Themed collection Boron Chemistry in the 21st Century: From Synthetic Curiosities to Functional Molecules

59 items
Highlight

The ultimate Lewis acid catalyst: using tris(pentafluorophenyl) borane to create bespoke siloxane architectures

Boranes are effective catalysts for bespoke siloxane synthesis via (modified) Piers–Rubinsztajn reactions, enabling complex macromolecular architectures with novel functionality, through careful selection of reaction components and conditions.

Graphical abstract: The ultimate Lewis acid catalyst: using tris(pentafluorophenyl) borane to create bespoke siloxane architectures
Highlight

The modern role of boron as a ‘magic element’ in biomedical science: chemistry perspective

This article discusses in a big-picture manner popular boron chemistries that are a focus in multidisciplinary applications.

Graphical abstract: The modern role of boron as a ‘magic element’ in biomedical science: chemistry perspective
Feature Article

Substitution at boron in BODIPYs

BODIPYs provide tunable electronic properties key to many applications. This article highlights structural modification at boron.

Graphical abstract: Substitution at boron in BODIPYs
Feature Article

Bringing out the potential of organoboron compounds by designing the chemical bonds and spaces around boron

This feature article highlights our recent study on new organoboron compounds and boron-mediated reactions, developed based on the concept of vacant boron p-orbital engineering in combination with peripheral space design for boron.

Graphical abstract: Bringing out the potential of organoboron compounds by designing the chemical bonds and spaces around boron
Communication

Nucleophilic strategies to construct –CF2– linkages using borazine-CF2Ar reagents

Using nucleophilic, boron-based –CF2Ar reagents, we demonstrate three methods to form C–CF bonds: (1) nucleophilic aromatic substitution, (2) palladium catalyzed cross-coupling, and (3) nucleophilic substitution.

Graphical abstract: Nucleophilic strategies to construct –CF2– linkages using borazine-CF2Ar reagents
Communication

An electron counting formula to explain and to predict hydrogenated and metallated borophenes

An electron counting rule for borophenes based on graphene and MgB2 helps to design metallated borophenes and borophanes, and suggests strategies to release 2D-borophenes from metal surfaces.

Graphical abstract: An electron counting formula to explain and to predict hydrogenated and metallated borophenes
From the themed collection: Chemical Communications HOT Articles 2022
Communication

Towards depeptidized aminoboronic acid derivatives through the use of borylated iminium ions

Herein, we use α-boryl iminium intermediates to access progressively depeptidized branched β-aminoboronic acids. We show the interaction of these compounds with carbohydrates and demonstrate their potential as synthetic building blocks.

Graphical abstract: Towards depeptidized aminoboronic acid derivatives through the use of borylated iminium ions
Communication

Azidoborolate anions and azidoborole adducts: isolable forms of an unstable borole azide

An unstable azidoborole derivative was prepared and indirectly identified through trapping in the form of neutral Lewis adducts and, quite surprisingly, in the form of the diazidoborolate complex anion.

Graphical abstract: Azidoborolate anions and azidoborole adducts: isolable forms of an unstable borole azide
Communication

Electrophilic activation of difunctional aminoboranes: B–N coupling versus intramolecular Cl/Me exchange

Upon electrophilic initiation, difunctional aminoboranes underwent either B–N coupling or an unexpected Cl/Me exchange reaction.

Graphical abstract: Electrophilic activation of difunctional aminoboranes: B–N coupling versus intramolecular Cl/Me exchange
Communication

Photochromic dithienylethene-containing four-coordinate boron(III) compounds with a spirocyclic scaffold

A series of photochromic four-coordinate spirocyclic boron(III) compounds that display thermally activated upconversion processes from the lower-lying unreactive excited state to the higher-lying photoreactive excited state is reported.

Graphical abstract: Photochromic dithienylethene-containing four-coordinate boron(iii) compounds with a spirocyclic scaffold
Communication

Synthesis of bis(2-pyridylthio)methyl zinc hydride and catalytic hydrosilylation and hydroboration of CO2

The zinc hydride compound, [Bptm]ZnH, is a catalyst for hydroboration of CO2 and carbonyl compounds.

