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Author: Jianliang Xiao (102)


Jan
2018

Crabtree's catalyst was encapsulated inside the pores of the sulfonated MIL-101(Cr) metal-organic framework by cation exchange. This hybrid catalyst is active for the heterogeneous hydrogenation of non-functionalized alkenes either in solution or in the gas phase. Moreover, encapsulation inside a well-defined hydrophilic microenvironment enhances catalyst stability and selectivity to hydrogenation over isomerization for substrates bearing ligating functionalities.

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Feb
2018

A highly effective hydroxylation reaction of aryl halides with water under synergistic organophotoredox and nickel catalysis is reported. The OH group of the resulting phenols originates from water, following deprotonation facilitated by an intramolecular base group on the ligand. Significantly, aryl bromides as well as less reactive aryl chlorides served as effective substrates to afford phenols with a wide range of functional groups.

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Jan
2018

Combination of optogenetics and pharmacology represents a unique approach to dissect neural circuitry with high specificity and versatility. However, conventional tools available to perform these experiments, such as optical fibers and metal cannula, are limited due to their tethered operation and lack of biomechanical compatibility. To address these issues, a miniaturized, battery-free, soft optofluidic system that can provide wireless drug delivery and optical stimulation for spatiotemporal control of the targeted neural circuit in freely behaving animals is reported.

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Oct
2017

Shape memory polymers (SMPs) can remember two or more distinct shapes, and thus can have a lot of potential applications. This paper presents combined experimental and theoretical studies on the wrinkling of single-crystal Si ribbons on SMPs and the temperature dependent evolution. Using the shape memory effect of heat responsive SMPs, this study provides a method to build wavy forms of single-crystal silicon thin films on top of SMP substrates.

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Oct
2017

The chemoselective alkylation and olefination of alkylnitriles with alcohols have been developed by simply controlling the reaction atmosphere. A binuclear rhodium complex catalyzes the alkylation reaction under argon through a hydrogen-borrowing pathway and the olefination reaction under oxygen through aerobic dehydrogenation. Broad substrate scope is demonstrated, permitting the synthesis of some important organic building blocks.

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Oct
2017

Methods for microfabrication of solderable and stretchable sensing systems (S4s) and a scaled production of adhesive-integrated active S4s for health monitoring are presented. S4s' excellent solderability is achieved by the sputter-deposited nickel-vanadium and gold pad metal layers and copper interconnection. The donor substrate, which is modified with "PI islands" to become selectively adhesive for the S4s, allows the heterogeneous devices to be integrated with large-area adhesives for packaging.

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Sep
2017

Due to their excellent mechanical and electrical properties, single-walled carbon nanotubes (SWNTs) can find broad applications in many areas, such as field-effect transistors, logic circuits, sensors and flexible electronics. High-density, horizontally aligned arrays of SWNTs are essential for high performance electronics. Many experimental studies have demonstrated that chemical vapor deposition growth of nanotubes on crystalline substrates such as sapphire offers a promising route to achieve such dense, perfectly aligned arrays.

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Aug
2017

Programmable, reversible and repeatable wrinkling of shape memory polymer (SMP) thin films on elastomeric polydimethylsiloxane (PDMS) substrates is realized, by utilizing the heat responsive shape memory effect of SMPs. The dependencies of wrinkle wavelength and amplitude on program strain and SMP film thickness are shown to agree with the established nonlinear buckling theory. The wrinkling is reversible, as the wrinkled SMP thin film can be recovered to the flat state by heating up the bilayer system.

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Jul
2017

A ruthenium pincer catalyst has been shown to be highly efficient for the hydrogenation of a wide range of α-ketimino esters derived from α-keto esters and chiral 2-methylpropyl-2-sulfinamide, affording chiral aryl glycine derivatives with high yields and diasteroselectivities (20 examples, dr values up to 99 : 1).

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Mar
2017

Iridacycles for hydrogenation and dehydrogenation reactions.

