Multifunctional Zn-N4 Catalysts for the Coupling of CO₂ with Epoxides into Cyclic Carbonates

The catalytic conversion of greenhouse gas CO2 into valuable chemicals is a vital goal toward carbon balance and sustainability. In recent decades, the chemical fixation of CO2 into cyclic carbonates has gained much attention. In this work, a series of zinc complexes bearing tetradentate aminopyridine (N4) ligands have been synthesized and characterized. These zinc complexes were applied to the coupling of CO2 with epoxides in excellent yields and with a broad substrate scope under cocatalyst- and solvent-free conditions. Moreover, the zinc catalysts could be readily recovered and reused five times without an obvious loss in catalytic activity. Based on spectroscopic characterizations and experimental results, catalyst Zn-3 (DAP-ZnBr2, DAP = 1,4-bis(2-pyridymethyl)-1,4-diazepane) has been found to be a multifunctional catalyst because of the presence of a Lewis acidic zinc center and a nuclephilic halide anion, and one pyridine is released for the activation of CO2 during the reaction

Multifunctional Zn-N4 Catalysts for the Coupling of CO₂ with Epoxides into Cyclic Carbonates

The catalytic conversion of greenhouse gas CO2 into valuable chemicals is a vital goal toward carbon balance and sustainability. In recent decades, the chemical fixation of CO2 into cyclic carbonates has gained much attention. In this work, a series of zinc complexes bearing tetradentate aminopyridine (N4) ligands have been synthesized and characterized. These zinc complexes were applied to the coupling of CO2 with epoxides in excellent yields and with a broad substrate scope under cocatalyst- and solvent-free conditions. Moreover, the zinc catalysts could be readily recovered and reused five times without an obvious loss in catalytic activity. Based on spectroscopic characterizations and experimental results, catalyst Zn-3 (DAP-ZnBr2, DAP = 1,4-bis(2-pyridymethyl)-1,4-diazepane) has been found to be a multifunctional catalyst because of the presence of a Lewis acidic zinc center and a nuclephilic halide anion, and one pyridine is released for the activation of CO2 during the reaction

Efficient Aliphatic C–H Oxidation and CC Epoxidation Catalyzed by Porous Organic Polymer-Supported Single-Site Manganese Catalysts

Bioinspired manganese complexes have emerged over recent decades as attractive catalysts for a number of selective oxidation reactions. However, these catalysts still suffer from oxidative degradation. In the present study, we prepared a series of porous Mn–N4 catalysts in which the catalytic units are embedded in the skeleton of porous organic polymers (POPs). These POP-based manganese catalysts demonstrated high reactivity in the oxidation of aliphatic C–H bonds and the asymmetric epoxidation of olefins. Furthermore, these catalysts could be readily recycled and reused due to their heterogeneous nature. Morphological characterization revealed that the Mn–N4 complex was individually distributed over a porous polymer network. Remarkably, the nature of the single-site catalyst prevented oxidative degradation during the reaction. The present work has thus developed a successful approach for bioinspired single-site manganese catalysts in which the oxidation reaction is confined to a specific channel in an enzyme-like mode

RhCl₃·3H₂O‑Catalyzed Regioselective C(sp²)–H Alkoxycarbonylation: Efficient Synthesis of Indole- and Pyrrole-2-carboxylic Acid Esters

The C2-selective C–H alkoxycarbonylation of indoles with alcohols and CO catalyzed by RhCl3·3H2O is disclosed that offers convenient access to diverse indole-2-carboxylic esters. The rhodium-based catalysts outperformed all other precious-metal catalysts investigated. In addition, this protocal was found applicable to the synthesis of pyrrole-2-carboxylic esters, and allowed the C–H alkoxycarbonylation in an intramolecular fashion. Preliminary mechanistic studies indicate that C–H cleavage is not likely involved in the rate-determining step, and a five-membered rhodacycle might be an intermediate involved in the reaction

RhCl₃·3H₂O‑Catalyzed Regioselective C(sp²)–H Alkoxycarbonylation: Efficient Synthesis of Indole- and Pyrrole-2-carboxylic Acid Esters

The C2-selective C–H alkoxycarbonylation of indoles with alcohols and CO catalyzed by RhCl3·3H2O is disclosed that offers convenient access to diverse indole-2-carboxylic esters. The rhodium-based catalysts outperformed all other precious-metal catalysts investigated. In addition, this protocal was found applicable to the synthesis of pyrrole-2-carboxylic esters, and allowed the C–H alkoxycarbonylation in an intramolecular fashion. Preliminary mechanistic studies indicate that C–H cleavage is not likely involved in the rate-determining step, and a five-membered rhodacycle might be an intermediate involved in the reaction

RhCl₃·3H₂O‑Catalyzed Regioselective C(sp²)–H Alkoxycarbonylation: Efficient Synthesis of Indole- and Pyrrole-2-carboxylic Acid Esters