Graphical abstract: Synthesis of bis(2-pyridylthio)methyl zinc hydride and catalytic hydrosilylation and hydroboration of CO2
Open Access Communication

Potential application of metallacarboranes as an internal reference: an electrochemical comparative study to ferrocene

Metallacarboranes are electrochemical analogs to ferrocene. Here the potential advent of metallacarboranes as internal reference systems is studied in various electrochemical conditions and aqueous and organic solvents with no need for derivatization.

Graphical abstract: Potential application of metallacarboranes as an internal reference: an electrochemical comparative study to ferrocene
Communication

Cesium carbonate mediated C–H functionalization of perhalogenated 12-vertex carborane anions

C–H functionalization of undecahalogenated carborane anions, [HCB11X11] (X = Cl, Br, I), is performed with Cs2CO3 in acetonitrile.

Graphical abstract: Cesium carbonate mediated C–H functionalization of perhalogenated 12-vertex carborane anions
Open Access Communication

o-Carborane-based fluorophores as efficient luminescent systems both as solids and as water-dispersible nanoparticles

A particular fluorene-derivative-based o-carborane π-conjugated system exhibits a strong solid-state luminescence efficiency, while preserving the luminescent properties as nanoparticles homogeneously dispersed in water.

Graphical abstract: o-Carborane-based fluorophores as efficient luminescent systems both as solids and as water-dispersible nanoparticles
Communication

New approaches to the functionalization of the 1-carba-closo-decaborate anion

Two new approaches to the functionalization of the 1-carba-closo-decaborate anion resulting in the formation of B–O and B–N bonds were developed.

Graphical abstract: New approaches to the functionalization of the 1-carba-closo-decaborate anion
Communication

Enantioselective synthesis of cyclic α-aminoboronates via copper-catalyzed dearomative borylation of 4-quinolinols

An enantioselective and regioselective dearomative borylation of 4-quinolinols was developed for synthesis of unprecedented heterocyclic α-amino boronates, a new class of compounds potentially relevant to drug discovery.

Graphical abstract: Enantioselective synthesis of cyclic α-aminoboronates via copper-catalyzed dearomative borylation of 4-quinolinols
Communication

AuB8: an Au–borozene complex

Photoelectron spectroscopy and quantum chemistry studies are used to investigate the structure and bonding of AuB8.

Graphical abstract: AuB8−: an Au–borozene complex
From the themed collection: Chemical Communications HOT Articles 2022
Communication

Kinetic stabilization allows structural analysis of a benzoborirene

The successful synthesis and first structural characterization by single crystal X-ray crystallography of a highly strained benzoborirene motif, as well as its reactivity towards selected electrophiles and nucleophiles are reported.

Graphical abstract: Kinetic stabilization allows structural analysis of a benzoborirene
Communication

Utilization of BODIPY-based redox events to manipulate the Lewis acidity of fluorescent boranes

This report describes the incorporation of BODIPY dyes into the ligand framework of a borane to generate a family of molecular boranes that are capable of exhibiting tunable Lewis acidities through BODIPY-based redox events.

Graphical abstract: Utilization of BODIPY-based redox events to manipulate the Lewis acidity of fluorescent boranes
Communication

Nematicidal activity of naphthalimide–boron cluster conjugates

The present work demonstrated the hitherto unknown biological activity of metallacarboranes.

Graphical abstract: Nematicidal activity of naphthalimide–boron cluster conjugates
Communication

Structurally rigidified cobalt bis(dicarbollide) derivatives, a chiral platform for labelling of biomolecules and new materials

A reaction sequence for an easy coupling of the conformationally restrained cobalta bis(dicarbollide)(1) ion with organic molecules is presented along with electrochemical studies and resolution of enantiomers.