Chem Commun (Camb) 2017 Mar 10;53(24):3399-3411. Epub 2017 Mar 10.
Chao Wang, Jianliang Xiao
Iridacycles are a group of cyclometalated metal complexes, which have recently been shown to be versatile catalysts for a range of reactions. This Feature Article provides an account of the work carried out by our groups. We start with an introduction to the variety of iridacycles and how they entered into catalysis.

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Nov
2016

Physiological mechano-acoustic signals, often with frequencies and intensities that are beyond those associated with the audible range, provide information of great clinical utility. Stethoscopes and digital accelerometers in conventional packages can capture some relevant data, but neither is suitable for use in a continuous, wearable mode, and both have shortcomings associated with mechanical transduction of signals through the skin. We report a soft, conformal class of device configured specifically for mechano-acoustic recording from the skin, capable of being used on nearly any part of the body, in forms that maximize detectable signals and allow for multimodal operation, such as electrophysiological recording.

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Mar
2017

Binuclear copper complex [{Cu(Sal)(NCMe)}] (Sal=salicylate) was found to be an active catalyst for the aerobic oxidation of N-aryl tetrahydroisoquinolines to the corresponding iminium ions, which could be trapped by a wide range of nucleophiles to form coupled products. The reactions took place under 1 bar of Oat room temperature with 1 mol % of the copper catalyst being sufficient in most cases, and are considerably accelerated by catalytic chloride anions. Mechanistic studies show that the Cudimer oxidizes the amine to the iminium ion, and this two-electron process requires O, whereby the resulting Cuis concomitantly reoxidised back to Cu.

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Mar
2017

N-Aryl tetrahydroisoquinolines were oxidised to dihydroisoquinolones through the relay catalysis of a binuclear paddle-wheel copper complex and a vitamin B1 analogue with oxygen as oxidant. Mechanistic studies revealed that the copper catalyst oxidises amines to the corresponding iminium salts, which are then oxygenated to lactam products by catalysis of the vitamin B1 analogue.

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Dec
1969

Transfer Hydrogenation in Water.

Chem Rec 2016 12 17;16(6):2768-2782. Epub 2016 Oct 17.
Xiaofeng Wu, Chao Wang, Jianliang Xiao
This article provides an account of our group's efforts in developing aqueous-phase transfer hydrogenation reactions. It is comprised of mainly two parts. The first part concentrates on asymmetric transfer hydrogenation in water, enabled by Noyori-Ikariya catalysts, while the second part is concerned with the achiral version of the reaction catalysed by a new class of catalysts, iridacycles.

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Oct
2016

An efficient synthesis of α-acylphosphoranes by palladium-catalyzed carbonylation of aryl iodides with carbon monoxide and stabilized phosphonium ylides has been developed. Featuring 44 examples, the protocol displayed a wide substrate scope under mild reaction conditions, showcasing its potential in synthetic organic chemistry.

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Aug
2016

A novel and efficient protocol for the synthesis of amides is reported which employs a BODIPY catalyzed oxidative amidation reaction between aromatic aldehydes and amines under visible light. Compared with the known Ru or Ir molecular catalysts and other organic dyes, the BODIPY catalyst showed higher reactivity toward this reaction. Mechanistic studies reveal that dioxygen could be activated through an ET and a SET pathway, forming active peroxides in situ, which are vital for the key step of the reaction, i.

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Jul
2016

A series of new Ir(III) complexes with carbene ligands that contain a range of benzyl wingtip groups have been prepared and fully characterised by NMR spectroscopy, HRMS, elemental analysis and X-ray diffraction. All the complexes were active in the acceptorless dehydrogenation of alcohol substrates in 2,2,2-trifluoroethanol to give the corresponding carbonyl compounds. The most active complex bore an electron-rich carbene ligand; this complex was used to catalyse the highly efficient and chemoselective dehydrogenation of a wide range of secondary alcohols to their respective ketones, with turnover numbers up to 1660.

