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By using biphenyl-2-ylphosphines functionalized with a remote tertiary amino group as a ligand, readily available acetylenic amides are directly converted into 2-aminofurans devoid of any electron-withdrawing and hence deactivating/stabilizing substituents. These highly electron-rich furans have rarely been prepared, let alone applied in synthesis, because of their high reactivities and low stabilities associated with the electron-rich nature of the furan ring. In this work, these reactive furans smoothly undergo either in situ intermolecular Diels-Alder reactions to deliver highly functionalized/substituted aniline products or intramolecular ones to furnish carbazole-4-carboxylates in mostly good to excellent yields. This work offers general and expedient access to this class of little studies electron-rich furans and should lead to exciting opportunities for their applications.

The asymmetric isomerization of alkyne to allene is the most efficient and the completely atom-economic approach to this class of versatile axial chiral structure. However, the state-of-the-art is limited to tert-butyl alk-3-ynoate substrates that possess requisite acidic propargylic C-H bonds. Reported here is a strategy based on gold catalysis that is enabled by a designed chiral bifunctional biphenyl-2-ylphosphine ligand. It permits isomerization of alkynes with nonacidic α-C-H bonds and hence offers a much-needed general solution. With chiral propargylic alcohols as substrates, 2,5-disubstituted 2,5-dihydrofurans are formed in one step in typically good yields and with good to excellent diastereoselectivities. With achiral substrates, 2,5-dihydrofurans are formed with good to excellent enantiomeric excesses. A novel center-chirality approach is developed to achieve a stereocontrol effect similar to an axial chirality in the designed chiral ligand. The mechanistic studies established that the precatalyst axial epimers are all converted into the catalytically active cationic gold catalyst owing to the fluxional axis of the latter.

Fabrics represent a unique platform for seamlessly integrating electronics into everyday experiences. The advancements in functionalizing fabrics at both the single fibre level and within constructed fabrics have fundamentally altered their utility. The revolution in materials, structures, and functionality at the fibre level enables intimate and imperceptible integration, rapidly transforming fibres and fabrics into next-generation wearable devices and systems. In this review, we explore recent scientific and technological breakthroughs in smart fibre-enabled fabrics. We examine common challenges and bottlenecks in fibre materials, physics, chemistry, fabrication strategies, and applications that shape the future of wearable electronics. We propose a closed-loop smart fibre-enabled fabric ecosystem encompassing proactive sensing, interactive communication, data storage and processing, real-time feedback, and energy storage and harvesting, intended to tackle significant challenges in wearable technology. Finally, we envision computing fabrics as sophisticated wearable platforms with system-level attributes for data management, machine learning, artificial intelligence, and closed-loop intelligent networks. [ABSTRACT FROM AUTHOR]

A newly developed P,N-bidentate ligand enables enantioselective intramolecular cyclopropanation by a reactive α-oxo gold carbene intermediate generated in situ. The ligand design is based on our previously proposed structure (with a well-organized triscoordinated gold center) of the carbene intermediate in the presence of a P,N-bidentate ligand. A C2-symmetric piperidine ring was incorporated in the ligand as the nitrogen-containing moiety. A range of racemic transformations of α-oxo gold carbene intermediates have been developed recently, and this new class of chiral ligands could enable their modification for asymmetric synthesis, as demonstrated in this study.

By functionalizing the privileged biphenyl-2-ylphosphine with a basic amino group at the rarely explored 3' position, the derived gold(I) complex possesses orthogonally positioned "push" and "pull" forces, which enable for the first time soft propargylic deprotonation and permit the bridging of a difference of >26 pK(a) units (in DMSO) between a propargylic hydrogen and a protonated tertiary aniline. The application of this design led to efficient isomerization of alkynes into versatile 1,3-dienes with synthetically useful scope under mild reaction conditions.

Most homogenous gold catalyses demand ≥ 0.5 mol% catalyst loading. Owing to the high cost of gold, these reactions are unlikely to be applicable in medium- or large-scale applications. Here we disclose a novel ligand design based on the privileged (1,1'-biphenyl)-2-ylphosphine framework that offers a potentially general approach to dramatically lowering catalyst loading. In this design, an amide group at the 3'-position of the ligand framework directs and promotes nucleophilic attack at the ligand gold complex-activated alkyne, which is unprecedented in homogenous gold catalysis considering the spatial challenge of using ligand to reach anti-approaching nucleophile in a linear P-Au-alkyne centroid structure. With such a ligand, the gold(I) complex becomes highly efficient in catalysing acid addition to alkynes, with a turnover number up to 99,000. Density functional theory calculations support the role of the amide moiety in directing the attack of carboxylic acid via hydrogen bonding.