Graphical abstract: Structurally rigidified cobalt bis(dicarbollide) derivatives, a chiral platform for labelling of biomolecules and new materials
Communication

Encapsulation of closo-dodecaiodododecaborate in 2-hydroxypropyl-γ-cyclodextrin prevents hemolysis

Na2B12I12 is a candidate X-ray contrast agent, but produces rapid hemolysis at the concentrations needed for medical imaging. Encapsulation within 2-hydroxypropyl-γ-cyclodextrin effectively protects red blood cells at substoichiometric levels.

Graphical abstract: Encapsulation of closo-dodecaiodododecaborate in 2-hydroxypropyl-γ-cyclodextrin prevents hemolysis
Open Access Communication

Binding affinity of aniline-substituted dodecaborates to cyclodextrins

Structure–activity relationships of dodecaborate-substituted nitroanilines as hosts in cyclodextrins have been elucidated.

Graphical abstract: Binding affinity of aniline-substituted dodecaborates to cyclodextrins
Communication

In situ generation of radical initiators using amine-borane complexes for carbohalogenation of alkenes

Atom transfer radical addition of alkyl halides to alkenes was developed using a low amount of a stable initiator, amine borane complexes.

Graphical abstract: In situ generation of radical initiators using amine-borane complexes for carbohalogenation of alkenes
Communication

Synthesis of isoxazoloazaborines via gold(I)-catalyzed propargyl aza-Claisen rearrangement/borylative cyclization cascade

Isoxazoloazaborines have been synthesized from 4-N-propargylaminoisoxazole via gold(I)-catalyzed propargyl aza-Claisen rearrangement followed by electrophilic borylative cyclization in 27–86% yields.

Graphical abstract: Synthesis of isoxazoloazaborines via gold(i)-catalyzed propargyl aza-Claisen rearrangement/borylative cyclization cascade
Communication

Hydroboration of vinyl halides with mesitylborane: a direct access to (mesityl)(alkyl)haloboranes

The direct access to (mesityl)(alkyl)haloboranes (Mes(Alk)BX) (X = Br, Cl) from mesitylborane dimer and vinyl halides is presented, revealing two accessible pathways, one of which being kinetically favoured.

Graphical abstract: Hydroboration of vinyl halides with mesitylborane: a direct access to (mesityl)(alkyl)haloboranes
Communication

Regiocontrolled synthesis of enantioenriched 2-substituted dehydropiperidines by stereospecific allyl–allyl cross-coupling of a chiral allylic boronate

Regiocontrolled cross-coupling of an optically enriched dehydropiperidinyl boronate with cinnamyl carbonates affords 2-allylated 3,4-dehydropiperidines exclusively with enantiospecificity up to 99%.

Graphical abstract: Regiocontrolled synthesis of enantioenriched 2-substituted dehydropiperidines by stereospecific allyl–allyl cross-coupling of a chiral allylic boronate
Communication

Refining boron–iodane exchange to access versatile arylation reagents

Aryl(Mes)iodonium salts, which are multifaceted aryl transfer reagents, are synthesized via boron-iodane exchange.

Graphical abstract: Refining boron–iodane exchange to access versatile arylation reagents
Communication

Ethyl-, vinyl- and ethynylcyanoborates: room temperature borate ionic liquids with saturated and unsaturated hydrocarbon chains

Salts of the anions [RB(CN)3] and [RBF(CN)2] (R = ethyl, vinyl, ethynyl) provide high thermal and electrochemical stabilities. The EMIm-salts are low viscosity room temperature ionic liquids with a wide liquid range.

Graphical abstract: Ethyl-, vinyl- and ethynylcyanoborates: room temperature borate ionic liquids with saturated and unsaturated hydrocarbon chains
Communication

Electrophilic and nucleophilic displacement reactions at the bridgehead borons of tris(pyridyl)borate scorpionate complexes

A ruthenium tris(pyridyl)borate complex is subjected to electrophilic and nucleophilic reactions at the bridgehead borons. These transformations allow for facile tuning of the properties and open up new pathways to functional scorpionate complexes.