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May
2016

By the use of 1-chloro-1,2-benziodoxol-3-one, an age-old reagent, the practical and efficient chlorination method is achieved. This hypervalent iodine reagent is amenable not only to the chlorination of nitrogen-containing heterocycles but also to selected classes of arenes, BODIPY dyes, and pharmaceuticals. In addition, the advantages, such as easy preparation and recyclable, air- and moisture-stable, in combination with the success in a gram-scale experiment grant this reagent great potential for industrial application.

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Apr
2016

Formulations and applications of micro- and nanoscale polymer particles have proliferated rapidly in recent years, yet knowledge of their mechanical behavior has not grown accordingly. In this study, we examine the ways that compressive strain, substrate surface energy, and particle size influence the shape memory cycle of polystyrene particles. Using nanoimprint lithography, differently sized particles are programmed into highly deformed, temporary shapes in contact with substrates of differing surface energies.

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Nov
2015

The mechanism of imine reduction by formic acid with a single-site iridicycle catalyst has been investigated by density functional theory (DFT), NMR spectroscopy, and kinetic measurements. The NMR and kinetic studies suggest that the transfer hydrogenation is turnover-limited by the hydride formation step. The calculations reveal that, amongst a number of possibilities, hydride formation from the iridicycle and formate probably proceeds by an ion-pair mechanism, whereas the hydride transfer to the imino bond occurs in an outer-sphere manner.

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Jun
2015

An efficient catalytic system for the alkylation of amines with either alcohols or amines under mild conditions has been developed, using cyclometallated iridium complexes as catalysts. The method has broad substrate scope, allowing for the synthesis of a diverse range of secondary and tertiary amines with good to excellent yields. By controlling the ratio of substrates, both mono- and bis-alkylated amines can be obtained with high selectivity.

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Jul
2015

A mild and operationally simple iron-catalyzed protocol for the selective aerobic oxidation of aromatic olefins to carbonyl compounds is described. Catalyzed by a Fe(III) species bearing a pyridine bisimidazoline ligand at 1 atm of O2, α- and β-substituted styrenes were cleaved to afford benzaldehydes and aromatic ketones generally in high yields with excellent chemoselectivity and very good functional group tolerance, including those containing radical-sensitive groups. With α-halo-substituted styrenes, the oxidation took place with concomitant halide migration to afford α-halo acetophenones.

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May
2015

The first allylic carbonylation reaction of allylic acetates with aryl boronic acids under carbon monoxide has been developed. Using Pd-PCy3 as a catalyst, a wide spectrum of allylic acetates was carbonylated in the presence of various aryl boronic acids, affording α,β-unsaturated aryl ketones in good to excellent yields. Preliminary studies indicate that carbon monoxide always inserts at the least substituted terminal allylic carbon and the resulting β,γ-unsaturated aryl ketones generally isomerise to the ketones obtained.

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Apr
2015

A new strategy has been developed for the oxidant- and base-free dehydrogenative coupling of N-heterocycles at mild conditions. Under the action of an iridium catalyst, N-heterocycles undergo multiple sp(3) CH activation steps, generating a nucleophilic enamine that reacts in situ with various electrophiles to give highly functionalized products. The dehydrogenative coupling can be cascaded with Friedel-Crafts addition, resulting in a double functionalization of the N-heterocycles.

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Mar
2015

A cyclometalated iridium complex is shown to catalyse the transfer hydrogenation of various nitrogen heterocycles, including but not limited to quinolines, isoquinolines, indoles and pyridinium salts, in an aqueous solution of HCO2H/HCO2Na under mild conditions. The catalyst shows excellent functional-group compatibility and high turnover number (up to 7500), with catalyst loadings as low as 0.01 mol % being feasible.

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Sep
2014

Cyclometalated iridium complexes are shown to be highly efficient and chemoselective catalysts for the transfer hydrogenation of a wide range of carbonyl groups with formic acid in water. Examples include α-substituted ketones (α-ether, α-halo, α-hydroxy, α-amino, α-nitrile or α-ester), α-keto esters, β-keto esters and α,β-unsaturated aldehydes. The reduction was carried out at substrate/catalyst ratios of up to 50 000 at pH 4.

