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Themed collection Celebrating the 80th Birthday of Professor Ei-ichi Negishi

53 articles
Editorial

In celebration of the 80th birthday of Professor Ei-ichi Negishi

Photo credit © Steve Scherer, Purdue University.

Graphical abstract: In celebration of the 80th birthday of Professor Ei-ichi Negishi
Review Article

Silylative coupling of olefins with vinylsilanes in the synthesis of functionalized alkenes

Recent developments in the sequential synthetic strategies including ruthenium-catalyzed silylative coupling followed by desilylation, leading to π-conjugated organic derivatives are presented.

Graphical abstract: Silylative coupling of olefins with vinylsilanes in the synthesis of functionalized alkenes
Review Article

Negishi coupling in the synthesis of advanced electronic, optical, electrochemical, and magnetic materials

Negishi coupling is an efficient and versatile tool for selective C–C bond formation in the synthesis of organic electronic, optical, electrochemical, and magnetic materials.

Graphical abstract: Negishi coupling in the synthesis of advanced electronic, optical, electrochemical, and magnetic materials
Review Article

Conquering three-carbon axial chirality of allenes

Axially chiral allenes are an important class of molecules widely existing in nature and also valuable chiral building blocks for organic synthesis. With more and more new protocols for racemic allenes and new chiral ligands being developed, a wide variety of novel and challenging transformations have been recently unveiled for the synthesis of this type of highly versatile compounds. In this review, we present a critical account of the enantioselective synthesis of axially chiral allenes.

Graphical abstract: Conquering three-carbon axial chirality of allenes
Review Article

Organometallic intermediate-based organic synthesis: organo-di-lithio reagents and beyond

Metal-mediated organic reactions have become one of the great frontiers of organic synthesis.

Graphical abstract: Organometallic intermediate-based organic synthesis: organo-di-lithio reagents and beyond
Research Article

A novel dynamic pseudo[1]rotaxane based on a mono-biotin-functionalized pillar[5]arene

A stable pillar[5]arene-based pseudo[1]rotaxane P1′ was synthesized by the click reaction, which exhibited a dynamic slow disassembly process upon adding a strong-polar solvent or competitive guest. Moreover, this dynamic behavior might be used as a switch to turn on or off the bioactivity of the biotin moiety in aqueous solution.

Graphical abstract: A novel dynamic pseudo[1]rotaxane based on a mono-biotin-functionalized pillar[5]arene
Research Article

Regio- and stereoselective multisubstituted olefin synthesis via hydro/carboalumination of alkynes and subsequent iron-catalysed cross-coupling reaction with alkyl halides

A new synthetic route towards multisubstituted olefins was developed based on the direct cross coupling of alkenyl aluminium reagents, prepared by hydro- and carboalumination, with alkyl halides in the presence of an iron catalyst.

Graphical abstract: Regio- and stereoselective multisubstituted olefin synthesis via hydro/carboalumination of alkynes and subsequent iron-catalysed cross-coupling reaction with alkyl halides
Research Article

Asymmetric synthesis of γ-aryl-substituted GABA derivatives via a highly diastereoselective Rh-catalyzed boronic acid addition at room temperature

A highly diastereoselective Rh-catalyzed boronic acid addition to enantiopure sulfinylimines at room temperature providing γ-aryl GABA derivatives has been described.

Graphical abstract: Asymmetric synthesis of γ-aryl-substituted GABA derivatives via a highly diastereoselective Rh-catalyzed boronic acid addition at room temperature
Research Article

Nickel-catalyzed decarboxylative arylation of azoles with perfluoro- and nitrobenzoates

This manuscript details a nickel-catalyzed method for the arylation of azole C–H bonds using perfluoro- and 2-nitro benzoates.

Graphical abstract: Nickel-catalyzed decarboxylative arylation of azoles with perfluoro- and nitrobenzoates
Research Article

Synthesis of morpholine or piperazine derivatives through gold-catalyzed cyclization reactions of alkynylamines or alkynylalcohols

A gold catalyzed reaction for the preparation of morpholine and piperazine derivatives from alkynylalcohols or alkynylamines was developed.