Graphical abstract: Electrophilic and nucleophilic displacement reactions at the bridgehead borons of tris(pyridyl)borate scorpionate complexes
Open Access Communication

Metal-free transfer hydrochlorination of internal C–C triple bonds with a bicyclo[3.1.0]hexane-based surrogate releasing two molecules of hydrogen chloride

A non-protic surrogate that contains two molecules of HCl for the synthesis of alkenyl chlorides from internal alkynes is reported. The HCl transfer is catalyzed by B(C6F5)3 and driven by release of strain and aromatization.

Graphical abstract: Metal-free transfer hydrochlorination of internal C–C triple bonds with a bicyclo[3.1.0]hexane-based surrogate releasing two molecules of hydrogen chloride
Communication

Amine-boranes reactions promoted by lanthanide(II) ions

This study shows for the first time the catalytic activity in amine-borane dehydrogenation for lanthanide(II) species and unveils the step-by-step transformations of the starting complexes into active catalytic intermediates.

Graphical abstract: Amine-boranes reactions promoted by lanthanide(ii) ions
Communication

Unlocking metal coordination of diborylamides through ring constraints

A new cyclic diborylamide ligand has been developed and successfully employed to synthesize low-coordinate iron(II) complexes.

Graphical abstract: Unlocking metal coordination of diborylamides through ring constraints
Communication

[closo-B10H8-1,10-(COOH)2]2−: a building block for functional materials?

A convenient synthesis of [closo-B10H8-1,10-(COOH)2]2− leads to a new class of stable diaminocarbonium ylides.

Graphical abstract: [closo-B10H8-1,10-(COOH)2]2−: a building block for functional materials?
Communication

Derivatization of an especially electron-rich diborane

Novel symmetric and unsymmetric diboranes with sp3-hybridized boron atoms and especially electron-donating bridging guanidinate substituents are synthesized and their properties analysed. Moreover, dismutation equilibria are disclosed.

Graphical abstract: Derivatization of an especially electron-rich diborane
Communication

Rhodium-catalyzed sequential B(3)-, B(4)-, and B(5)-trifunctionalization of o-carboranes with three different substituents

A Rh-catalyzed one-pot trifunctionalization of o-carboranes with three different substituents via sequential B(3)–, B(4)–, and B(5)–H activation has been developed.

Graphical abstract: Rhodium-catalyzed sequential B(3)-, B(4)-, and B(5)-trifunctionalization of o-carboranes with three different substituents
Communication

Pd-Catalyzed coupling of benzyl bromides with BMIDA-substituted N-tosylhydrazones: synthesis of trans-alkenyl MIDA boronates

A series of trans-alkenyl MIDA boronates have been prepared by palladium-catalyzed cross-coupling reaction of N-methyliminodiacetyl boronate (BMIDA)-substituted N-tosylhydrazone and benzyl bromides.

Graphical abstract: Pd-Catalyzed coupling of benzyl bromides with BMIDA-substituted N-tosylhydrazones: synthesis of trans-alkenyl MIDA boronates
Communication

Cu-mediated vs. Cu-free selective borylation of aryl alkyl sulfones

Borylation of cyclic aryl–alkyl sulfones gives boronate esters by selective cleavage of C(sp2)–SO2 or C(sp3)–SO2 bonds via Cu-mediated or Cu-free processes.

Graphical abstract: Cu-mediated vs. Cu-free selective borylation of aryl alkyl sulfones
Communication

Intramolecular rotations and electronic states of iron in the iron bis(dicarbollide) complex Fe[(C2B9H11)2] studied by a 57Fe nuclear probe and computational methods

The rotation of iron bis(dicarbollide) complexes was characterized by Mössbauer spectroscopy and computational methods. Unexpected FeII-like character in the 8-dioxane iron bis(dicarbollide) adduct was discovered.

Graphical abstract: Intramolecular rotations and electronic states of iron in the iron bis(dicarbollide) complex Fe[(C2B9H11)2] studied by a 57Fe nuclear probe and computational methods
Communication

Borole-based half-sandwich complexes of germanium and tin

The synthesis and initial observations regarding the reactivity of borole-based half-sandwich complexes with apical divalent group 14 elements germanium and tin are described.

