 - 1243

Опубликована: Май 13, 2020

ConspectusIn organic synthesis, ligand-modified copper(I) hydride (CuH) complexes have become well-known reagents and catalysts for selective reduction, particularly toward Michael acceptors carbonyl compounds. Recently, our group others found that these undergo migratory insertion (hydrocupration) with relatively unactivated electronically unpolarized olefins, producing alkylcopper intermediates can be leveraged to forge a variety of useful bonds. The resulting formal hydrofunctionalization reactions formed the basis resurgence research in CuH catalysis. This Account chronicles development this concept group, highlighting its origin context asymmetric hydroamination, evolution more general C–X bond-forming reactions, applications addition olefin-derived nucleophiles derivatives.Hydroamination, an olefin into N–H bond amine, is process significant academic industrial interest, due potential transform widely available alkenes alkynes valuable complex amines. We developed polarity-reversed strategy catalytic enantioselective hydroamination relying on reaction olefins generate chiral organocopper intermediates, which are intercepted by electrophilic amine reagents. By engineering auxiliary ligand, electrophile, conditions, scope method has since been extended include many types including challenging internal olefins. Further, expanded enable synthesis primary, secondary, tertiary amines as well amides, N-alkylated heterocycles, anilines. All exhibit high regio- stereoselectivity and, mild conditions required, excellent tolerance heterocycles polar functional groups.Though generation species from was originally devised means solve problem, we soon could react efficiently unexpectedly broad range electrophiles, alkyl halides, silicon reagents, arylpalladium species, derivatives. ability function precursors nucleophilic proved advantageous because it overcomes disadvantages associated traditional organometallic removing need pregeneration nucleophile separate operation, CuH-catalyzed feature improved step economy, enhanced tolerance, catalyst control over stereoselectivity. Following paradigm, feedstock such allene, butadiene, styrene employed alkylation ketones, imines, aldehydes.

Язык: Английский

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Catalytic intermolecular hydroaminations of unactivated olefins with secondary alkyl amines

Science, Год журнала: 2017, Номер 355(6326), С. 727 - 730

Опубликована: Фев. 16, 2017

Hydroamination gets a light push uphill of olefins is broadly useful method for making carbon-nitrogen bonds. However, when both the amine and olefin have multiple alkyl substituents, reaction can become energetically unfavorable. Musacchio et al. used energy in blue to surmount this obstacle (see Perspective by Buchanan Hull). A photo-excited iridium complex oxidized amine, which turn bonded efficiently olefin, after thiophenol cocatalyst shuttled electron back. The could operate across wide range partners. Science , issue p. 727 ; see also 690

Язык: Английский

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