Graphical abstract: Synthesis of morpholine or piperazine derivatives through gold-catalyzed cyclization reactions of alkynylamines or alkynylalcohols
Research Article

Sulfur-containing stable five-membered “cycloallene” complexes: 1-thia-2-zircona- and 1-thia-2-titanacyclopenta-3,4-dienes

Stable five-membered sulfur-containing metallacyclic allenes, 1-thia-2-metallacyclopenta-3,4-diene, were synthesized from the reactions of low-valent zirconocene or titanocene with alkynylthioamides.

Graphical abstract: Sulfur-containing stable five-membered “cycloallene” complexes: 1-thia-2-zircona- and 1-thia-2-titanacyclopenta-3,4-dienes
Research Article

A mechanistic study on the SHi reaction at tin atoms in a radical cascade reaction

A kinetic study on the intramolecular direct radical substitution reaction on tin atoms was undertaken.

Graphical abstract: A mechanistic study on the SHi reaction at tin atoms in a radical cascade reaction
Research Article

1,3-Dipolar cycloaddition reactions of phthalic anhydrides with an azomethine ylide

A series of phthalic anhydrides underwent a 1,3-dipolar cycloaddition reaction with N-benzylazomethine ylide to produce unstable spiro(isobenzofuran-1,5′-oxazolidin)-3-ones, which underwent a subsequent reductive ring-opening reaction to afford 1(3H)-isobenzofuranones.

Graphical abstract: 1,3-Dipolar cycloaddition reactions of phthalic anhydrides with an azomethine ylide
Research Article

Atroposelective synthesis of axially chiral P,S-ligands based on arynes

An unprecedented atropo-diastereoselective aryl–aryl coupling via arynes allows for the modular synthesis of enantiopure P,S-ligands.

Graphical abstract: Atroposelective synthesis of axially chiral P,S-ligands based on arynes
Research Article

An ortho-directed C–H borylation/Suzuki coupling sequence in the formation of biphenylbenzylic amines

ortho-C–H borylation of benzylic amines has been used in conjunction with a Suzuki–Miyaura coupling reaction to access biphenylbenzylic amines in good yields and requiring a single purification step.

Graphical abstract: An ortho-directed C–H borylation/Suzuki coupling sequence in the formation of biphenylbenzylic amines
Research Article

Copper-catalysed cross-couplings of arylboronate esters with aryl and heteroaryl iodides and bromides

Cu-catalysed cross-coupling for mono- and di-arylations of aryl and heteroaryl iodides and bromides is achieved with arylboronate esters.

Graphical abstract: Copper-catalysed cross-couplings of arylboronate esters with aryl and heteroaryl iodides and bromides
Research Article

Aerobic oxidation of cyclohexanones to phenols and aryl ethers over supported Pd catalysts

ZrO2 supported palladium catalysts promoted the aerobic oxidation of cyclohexanones to give phenols and aryl ethers.

Graphical abstract: Aerobic oxidation of cyclohexanones to phenols and aryl ethers over supported Pd catalysts
Research Article

Formal base-free homolytic aromatic substitutions via photoredox catalysis

We developed a simple and convenient method to assemble biaryls exploiting a photoredox catalyst and visible light.

Graphical abstract: Formal base-free homolytic aromatic substitutions via photoredox catalysis
Open Access Research Article

A one-pot dilithiation–lithium–zinc exchange–Negishi coupling approach to 2,6-di(hetero)aryl substituted dithienothiazines – a novel class of electronically fine-tunable redox systems

2,6-Di(hetero)aryl substituted dithienothiazines with fine-tunable electronic properties are efficiently accessible by lithiation–lithium–zinc exchange–Negishi cross-coupling in a one-pot fashion.