The C2-selective C–H alkoxycarbonylation of indoles with alcohols and CO catalyzed by RhCl3·3H2O is disclosed that offers convenient access to diverse indole-2-carboxylic esters. The rhodium-based catalysts outperformed all other precious-metal catalysts investigated. In addition, this protocal was found applicable to the synthesis of pyrrole-2-carboxylic esters, and allowed the C–H alkoxycarbonylation in an intramolecular fashion. Preliminary mechanistic studies indicate that C–H cleavage is not likely involved in the rate-determining step, and a five-membered rhodacycle might be an intermediate involved in the reaction

RhCl₃·3H₂O‑Catalyzed Regioselective C(sp²)–H Alkoxycarbonylation: Efficient Synthesis of Indole- and Pyrrole-2-carboxylic Acid Esters

The C2-selective C–H alkoxycarbonylation of indoles with alcohols and CO catalyzed by RhCl3·3H2O is disclosed that offers convenient access to diverse indole-2-carboxylic esters. The rhodium-based catalysts outperformed all other precious-metal catalysts investigated. In addition, this protocal was found applicable to the synthesis of pyrrole-2-carboxylic esters, and allowed the C–H alkoxycarbonylation in an intramolecular fashion. Preliminary mechanistic studies indicate that C–H cleavage is not likely involved in the rate-determining step, and a five-membered rhodacycle might be an intermediate involved in the reaction

Additional file 1 of The genome of the rice planthopper egg parasitoid wasps Anagrus nilaparvatae casts light on the chemo- and mechanosensation in parasitism

Additional file 1: Table S1. Statistics of Illumina sequence data. Table S2. Statistics of PacBio SMRT sequencing data. Table S3. Results of the BUSCO assessment. Table S4. Classification of repeat sequences. Table S5. Functional annotation of Anagrus nilaparvatae genome. Fig. S1. Kmer Distribution of Anagrus nilaparvatae genome. Fig. S2. Interspersed repeat landscape of the Anagrus nilaparvatae genome. Fig. S3. Distributions of the structural characters of the genes predicted in the Anagrus nilaparvatae genome. Fig. S4. GO functional classification of the Anagrus nilaparvatae predicted genes. Fig. S5. KOG function classification of the predicted genes of Anagrus nilaparvatae. Fig. S6. Maximum-likelihood tree of CSPs of Anagrus nilaparvatae and other Hymenopteras. Fig. S7. Maximum-likelihood tree of NPC2s of Anagrus nilaparvatae and other Hymenopteras. Fig. S8. Maximum-likelihood tree of ORs of Anagrus nilaparvatae and other Hymenopteras. Fig. S9. Maximum-likelihood tree of GRs of Anagrus nilaparvatae and other Hymenopteras. Fig. S10. Maximum-likelihood tree of IRs of Anagrus nilaparvatae and other Hymenopteras. Fig. S11. Maximum-likelihood tree of SNMPs of Anagrus nilaparvatae and other Hymenopteras. Fig. S12. Maximum-likelihood tree of TRPs of Anagrus nilaparvatae and other Hymenopteras

Structure-Based Discovery of a Series of NSD2-PWWP1 Inhibitors

Overexpression, point mutations, or translocations of protein lysine methyltransferase NSD2 occur in many types of cancer cells. Therefore, it was recognized as onco-protein and considered as a promising anticancer drug target. NSD2 consists of multiple domains including a SET catalytic domain and two PWWP domains binding to methylated histone proteins. Here, we reported our efforts to develop a series of NSD2-PWWP1 inhibitors, and further structure-based optimization resulted in a potent inhibitor 38, which has high selectivity toward the NSD2-PWWP1 domain. The detailed biological evaluation revealed that compound 38 can bind to NSD2-PWWP1 and then affect the expression of genes regulated by NSD2. The current discovery will provide a useful chemical probe to the future research in understanding the specific regulation mode of NSD2 by PWWP1 recognition and pave the way to develop potential drugs targeting NSD2 protein

Structure-Based Discovery of a Series of NSD2-PWWP1 Inhibitors

Overexpression, point mutations, or translocations of protein lysine methyltransferase NSD2 occur in many types of cancer cells. Therefore, it was recognized as onco-protein and considered as a promising anticancer drug target. NSD2 consists of multiple domains including a SET catalytic domain and two PWWP domains binding to methylated histone proteins. Here, we reported our efforts to develop a series of NSD2-PWWP1 inhibitors, and further structure-based optimization resulted in a potent inhibitor 38, which has high selectivity toward the NSD2-PWWP1 domain. The detailed biological evaluation revealed that compound 38 can bind to NSD2-PWWP1 and then affect the expression of genes regulated by NSD2. The current discovery will provide a useful chemical probe to the future research in understanding the specific regulation mode of NSD2 by PWWP1 recognition and pave the way to develop potential drugs targeting NSD2 protein