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Jul
2014

The first examples of a Pd-catalyzed carbonylation of aryl boronic acids with sp(3) carbon partners are presented. Various boronic acids were shown to react with 1,3-diesters and 1,3-diketones to afford structurally unique carbonyl compounds. By employing 2-substituted 1,3-diesters, synthetically-challenging quaternary carbon centres were accessed.

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Jun
2014

Selective α-oxidation of ethers under aerobic conditions is a long-pursued transformation; however, a green and efficient catalytic version of this reaction remains challenging. Herein, we report a new family of iron catalysts capable of promoting chemoselective α-oxidation of a range of ethers with excellent mass balance and high turnover numbers under 1 atm of O2 with no need for any additives. Unlike metalloenzymes and related biomimetics, the catalyst produces H2 as the only byproduct.

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Mar
2014

Chiral molecules, such as alcohols, are vital for the manufacturing of fine chemicals, pharmaceuticals, agrochemicals, fragrances, and novel materials. These molecules need to be produced in high yield and high optical purity and preferentially catalytically. Among all the asymmetric catalytic reactions, asymmetric hydrogenation with H2 (AH) is the most widely used in the industry.

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Jan
2014

Cyclometalated iridium complexes are found to be versatile catalysts for the direct reductive amination (DRA) of carbonyls to give primary amines under transfer-hydrogenation conditions with ammonium formate as both the nitrogen and hydrogen source. These complexes are easy to synthesise and their ligands can be easily tuned. The activity and chemoselectivity of the catalyst towards primary amines is excellent, with a substrate to catalyst ratio (S/C) of 1000 being feasible.

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Mar
2014

A highly effective visible light-promoted "radical-type" coupling of N-heteroarenes with aryldiazonium salts in water has been developed. The reaction proceeds at room temperature with [Ru(bpy)3 ]Cl2 ⋅6 H2 O as a photosensitizer and a commercial household light bulb as a light source. Pyridine and a variety of substituted pyridines are effective substrates under these reaction conditions, and only monosubstituted products are formed with different regioselectivities.

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Jan
2014

DMSO methylates a broad range of amines in the presence of formic acid, providing a novel, green and practical method for amine methylation. The protocol also allows the one-pot transformation of aromatic nitro compounds into dimethylated amines in the presence of a simple iron catalyst.

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Jan
2014

An unprecedented Rh-catalyzed direct methylation of ketones with N,N-dimethylformamide (DMF) is disclosed. The reaction shows a broad substrate scope, tolerating both aryl and alkyl ketones with various substituents. Mechanistic studies suggest that DMF delivers a methylene fragment followed by a hydride in the methylation process.

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Dec
1969

We created graphene blisters that cover and seal an annular cylinder-shaped microcavity in a SiO2 substrate filled with a gas. By controlling the pressure difference between the gas inside and outside of the microcavity, we switch the graphene membrane between multiple stable equilibrium configurations. We carried out experiments starting from the situation where the pressure of the gas inside and outside of the microcavity is set equal to a prescribed charging pressure, p0 and the graphene membrane covers the cavity like an annular drum, adhered to the central post and the surrounding substrate due to van der Waals forces.

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Feb
2014

The direct deformation and shape recovery of micron-sized polystyrene particles via nanoimprint lithography is reported. The recovery of the programmed PS particles can be utilized to create a range of smart Janus particles with contrasting properties in conductivity and topography, by use of metal-layer constrained recovery.

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Dec
1969

Asymmetric reductive amination (ARA) affords synthetically valuable chiral amines straightforwardly. This chapter reviews the recent advances made in the area, focusing on ARA by hydrogenation, transfer hydrogenation, organocatalytic reduction, and biocatalytic reduction.