Graphical abstract: A one-pot dilithiation–lithium–zinc exchange–Negishi coupling approach to 2,6-di(hetero)aryl substituted dithienothiazines – a novel class of electronically fine-tunable redox systems
Research Article

Mechanistic studies and optimisation of a Pd-catalysed direct arylation reaction using phosphine-free systems

The mechanistic study of the initial step in direct arylation provides valuable insight for optimising reaction conditions.

Graphical abstract: Mechanistic studies and optimisation of a Pd-catalysed direct arylation reaction using phosphine-free systems
Research Article

An alkyne hydrosilylation–Hiyama coupling approach to highly functionalised 1,3-dienes

A high yielding and completely stereoselective hydrosilylation–Hiyama protocol has been established for the synthesis of highly functionalised E,E-dienes.

Graphical abstract: An alkyne hydrosilylation–Hiyama coupling approach to highly functionalised 1,3-dienes
Open Access Research Article

Regio- and stereoselective synthesis of α-hydroxy-β-azido tetrazoles

Unreported α-hydroxy-β-azido tetrazoles are prepared in a single step and mild conditions from readily available epoxy nitriles.

Graphical abstract: Regio- and stereoselective synthesis of α-hydroxy-β-azido tetrazoles
Research Article

A divergent synthesis of 3,10-dialkylpicenes

A series of 3,10-dialkylated picenes has been synthesized through sequential Ni-catalyzed alkynylation of a C–O bond, alkylation, and hydrogenation.

Graphical abstract: A divergent synthesis of 3,10-dialkylpicenes
Research Article

New building blocks for iminosugars: a concise synthesis of polyhydroxylated N-alkoxypiperidines through an intramolecular azepine ring contraction

Polyhydroxylated piperidines are a functionally rich class of biologically active molecules that have broad therapeutic potential.

Graphical abstract: New building blocks for iminosugars: a concise synthesis of polyhydroxylated N-alkoxypiperidines through an intramolecular azepine ring contraction
Open Access Research Article

Synthesis of bisarylethyne–peptide conjugates

Convenient preparation of bisarylethyne–peptide conjugates, and a mild procedure for the H- or D-reduction of the bisarylethyne triple bond.

Graphical abstract: Synthesis of bisarylethyne–peptide conjugates
Research Article

An iodine-promoted Meyer–Schuster rearrangement for the synthesis of α-iodo unsaturated ketones

A facile and efficient iodine-promoted Meyer–Schuster rearrangement of propargyl alcohols for the synthesis of α-iodo-α,β-unsaturated ketones is presented.

Graphical abstract: An iodine-promoted Meyer–Schuster rearrangement for the synthesis of α-iodo unsaturated ketones
Research Article

A highly stereo-controlled protocol to prepare pipecolic acids based on Heck and cyclohydrocarbonylation reactions

A consecutive series of metal-catalyzed reactions for the preparation of enantiomerically pure piperidine derivatives.

Graphical abstract: A highly stereo-controlled protocol to prepare pipecolic acids based on Heck and cyclohydrocarbonylation reactions
Research Article

Metal catalyzed cross-coupling of aryl and benzyl methyl sulfides: nickel catalyzed Caryl–Csp3 and Csp3–Csp3 bond formations

The nickel catalyzed functionalization of CAr–SMe and Csp3–SMe bonds by direct exchange of the sulfur atom with an activated sp3-carbon has been developed. The protocol allows the conversion of aryl and benzyl methyl sulfides to trimethylsilylated products in good yields.

Graphical abstract: Metal catalyzed cross-coupling of aryl and benzyl methyl sulfides: nickel catalyzed Caryl–Csp3 and Csp3–Csp3 bond formations
Research Article

Synthetic strategies toward the decalin motif of maklamicin and related spirotetronates

Controlling the selectivity of an intramolecular Diels–Alder cycloaddition (IMDA) allows efficient synthetic access to the decalin motif of spirotetronates.

