The highly efficient synthesis of chiral indolines fused with an azabicyclo[2.2.1]heptanone moiety is achieved by an asymmetric dearomatization reaction of indoles with cyclobutanones. A new chiral imidodiphosphorimidate (IDPi) catalyst is synthesized and exhibits extraordinary activity in promoting a cascade Friedel-Crafts/semipinacol rearrangement. Target molecules are prepared in good yields (up to 95%) with excellent enantioselectivity (up to 98% ee) with operational convenience. Combined experimental and computational studies provide detailed mechanistic insights into the energy landscape and origin of the stereochemical induction of the reaction.

A one-pot, dehydrogenation-based Ir/Co/Cu triple catalysis has been developed for formal asymmetric borylation of homobenzylic C(sp(3))-H bonds, furnishing enantioenriched organoboronates with a beta-stereocenter directly from simple arylalkanes. Mechanistic studies indicate that the Ir catalyst is responsible for dehydrogenation of arylalkanes to 1-arylalkenes, followed by Cu-catalyzed regio- and enantioselective protoboration of (E)-arylalkenes; the introduction of Co-catalyzed stereoisomerization of the (Z)-alkenes to (E)-isomers was found to have a beneficial effect on the productivity and enantioselectivity.

We report herein that nickel-mediated trifluoromethylation of chlorinated and brominated phenol derivatives ClArOTs and BrArOTf gave chloro(bromo)trifluoromethylarenes through the chemoselective cleavage of Ar-O bonds. Furthermore, under similar reaction conditions, the chemoselective trifluoromethylation of Ar-Cl and Ar-Br bonds of ClArOPiv and BrArOTs was achieved to give trifluoromethylated phenol derivatives.

Dearomatization of indole derivatives offers a straightforward approach to accessing the indoline framework. However, highly efficient dearomatization of indoles bearing electron-deficient groups remains underdeveloped. Herein, a nickel-catalyzed intermolecular hydroalkylative dearomatization reaction of indoles with simple alkyl bromides through a single-electron-transfer process is reported. A wide variety of indole derivatives bearing various functional groups were compatible with this protocol and reacted with primary, secondary, or tertiary alkyl bromides to afford a series of indolines in good yields (up to 82%) and with excellent diastereoselectivity (up to >20:1). Notably, a nickel-mediated hydrogen-atom-transfer process was observed when terminal alkyl bromides were employed as the radical precursors, which resulted in branched products.

Research on the genus Streptacidiphilus was mainly focused on the isolation and identification of new species, with relatively less emphasis on the study of secondary metabolites. A new aluminium-complex alumioxamine (3), and two known compounds desferrioxamine E (1) and ferrioxamine E (2) were isolated from the fermentation broth of Streptacidiphilus jiangxiensis CGMCC 4.1857. Their structures were elucidated by MS, IR, NMR and single crystal X-ray diffraction technologies. Structurally, compound 3 features aluminum(III) as the central atom, which is bonded to six oxygen atoms of the ligand, forming a hexadentate complex. Furthermore, in vitro cytotoxicity assays showed that compound 1 exhibited potential inhibitory activity against four human tumor cell lines (Hela, PANC1, A375 and MHCC-97H) at a concentration of 100 mu mol/L with cell viability ranging from 4.8% to 66.4%.

The conversion of C1 molecules, COx (CO and CO2), to valuable chemical products has garnered ever-increasing attention. Among many routes, the hydrogenation via thermal catalysis is particularly promising as a key clean energy technology with the increasing supply of green H-2. Zinc-based mixed oxide catalysts exhibit exceptional catalytic performance in the COx hydrogenation to value-added hydrocarbons, especially in combination with zeolite. This review overviews the recent achievements in understanding the active sites and reaction mechanisms of COx hydrogenation on zinc-based mixed oxide catalysts, focusing on three most-studied zinc-based mixed oxide catalysts, namely ZnCrOx, ZnAlOx and ZnZrOx. The challenges and future directions are also discussed.

Chiral phosphine-catalyzed asymmetric (4+2) annulation of the amide-based Morita-Baylis-Hillman (MBH) carbonates with beta,gamma-unsaturated butenolides has been developed to give enantiomer-enriched bicyclic delta-lactam gamma-butyrolactone compounds. The amide-based MBH carbonates were first used as acceptor and aza-C4 synthon in phosphine catalysis. Under mild reaction conditions, a variety of amide-based MBH carbonates and unsaturated butenolides were well tolerated to provide chiral bicyclic delta-lactam gamma-butyrolactone derivatives in high yields with excellent enantioselectivities as well as diastereoselectivities. A plausible reaction mechanism was also proposed based on control experiments and DFT calculations.

Improving fluorescence emission efficiency is essential to develop novel luminescent materials. However, the low water solubility of conventional fluorescent dyes is a serious obstacle to broadening the application scope. Herein, a green protocol have been proposed: Two poorly water-soluble naphthalimide derivatives MONI and MANI with high fluorescent quantum yields (larger than 0.95 in toluene solution) were loaded in three different sizes of cyclodextrin (CD; alpha, beta, gamma-CD) with high water solubility. To further check the feasibility of the proposal, density functional theory (DFT) and time dependent-DFT (TD-DFT) methods combining the Own N-layer Integrated molecular Orbital molecular Mechanics (ONIOM) model with dispersion correction were employed to investigate the geometric and electronic structures of complexes CDMXNI (X = N, O) in the excited-state process. TD-DFT calculations predict that the fantastic emission behavior of MXNI can be reserved after binding with CD, even improving fluorescent intensity in aqueous solution. Basis set superposition error (BSSE) correction and symmetry adapted perturbation theory (SAPT) were adopted to estimate the complexation energies and weak noncovalent interactions. The middle-sized beta-CD is the perfect candidate to allow fluorescent molecules to settle into its cavity, forming an inclusion complex. Energy decomposition analysis (EDA) indicates that dispersion is superior to electrostatics interaction in embedding-type beta-CDMXNI, while it is contrary in alpha,gamma-CDMXNI. NMR calculations further prove the existence of a strong intermolecular hydrogen bond interaction between host and guest. Weak interactions that limited molecular vibration and hampered the nonradiative inactivation channel are conducive to the enhanced emission intensity.

