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.

Protein glycosylation is the most complex and diverse form of post-translational modification in human body. Meanwhile, glycosylation of peptides and proteins emerges as a promising strategy to improve the pharmacokinetic profile of peptide- and protein-based therapeutics. Owing to the importance of protein glycosylation, rigorous evaluation of the relationship between the precise structure and biological function of glycoproteins has to be per-formed. Recently, chemical synthesis, chemoenzymatic synthesis and semisynthesis strategy have attracted extensive attentions towards the prepara-tion of structurally defined glycopeptides and glycoproteins; the obtained synthetic glycoforms thus enable the thorough investigation of specific effects of protein glycosylation. This review highlights the recent progress in the development of novel strategies, preparation of homogeneous glycoproteins and exploration of structure-activity relationships. On this basis, the challenges and prospects are discussed.

Herein, we have developed a strategy of Rh(III)-catalyzed C–H activation of N-nitrosoanilines and iodonium ylides to construct novel tetralydrocarbzol-4-one scaffolds, which provided valuable templates for sequential C-H functionalization such as alkylation, alkenyla-tion, amidation and (hetero)arylation at C5-position of tetralydrocarbzol-4-one with different coupling partners. Gram-scale synthesis and further transformation of tetralydrocarbzol-4-one derivatives to Ondansetron and its analogues demonstrated the utility of this protocol, which enabled the concise and diverse construction of biologically active molecules.

By employing thiazole and 4-chlorothiazole as the A′ units, two A-D-A′-D-A type nonfused-ring electron acceptors (NFREAs) Tz-H and Tz-Cl were designed and synthesized. Replacing thiazole in Tz-H with 4-chlorothiazole can not only remarkably shorten the synthetic route through C-H direct arylation but also enhance molecular planarity with the simultaneous incorporation of S···N and S···Cl non-covalently conformational locks (NoCLs). The photovoltaic devices based on PM6:Tz-Cl exhibited a power conversion efficiency as high as 11.10%, much higher than that of PM6:Tz-H (6.41%), mainly due to more efficient exciton dissociation, better and more balanced carrier mobility, less charge recombination, and more favorable morphology. These findings demonstrate the great potential of NoCLs in achieving low-cost and high-performance NFREAs.

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.

Lobophorins (LOBs) belong to a large family of spirotetronate antibiotics with antibacterial and antitumor activities. In this study, we demonstrated the function of LobP1, a P450 monooxygenase encoded in the LOB biosynthetic gene cluster, by in vivo deletion and in vitro biochemical assays. The disruption of lobP1 led to the isolation of three new LOBs derivatives (3‒5) and three known ones (6‒8) without the hydroxyl group at C-32. LobP1 was shown to have relatively broad substrate scope. Determing the kinetic parameters of LobP1 towards different substrates revealed that LobP1 preferred substrate with a nitrosugar. The major product LOB E (6) from the ∆lobP1 mutant displayed better cytotoxic activities against several cancer cell lines than LOB B, the C-32 hydroxlated counterpart.

Usually, the aniline-based late-transition-metal catalysts often require bulky steric substituents on both sides of the ortho-aryl position to achieve efficient suppression of chain transfer in ethylene polymerization. In this contribution, we demonstrated that α-diimine catalysts based on naphthylamine with only one bulky ortho-aryl substituent also demonstrated excellent capabilities to suppress the chain transfer. Firstly, a class of α-diimine nickel and palladium complexes with only one o-aryl-dibenzhydryl or o-aryl-dibenzosuberyl substituent were synthesized and characterized. Secondly, the as-prepared naphthylamine-based nickel catalysts demonstrated outstanding activities and yielded lightly branched (16-40/1000C) polyethylenes with very high molecular weights (445.8-854.3 kg/mol) in ethylene polymerization. In comparison, the corresponding palladium catalysts showed moderate activities, generating moderately branched polyethylenes with moderate molecular weights (21.6-82.0 kg/mol). Moreover, the palladium catalysts could also copolymerize ethylene and methyl acrylate (MA), albeit in low activity (level of 103 g·mol-1·h-1)，providing E-MA copolymers with low to moderate molecular weight (1.4-16.3 kg/mol) and a moderate level of incorporation ratio (2.4-7.4 mol%) and branching density. As compared with aniline-based nickel and palladium catalysts, the naphthylamine-based catalysts displayed a superior ability to suppress the chain transfer reactions and could give access to (co)polymers with orders of magnitude higher molecular weight in ethylene (co)polymerization.