Graphical abstract: Borole-based half-sandwich complexes of germanium and tin
Communication

Nucleophilic borylation of fluorobenzenes with reduced arylboranes

Two challenging but rewarding topics in chemical synthesis are C–F-bond activation and development of B-centered nucleophiles. We have now tackled both subjects by forming aryl–B bonds via SNAr-type reactions on fluorobenzenes under mild conditions.

Graphical abstract: Nucleophilic borylation of fluorobenzenes with reduced arylboranes
Open Access Communication

C,C′-Ru to C,B′-Ru isomerisation in bis(phosphine)Ru complexes of [1,1′-bis(ortho-carborane)]

The transformation of C,C′-bound bis(ortho-carborane) to C,B′-bound is reported for the first time.

Graphical abstract: C,C′-Ru to C,B′-Ru isomerisation in bis(phosphine)Ru complexes of [1,1′-bis(ortho-carborane)]
Communication

Competitive gold/nickel transmetalation

Transmetalation is a key method for the construction of element–element bonds.

Graphical abstract: Competitive gold/nickel transmetalation
Communication

[Mes-B-TMP]+ borinium cation initiated cyanosilylation and catalysed hydrosilylation of ketones and aldehydes

Aryl amino borinium cation can serve as the catalyst for hydrosilylation of ketones and aldehydes.

Graphical abstract: [Mes-B-TMP]+ borinium cation initiated cyanosilylation and catalysed hydrosilylation of ketones and aldehydes
Communication

Harnessing the electronic differences between CAAC-stabilised 1,4-diborabenzene and 9,10-diboraanthracene for synthesis

The oxidation of cyclic alkyl(amino)carbene-stabilised closed-shell 1,4-diborabenzene and the related open-shell singlet biradical 9,10-diboraanthracene with elemental chalcogens yields bicyclic compounds with different lengths of chalcogen bridges.

Graphical abstract: Harnessing the electronic differences between CAAC-stabilised 1,4-diborabenzene and 9,10-diboraanthracene for synthesis
Communication

Transborylation of alkenylboranes with diboranes

Exchange of boryl moieties is possible between alkenylboranes and diboron reagents as a stereospecific cross-metathesis with formation of mixed diboron reagents. DFT calculations propose a mechanism with both symmetric and non-symmetric diboron reagents.

Graphical abstract: Transborylation of alkenylboranes with diboranes
Communication

KB3H8: an environment-friendly reagent for the selective reduction of aldehydes and ketones to alcohols

Selective reduction of aldehydes and ketones to alcohols using KB3H8 was achieved in water and THF.

Graphical abstract: KB3H8: an environment-friendly reagent for the selective reduction of aldehydes and ketones to alcohols
Communication

Carbon monoxide bond cleavage mediated by an intramolecular frustrated Lewis pair: access to new B/N heterocycles via selective incorporation of single carbon atoms

The interaction of carbon monoxide with an intramolecular FLP and a strong electrophile leads to rapid cleavage of the CO triple bond and enables the formation of new B/N heterocycles via selective incorporation of single carbon atoms.

Graphical abstract: Carbon monoxide bond cleavage mediated by an intramolecular frustrated Lewis pair: access to new B/N heterocycles via selective incorporation of single carbon atoms
Communication

Lewis acid activation of Weiss’ reagents ([PhI(Pyr)2]2+) with boranes and isolation of [PhI(4-DMAP)]2+

I(III) reagent [PhI(Pyr)2]2+ (Weiss’ reagent) can be activated with borane Lewis acids in which a pyridine ligand is abstracted giving a more reactive derivative of the reagents.

Graphical abstract: Lewis acid activation of Weiss’ reagents ([PhI(Pyr)2]2+) with boranes and isolation of [PhI(4-DMAP)]2+
Communication

Access to adducts of parent iminoborane isomers, HBNH and NBH2, using frustrated Lewis pair chelation

A general frustrated Lewis pair chelation approach was used to access the parent iminoborane isomers HBNH and NBH2.