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Oct
2013

Asymmetric hydrogenation of imines leads directly to chiral amines, one of the most important structural units in chemical products, from pharmaceuticals to materials. However, highly effective catalysts are rare. This article reveals that combining an achiral pentamethylcyclopentadienyl (Cp*)-iridium complex with a chiral phosphoric acid affords a catalyst that allows for highly enantioselective hydrogenation of imines derived from aryl ketones, as well as those derived from aliphatic ones, with ee values varying from 81 to 98 %.

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Sep
2013

A cyclometallated iridium complex containing an imino ligand has been shown to catalyse the hydrogenation of imines. The catalyst is highly active and selective for imino bonds, with a wide variety of imines being hydrogenated in less than 1 hour at a substrate/catalyst (S/C) ratio of 2000 at 20 bar H2 pressure and 75 °C.

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Aug
2013

Cyclometallated Cp*Ir(N^C)Cl complexes derived from N-aryl ketimines are highly active catalysts for the reduction of N-heterocycles under ambient conditions and 1 atm H2 pressure. The reaction tolerates a broad range of other potentially reducible functionalities and does not require the use of specialised equipment, additives or purified solvent.

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Jun
2013

Levulinic acid (LA) is transformed into pyrrolidinones via iridium-catalysed reductive amination using formic acid as the hydrogen source under aqueous conditions. The catalytic system is the most active and performs under the mildest conditions ever reported for the reductive amination of LA.

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May
2013

In arthropods, evolution has created a remarkably sophisticated class of imaging systems, with a wide-angle field of view, low aberrations, high acuity to motion and an infinite depth of field. A challenge in building digital cameras with the hemispherical, compound apposition layouts of arthropod eyes is that essential design requirements cannot be met with existing planar sensor technologies or conventional optics. Here we present materials, mechanics and integration schemes that afford scalable pathways to working, arthropod-inspired cameras with nearly full hemispherical shapes (about 160 degrees).

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May
2013

We present a unique experimental configuration that allows us to determine the interfacial forces on nearly parallel plates made from the thinnest possible mechanical structures, single and few layer graphene membranes. Our approach consists of using a pressure difference across a graphene membrane to bring the membrane to within ~10-20 nm above a circular post covered with SiOx or Au until a critical point is reached whereby the membrane snaps into adhesive contact with the post. Continuous measurements of the deforming membrane with an AFM coupled with a theoretical model allow us to deduce the magnitude of the interfacial forces between graphene and SiOx and graphene and Au.

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Mar
2013

Reductive amination of various ketones and aldehydes by transfer hydrogenation under aqueous conditions has been developed, by using cyclometallated iridium complexes as catalysts and formate as hydrogen source. The pH value of the solution is shown to be critical for a high catalytic chemoselectivity and activity, with the best pH value being 4.8.

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Dec
1969

Strain engineered graphene has been predicted to show many interesting physics and device applications. Here we study biaxial compressive strain in graphene/hexagonal boron nitride heterostructures after thermal cycling to high temperatures likely due to their thermal expansion coefficient mismatch. The appearance of sub-micron self-supporting bubbles indicates that the strain is spatially inhomogeneous.

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Jan
2013

Cyclometalation of [Cp*IrCl(2)](2) with ketimine ligands generated very active catalysts for transfer hydrogenation of imines as well as reductive amination. The synthesis and X-ray diffraction structures of three such complexes are disclosed in this paper. The hydrides of two complexes, key intermediates in hydrogenation, have been isolated and their structures determined by X-ray diffraction as well.

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May
2012

A new ferrocenyl oxazaphospholidine oxide 3 was synthesized together with its P-epimer 2 in the reaction of ferrocene lithium with phosphoramidite chloride 1. 3 was successfully derivatized into planar chiral 1,2-ferrocenes, including phosphine ligands, via highly diastereoselective ortho-lithiation and subsequent functionalization; these compounds display opposite planar chirality to those obtained from 2. Some of these 1,2-ferrocenes were further lithiated, allowing for the introduction of a free phosphine group at the oxazaphospholidine ring.

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