Graphical abstract: Synthetic strategies toward the decalin motif of maklamicin and related spirotetronates
Research Article

Pd(II)-catalyzed asymmetric addition of arylboronic acids to cyclic N-sulfonyl ketimine esters and a DFT study of its mechanism

A highly efficient palladium-catalyzed asymmetric arylation of cyclic ketimine esters is developed, which provides the desired product in up to 99% yield with up to 99% ee. The mechanism of enantioselection is studied using DFT calculation.

Graphical abstract: Pd(ii)-catalyzed asymmetric addition of arylboronic acids to cyclic N-sulfonyl ketimine esters and a DFT study of its mechanism
Research Article

Cleavage of the C–C triple bond of ketoalkynes: synthesis of 4(3H)-quinazolinones

A novel strategy to 4(3H)-quinazolinones from ketoalkynes and o-aminobenzamides through C–C triple bond fragmentation and two C–N bond formations under external oxidant and metal free conditions.

Graphical abstract: Cleavage of the C–C triple bond of ketoalkynes: synthesis of 4(3H)-quinazolinones
Research Article

Asymmetric synthesis of (αS)-polyfluoroalkylated N-Boc-prolinols by the diethyl zinc-induced asymmetric Meerwein–Ponndorf–Verley reduction of perfluoroalkyl N-Boc-pyrrolidyl ketones

Asymmetric synthesis of (αS)-polyfluoroalkylated prolinols by the asymmetric Meerwein–Ponndorf–Verley-type reduction of perfluoroalkyl N-Boc-pyrrolidyl ketones with Et2Zn has been developed.

Graphical abstract: Asymmetric synthesis of (αS)-polyfluoroalkylated N-Boc-prolinols by the diethyl zinc-induced asymmetric Meerwein–Ponndorf–Verley reduction of perfluoroalkyl N-Boc-pyrrolidyl ketones
Research Article

Cationic iridium-catalyzed C–H alkylation of 2-substituted pyridine N-oxides with acrylates

The reaction of 2-arylmethyl-, 2-aryl-, and 2-alkyl substituted pyridine N-oxides with acrylates proceeded in the presence of a cationic Ir-rac-BINAP catalyst under heating conditions.

Graphical abstract: Cationic iridium-catalyzed C–H alkylation of 2-substituted pyridine N-oxides with acrylates
Research Article

Synthesis of (−)-mesembrine using the quaternary carbon-constructing allylic substitution

The allylic substitution for construction of quaternary carbons is used for synthesis of (−)-mesembrine.

Graphical abstract: Synthesis of (−)-mesembrine using the quaternary carbon-constructing allylic substitution
Research Article

Phase-transfer-catalyzed asymmetric desymmetrizations of cyclopentanones

Highly enantioselective phase-transfer-catalyzed epoxide-opening reaction and isomerization of cyclopentanones were achieved.

Graphical abstract: Phase-transfer-catalyzed asymmetric desymmetrizations of cyclopentanones
Research Article

Selective monoalkylation of amines with light electrophiles using a flow microreactor system

The challenging direct monoalkylation of primary and secondary amines with small triflates (C1 to C3) was accomplished in a flow microreactor by virtue of efficient mixing and short reaction times.

Graphical abstract: Selective monoalkylation of amines with light electrophiles using a flow microreactor system
Research Article

CO-enabled rhenium hydride catalyst for directed C(sp2)–H bond alkylation with olefins

We report the first example of CO-enabled rhenium hydride complex-catalyzed inter- and intra-molecular hydroarylation of activated alkenes, with a broad reaction scope.

Graphical abstract: CO-enabled rhenium hydride catalyst for directed C(sp2)–H bond alkylation with olefins
Research Article

Remarkable electron-withdrawing effect of the Ph2P(O)-ethynyl group: Ph2P(O)-ethynyl-substituted aryl halides and copper acetylides for tailor-made Sonogashira couplings

Ph2P(O)-ethynylphenyl bromide showed higher reactivity in Sonogashira couplings than phenylethynylphenyl bromide because of the electron-withdrawing nature of the Ph2P(O) group.