Graphical abstract: Access to adducts of parent iminoborane isomers, HBNH and NBH2, using frustrated Lewis pair chelation
Communication

Carboxyboranylamino ethanol: unprecedented discovery of boron agents for neutron capture therapy in cancer treatment

Carboxyboranylamino ethanol is cell membrane permeable and has low cytotoxicity. It shows high molecular docking scores and improved antitumor efficacy in vitro.

Graphical abstract: Carboxyboranylamino ethanol: unprecedented discovery of boron agents for neutron capture therapy in cancer treatment
Communication

Thiophene-fused boracycles as photoactive analogues of diboraanthracenes

Photoactive thiophene-fused boracycle analogues of diboraanthracenes.

Graphical abstract: Thiophene-fused boracycles as photoactive analogues of diboraanthracenes
Communication

Isolation and reactivity of a gold(I) hydroxytrifluoroborate complex stabilized by anion-π+ interactions

A new ambiphilic phosphine-xanthylium ligand is described, along with its ability to stabilize a catalytically competent Au–μ(OH)–BF3 complex via anion-πinteractions.

Graphical abstract: Isolation and reactivity of a gold(i) hydroxytrifluoroborate complex stabilized by anion-π+ interactions
Communication

A strongly Lewis-acidic and fluorescent borenium cation supported by a tridentate formazanate ligand

A fluorescent, strongly Lewis-acidic borenium cation (Gutmann–Beckett acceptor number >100) was created using a tridentate formazanate ligand. This cation shows a potential utility as a colourimetric reactivity probe.

Graphical abstract: A strongly Lewis-acidic and fluorescent borenium cation supported by a tridentate formazanate ligand
Open Access Communication

A boron–nitrogen transborylation enabled, borane-catalysed reductive cyanation of enones

The borane-catalysed hydrocyanation of enones has been developed and applied across a series of substrates including those being functional groups susceptible to reduction.

Graphical abstract: A boron–nitrogen transborylation enabled, borane-catalysed reductive cyanation of enones
Open Access Communication

Carborane photochromism: a fatigue resistant carborane switch

A dithienylethene molecule involving carborane clusters shows remarkable fatigue resistance and high contrast visual colour changes when irradiated with alternating ultraviolet and visible light.

Graphical abstract: Carborane photochromism: a fatigue resistant carborane switch
Communication

Photoredox B–H functionalization to selective B–N(sp3) coupling of nido-carborane with primary and secondary amines

B–N(sp3) coupling of nido-carborane with organic amines by photoredox catalysis leads to nitrogen-containing nido-carboranes in moderate to good yields.

Graphical abstract: Photoredox B–H functionalization to selective B–N(sp3) coupling of nido-carborane with primary and secondary amines
Communication

B(C6F5)3-Catalyzed site-selective N1-alkylation of benzotriazoles with diazoalkanes

The site-selective N1-alkylation of benzotriazoles with diazoalkanes is achieved using 10 mol% of B(C6F5)3 as a catalyst.

Graphical abstract: B(C6F5)3-Catalyzed site-selective N1-alkylation of benzotriazoles with diazoalkanes
Communication

Facile proton-coupled electron transfer enabled by coordination-induced E–H bond weakening to boron

Coordination induced bond weakening (CIBW) leads to facile PCET at various E–H bonds.

Graphical abstract: Facile proton-coupled electron transfer enabled by coordination-induced E–H bond weakening to boron
59 items

About this collection

This special collection, Guest Edited by Robert J. Gilliard (University of Virginia), Rosario Núñez (Institut de Ciència de Materials de Barcelona) and Caleb Martin (Baylor University), covers all areas of boron chemistry with an emphasis on synthesis and reactivity. This includes small molecules, boron clusters, frustrated Lewis pairs, borylation, catalysis, and ligand development.

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