Pd-catalyzed asymmetric allylic C−H functionalization has emerged as a powerful tool to access chiral, densely functionalized molecules from easily ac-cessible alkenes, enabling the increase of the step- or atom-economy by minimizing functional group manipulations for preparing allylating reagents. Due to the inadequacy of stereoselection strategies, the asymmetric allylic C-H functionalization is still in the early stage. In this essay, we will describe our journey to identification of asymmetric catalytic systems, mechanism of allylic C−H activation, control of stereo- and regioselectivity, and applica-tions in asymmetric synthesis.

The utilization of cyclobutanones as the synthon in transition metal catalysis has been made great success. Because C(carbonyl)−C bond of cyclobutanones can be cleaved through strain release. Despite those advancements, the main catalysts in literature are Rh catalysts or Ni catalysts and the reaction with C–H bond is still underdeveloped. Herein, we realized the first palladium-catalyzed skeletal reorganisation of cyclobutanones invoving successive cleavage of C(carbonyl)−C bonds and C−H bond cleavage, which con-stitutes an rapid access to diverse indanones.

The [2.2]paracyclophane-derived oxazole-pyrimidine ligands with planar chirality (PYMCOX) were designed, synthesized and successfully applied in nickel-catalyzed asymmetric 1,2-reduction of α,β-unsaturated ketones, affording the chiral allylic alcohols with up to 99% yield and 99% ee. Meanwhile, this reduction reaction could be conducted on gram-scale without loss of activity and enantioselectivity, and the chiral ligand could be conveniently recovered with high yield.

A straightforward electrochemical hydrogenation of benzo[b]thiophene 1,1-dioxides with HFIP as the hydrogen donor has been re-ported in an undivided cell under metal-free conditions. Moreover, the tolerance of various functional groups and scaled-up experi-ments showed the practicability and potential applications of this methodology.

A phosphine-catalyzed [4+3] annulation between dinucleophilic indole derivatives and Morita−Baylis−Hillman (MBH) carbonates was discovered by using the N1 and N4′ or C4′ nucleophilicities of indole precursors, which provides an efficient and facile access to in-dole-1,2-fused 1,4-diazepinones and azepines in good to high yields in one step, in which indoles act as four atom synthons. Various transformations of products illustrate promising applications of the given protocols.

Besides serving as therapeutic agents and building blocks for glycoprotein synthesis, homogeneous synthetic glycopeptides also benefit understanding function of specific glycoform. However, the selectivity coupling of oligosaccharides to a given peptide remains challenging despite the fact that the synthesis of structure-defined complex oligosaccharides has been greatly facilitated by chemoenzymatic based approaches. Herein, a Ca2+-promoted glycosylation approach was developed to exclusively modify phenolic peptide using a panel of biologically important glycans.

Long-wavelength fluorescence of carbon dots (CDs) show the great importance in multiple fields, especially for the biochemical sensing. Here we proposed one type of CDs doped with nitrogen and sulfur through the hydrothermal method, which exhibited the obvious yel-low-fluorescence in aqueous. Importantly, their fluorescence intensity of CDs decreased with pH decreasing in the acidic range, thus a linear relationship between pH and fluorescence intensity was established, and exhibiting the potential of pH sensing. Additionally, in-troducing tigecycline into CDs resulted in their decreased fluorescence, thus we further established a strategy of detecting tigecycline with the concentration range of 200 μM to 7 nM. Meanwhile, we elucidated the static quenching as the major mechanism for CDs responding tigecycline, which was induced by the formed new complex between CDs and tigecycline. Furthermore, the practicality of the method was verified by examining the recovery of tigecycline in the actual lake-water samples.

Herein we report a condition-controlled divergent synthesis of spiro indene-2,1’-isoindolinones and spiro isochroman-3,1’-isoindolinones through cobalt-catalyzed formal [4 + 1] and [4 + 1 + 1] spirocyclization of aromatic amides with 2-diazo-1H-indene-1,3(2H)-dione. When the reaction is carried out under air in ethyl acetate, spiro indene-2,1’-isoindolinones are formed through Co(II)-catalyzed C−H/N−H [4 + 1] spirocyclization. When the reaction is run under O2 in CH3CN, on the other hand, spiro isochroman-3,1’-isoindolinones are generated through Baeyer-Villiger oxidation of the in situ formed spiro indene-2,1’-isoindolinones with O2 as a cheaper and environmental-friendly oxygen source. In general, these protocols have advantages such as using non-precious and earth-abundant metal catalyst, no extra additive, high efficiency and regioselectivity. A gram-scale synthesis and the removal of the directing group further highlight its utility.

Hydrogen bonding is a vital driving force for organizing the hierarchy molecular structure, especially in biologic field. Due to its directionality, selectivity and moderate strength, hydrogen bonding has been extensively introduced into the molecular recognition, sensing and electronic devices. Electric meas-urements at single-molecule level facilitate the investigation of hydrogen bonds and provide a comprehensive understanding of the electron transport properties governed by the hydrogen bonding, which is essential for the development of self-assembled electronic systems. This review provides a de-tailed overview of recent advancements in constructing single-molecule junctions utilizing intramolecular and intermolecular hydrogen bonding. We first introduce the methods utilized for characterizing the electric and dynamic properties of non-covalent interactions. Next, we discuss the mechanisms of electron transport, relevant influencing factors, and typical applications utilizing electrical signals based on single-molecule junctions. Finally, we propose our perspective on the existing challenges and prospective opportunities in utilizing hydrogen bonding for electronic device applications.