Graphical abstract: Remarkable electron-withdrawing effect of the Ph2P(O)-ethynyl group: Ph2P(O)-ethynyl-substituted aryl halides and copper acetylides for tailor-made Sonogashira couplings
Research Article

4-Alkenyl-5H-1,2,3-oxathiazole 2,2-dioxides in catalytic and enantioselective [4 + 2] cycloaddition through iminium activation. Straightforward access to the trans-decaline framework and to densely functionalized cyclohexanes

4-Alkenyl-5H-1,2,3-oxathiazole 2,2-dioxides undergo Michael/Michael cascade reaction with enals through iminium/enamine activation.

Graphical abstract: 4-Alkenyl-5H-1,2,3-oxathiazole 2,2-dioxides in catalytic and enantioselective [4 + 2] cycloaddition through iminium activation. Straightforward access to the trans-decaline framework and to densely functionalized cyclohexanes
Research Article

Deuterative cyclization of sulfanyl 1,6-diynes: complete and monodeuteration of functional groups on heterocycles

Regioselective H/D exchange reaction of functional groups on heterocycles proceeded via a transition metal-free reductive cyclization of sulfanyl 1,6-diynes using sodium borodeuteride/ethanol-D1.

Graphical abstract: Deuterative cyclization of sulfanyl 1,6-diynes: complete and monodeuteration of functional groups on heterocycles
Research Article

Thieno[2,3,a]carbazole donor-based organic dyes for high efficiency dye-sensitized solar cells

A new class of D–π-A organic dyes based on thieno[2,3,a]carbazole as an electron donor showed high efficiencies for dye-sensitized solar cells.

Graphical abstract: Thieno[2,3,a]carbazole donor-based organic dyes for high efficiency dye-sensitized solar cells
Research Article

N-heterocyclic carbene-based ruthenium-catalyzed direct amidation of aldehydes with amines

Ru-catalyzed dehydrogenative amide synthesis from aldehydes and amines was achieved, based on the idea of using a hemiaminal intermediate to generate the active Ru-hydride species.

Graphical abstract: N-heterocyclic carbene-based ruthenium-catalyzed direct amidation of aldehydes with amines
Research Article

Co-catalysis between DABCO and a Brønsted acid in the catalytic [4 + 2] annulation of isatin with but-3-yn-2-one and mechanistic investigations

Catalytic amounts of the base catalyst DABCO in cooperation with a proton source afford the [4 + 2] cycloadducts of isatins with but-3-yn-2-one in moderate to good yields. Moreover, related plausible mechanisms have been proposed in detail based on control and deuterium labeling experiments.

Graphical abstract: Co-catalysis between DABCO and a Brønsted acid in the catalytic [4 + 2] annulation of isatin with but-3-yn-2-one and mechanistic investigations
Research Article

Synthesis and characterization of N-2-aryl-1,2,3-triazole based iridium complexes as photocatalysts with tunable photoredox potential

N-2-Aryl chelated 1,2,3-triazole-Ir(III) complexes with various substituents were prepared for the first time.

Graphical abstract: Synthesis and characterization of N-2-aryl-1,2,3-triazole based iridium complexes as photocatalysts with tunable photoredox potential
Research Article

Binary reducing agents containing dichloroindium hydride for the selective, partial, or tandem reductions of bifunctional compounds consisting of halo-nitriles, halo-esters and halo-carboxylic acids

Selective, partial, or tandem reductions of bifunctional organic halides is reported.