Divergent and selective synthesis has been widely achieved in transition-metal-catalyzed reactions through a ligand property tuning strategy. However, ligand-loading-controlled divergent synthesis has rarely been reported. Due to changes in ligand loading, different metal complexes should be formed and exhibit diverse catalytic properties. Herein, we disclose a Ni/photoredox-catalyzed divergent and selective coupling between redox-active methylenecyclopropanes and aryl bromides through ligand loading adjustment, providing ranges of alkyne derivatives and dibenzylethylene derivatives. Two different catalytic cycles are proposed to demonstrate the generation of two sets of products, where homopropargyl radicals and nickelacyclobutane species should be crucial intermediates in the corresponding catalytic cycle, respectively. Diverse alkyne and dibenzylethylene derivatives were obtained via selective coupling of redox-active MCPs and ArBr under Ni/photoredox catalysis. The nickel/ligand loading tuning method played a crucial role in this divergent synthesis protocol.

Asymmetric hydrogenation of carbon rings in (hetero)arenes is one of the most direct and efficient methods for preparing saturated and partially saturated chiral six membered carbon ring compounds. While significant challenges in terms of low reactivity and selectivity remain, some breakthroughs have been made in this field of carbocycle-selective asymmetric hydrogenation of (hetero)arenes in recent years. The research progress of transition metal catalyzed carbocycle-selective asymmetric hydrogenation of (hetero)arenes in the past few decades is summarized, and the prospects of further developments are also discussed.

Tertiary alcohols with adjacent nucleophilic labile groups are prevalent in bioactive molecules but are challenging to synthesize. Herein we introduce a direct, protecting group-free method to access alpha-tertiary hydroxy oximes via photochemical 1,3-boronate rearrangement. This reaction delivers high yields (up to 94%) using readily available boronic acids, is scalable to gram quantities, and allows for further derivatization to other nitrogen-containing molecules.

A hypervalent iodine-reagent-based C-H functionalization strategy was utilized to synthesize diaryl ethers. This method directly transforms various arenes into their corresponding diaryliodonium salts, followed by a C-O coupling reaction to produce structurally diverse diaryl ethers. The efficacy of this approach in the late-stage structural modifications of complex molecules was demonstrated.

The transition metal-catalyzed meta-C-H functionalization of alcohols and their hydroxylamine derivatives remains underdeveloped. Herein, we report an efficient meta-C-H arylation of both phenylethyl and benzylic alcohols and their hydroxylamine derivatives using a readily removable oxime ether directing group. Using electronically activated 2-carbomethoxynorbornene as the transient mediator and 3-trifluoromethyl-2-pyridone as the enabling ligand, this reaction features a broad substrate scope and good functional group tolerance. More importantly, with this oxime-directed meta-C-H functionalization, this method provides a dual approach for efficient access to both meta-substituted alcohols and hydroxylamines using two sets of simple deprotection conditions. This protocol leads to the efficient synthesis of bioactive compounds possessing promising reactivities for the treatment of pulmonary fibrosis.

Living crystallization-driven self-assembly (CDSA) has emerged as an efficient strategy to generate nanofibers of pi-conjugated polymers (CPNFs) in a controlled fashion. However, reports of donor-acceptor (D-A) heterojunction CPNFs are extremely rare. The preparation of these materials remains a challenge due to the lack of rational design guidelines for the D-A pi-conjugated units. Herein, we report a versatile CDSA strategy based upon carefully designed D-A-co-oligomers in which electron-deficient benzothiadiazole (BT) or dibenzo[b,d]thiophene 5,5-dioxide (FSO) units are attached to the two ends of an oligo(p-phenylene ethynylene) heptamer [BT-OPE7-BT, FSO-OPE7-FSO]. This arrangement with the electron-deficient groups at the two ends of the oligomer enhances the stacking interaction of the A-D-A pi-conjugated structure. In contrast, D-A-D structures with a single BT in the middle of a string of OPE units disrupt the packing. We employed oligomers with a terminal alkyne to synthesize diblock copolymers BT-OPE7-BT-b-P2VP and BT-OPE7-BT-b-PNIPAM (P2VP = poly(2-vinylpyridine), PNIPAM = poly(N-isopropylacrylamide)) and FSO-OPE7-FSO-b-P2VP and FSO-OPE7-FSO-b-PNIPAM. CDSA experiments with these copolymers in ethanol were able to generate CPNFs of controlled length by both self-seeding and seeded growth as well as block comicelles with precisely tunable length and composition. Furthermore, the D-A CPNFs with a BT-OPE7-BT-based core demonstrate photocatalytic activity for the photooxidation of sulfide to sulfoxide and benzylamine to N-benzylidenebenzylamine. Given the scope of the oligomer compositions examined and the range of structures formed, we believe that the living CDSA strategy with D-A-based co-oligomers opens future opportunities for the creation of D-A CPNFs with programmable architectures as well as diverse functionalities and applications.