Nickel(II) complexes with pyrazole-based ligands are widely employed in catalysis of ethylene oligomerization and subsequent Friedel-Crafts alkylation of toluene. We have prepared ten new nickel(II) dibromide complexes with various substituted bis(azolyl)methanes. They have been characterized using 1H NMR, IR, high resolution mass spectrometry and elemental analysis. The structures of three complexes have been unambiguously established using X-ray diffraction. It was found that these complexes in the presence of Et2AlCl or Et3Al2Cl3 are active both in ethylene oligomerization and Friedel-Crafts alkylation processes (activity up to 3720 kgoligomer·mol[Ni]−1·h−1). The use of Et3Al2Cl3 results in the higher share of alkylated products (up to 60%). Moreover, catalytic systems activated with Et3Al2Cl3 produced small amounts of odd carbon number olefins (up to 0.8%). The Friedel-Crafts alkylation was used as a trap for previously undetected short-chain odd carbon number olefins (C3 and C5).

A transition-metal free three-component coupling reaction of azaindoles, C60, and bromoalkanes/triphenylamines has been developed to provide an efficient access to diverse azaindole functionalized 1,4-C60 adducts. This protocol exhibits low cost, operational-simplicity, wide substrate scope, and mild and convenient conditions.

A transition-metal-free one-pot direct synthesis of tetrathiophosphates (R1S)2P(S)SR2 from white phosphorus (P4), through inter-mediate S-sodium S,S-dialkylphosphorotetrathioates (R1S)2P(S)SNa, is presented. In the presence of NaSH, various disulfides such as diaryl disulfides and dialkyl disulfides are easily coupled with P4 to give S-sodium S,S-dialkylphosphorotetrathioates (R1S)2P(S)SNa in almost quantitative yield, which react with alkyl halides in one pot to generate (R1S)2P(S)SR2. Furthermore, S-(2-cyanoethyl)-substituted tetrathiophosphates (R1S)2P(S)SCH2CH2CN are successfully designed as a kind of tetrathiophosphorylation reagents to react with diaryl iodonium salts involving deprotection-dealkylation process.

The stereoselective preparation of fullerene bis-adducts through nontethered methods remains difficult due to the significant amount of regioisomers produced. The trans-4 aziridino[60]fullerenes, C60(NC6H4R)n (n = 1 or 2, R = OMe, OEt, OBu), were selectively synthesized even without a catalyst by reacting octabromofullerene with the corresponding aniline. Nuclear magnetic resonance spectroscopy, UV-vis spectroscopy, and X-ray structural analysis provided convincing characterization of the compounds. A possible reaction process was proposed to clarify the synthesis of highly regioselective trans-4-bisaziridino[60]fullerenes. The possible use of these aziridino[60]fullerene derivatives as propellant stabilizers was also explored.

In recent years, there has been a shift towards using nonfullerene electron acceptors in organic solar cells (OSCs) as a replacement for fullerene derivatives. This change requires polymer donors that possess compatible physical properties, such as absorption range, HOMO energy level, miscibility, and crystallinity. Moreover, the high cost and poor batch-to-batch reproducibility of polymer donors also hinder future large-scale manufacturing. These emphasize the need to explore alternative types of polymer donors. The imide-functionalized building units possess several key attributes that make their polymers highly promising for non-fullerene OSCs. These attributes include ease of synthesis, strong electron-withdrawing ability, rigid and co-planar structure, and the ability to easily tune solubility through imide side chains. In this review, we summarized the synthetic routes of imide building units, and the struc-tural evolution of imide-functionalized polymer donors by focusing on the effects of polymer structure on their physical, optoelec-tronic, and photovoltaic properties. We hope that this mini-review will serve as a catalyst for future research on imide-functionalized polymers toward high-performance, cost-effective, and durable organic solar cells (OSCs).

A photo-triggered cascade cyclization of silyl enolate to prepare angularly fused tricyclic scaffold is developed. The reaction demonstrates good substrate scope and stereo-selectivity. The excellent stereo- and regio-selectivity for this cascade reaction is elucidated via conformational analysis and DFT calculation, respectively.

We developed a novel Pd-catalyzed [4 + 4] cycloaddition of benzofuran-derived azadienes with homo-TMM all-carbon 1,4-dipoles in situ generated from α-allyl malonate derivatives, affording an array of benzofuro[3,2-b]azocines with good to excellent yields (up to 96%) and exclusive regioselectivities. This methodology featured mild reaction conditions and good functional group tolerance. The synthetic utility was demonstrated by a gram-scale reaction. Furthermore, the catalytic asymmetric [4 + 4] cycloaddition version has also been explored.

We herein report a simple ether-directed iridium-catalyzed site- and enantioselective C(sp2)-H borylation of benzhydryl ethers for the first time. Various chiral benzhydryl ethers were obtained with high enantioselectivities in the presence of a tailor-made chiral bi-dentate boryl ligand. We found that the kinetic resolution relay significantly amplified the enantioselectivity. The synthetic utility of the current method was demonstrated by gram-scale C-H borylation and C-B bond transformations.

Cathode interlayers (CILs) play an essential role in achieving efficient organic solar cells (OSCs). However, the electronic structure at the electrode/CIL/active layer interfaces and the underlying mechanisms for electron collection remain unclear, which becomes a major obstacle to develop high-performance CILs. Herein, we investigate the relationship of the electron collection abilities of four cross-linked and n-doped CILs (c-NDI:P0, c-NDI:P1, c-NDI:P2, c-NDI:P3) with their electronic structure of space charge region at hetero-junction interface. By accurately calculating the depletion region width according to the barrier height, doping density and permittivi-ty, we put forward that the optimal thickness of CIL should be consistent with the depletion region width to realize the minimum en-ergy loss. As a result, the depletion region width is largely reduced from 13 nm to 0.8 nm at the indium tin oxide (ITO)/c-NDI:P0 in-terface, resulting in a decent PCE of 17.7% for the corresponding inverted OSCs.