Graphical abstract: Binary reducing agents containing dichloroindium hydride for the selective, partial, or tandem reductions of bifunctional compounds consisting of halo-nitriles, halo-esters and halo-carboxylic acids
Research Article

Cationic Pd(II)-catalyzed cyclization of N-tosyl-aniline tethered alkynyl ketones initiated by hydropalladation of alkynes: a facile way to 1,2-dihydro or 1,2,3,4-tetrahydroquinoline derivatives

A cationic Pd(II)-catalyzed intramolecular alkyne-carbonyl reductive coupling reaction of N-tosyl-aniline tethered alkynyl ketones under transfer hydrogenation conditions to give hydroquinolines is developed.

Graphical abstract: Cationic Pd(ii)-catalyzed cyclization of N-tosyl-aniline tethered alkynyl ketones initiated by hydropalladation of alkynes: a facile way to 1,2-dihydro or 1,2,3,4-tetrahydroquinoline derivatives
Research Article

A chiral bicyclo[2.2.2]octa-2,5-diene ligand substituted with the ferrocenyl group and its use for rhodium-catalyzed asymmetric 1,4-addition reactions

New chiral diene ligand, Fc,Ph-bod, showed higher enantioselectivity than Ph-bod in the rhodium-catalyzed asymmetric 1,4-addition of aryl- and alkenylboronic acids.

Graphical abstract: A chiral bicyclo[2.2.2]octa-2,5-diene ligand substituted with the ferrocenyl group and its use for rhodium-catalyzed asymmetric 1,4-addition reactions
Research Article

Copper(II)-catalyzed methoxylation of unactivated (hetero)aryl C–H bonds using a removable bidentate auxiliary

A copper-catalyzed methoxylation of unactivated (hetero)aryl C–H bonds has been developed.

Graphical abstract: Copper(ii)-catalyzed methoxylation of unactivated (hetero)aryl C–H bonds using a removable bidentate auxiliary
Research Article

Chiroptical sensing of oligonucleotides with a cyclic octapyrrole

A cyclic octapyrrole shows a strong chiroptical response upon complexation with an oligonucleotide that has high thymine content.

Graphical abstract: Chiroptical sensing of oligonucleotides with a cyclic octapyrrole
Open Access Research Article

Polycyclic imidazo[1,2-a]pyridine analogs – synthesis via oxidative intramolecular C–H amination and optical properties

Oxidative C–H amination has proved to be an efficient strategy to construct pyrido[2′,1′:2,3]imidazo[4,5-b]indoles and their π-expanded analogs.

Graphical abstract: Polycyclic imidazo[1,2-a]pyridine analogs – synthesis via oxidative intramolecular C–H amination and optical properties
Research Article

Efficient access to 1H-indazoles via copper-catalyzed cross-coupling/cyclization of 2-bromoaryl oxime acetates and amines

A novel synthesis of 1H-indazoles via copper-catalyzed cross-coupling/cyclization of 2-bromoaryl oxime acetates and amines is reported.

Graphical abstract: Efficient access to 1H-indazoles via copper-catalyzed cross-coupling/cyclization of 2-bromoaryl oxime acetates and amines
Research Article

Brønsted acid-catalyzed synthesis of carbazoles from 2-substituted indoles

A simple and efficient approach for the synthesis of disubstituted carbazoles has been developed from o-haloanilines and terminal alkynes using a two-step strategy, namely, Sonogashira coupling and intramolecular cyclization.

Graphical abstract: Brønsted acid-catalyzed synthesis of carbazoles from 2-substituted indoles
Tutorial Account

Catalytic dehydrogenative aromatization: an alternative route to functionalized arenes

Catalytic dehydrogenative aromatization has emerged as an efficient and environmentally friendly way to access functionalized arenes in recent years.

Graphical abstract: Catalytic dehydrogenative aromatization: an alternative route to functionalized arenes
53 articles

About this collection

Professor Ei-ichi Negishi, the Noble laureate in 2010, will celebrate his 80th birthday in 2015. Organic Chemistry Frontiers is delighted to present an online themed collection dedicated to this special occasion. Guest Editors of this themed collection are Bruce H. Lipshutz (UC Santa Barbara) and
Tamotsu Takahashi (Hokkaido University).

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