Design, Synthesis, and Antifungal Activities of Novel Potent Fluoroalkenyl Succinate Dehydrogenase Inhibitors.

The development of new fungicide molecules is a crucial task for agricultural chemists to enhance the effectiveness of fungicides in agricultural production. In this study, a series of novel fluoroalkenyl modified succinate dehydrogenase inhibitors were synthesized and evaluated for their antifungal activities against eight fungi. The results from the antifungal assay demonstrated that compound exhibited superior activity against with an EC value of 0.

Rational modification of melatonin for broad-spectrum antifungal agents discovery.

Natural products, known for their environmental safety, are regarded as a significant basis for the modification and advancement of fungicides. Melatonin, as a low-cost natural indole, exhibits diverse biological functions, including antifungal activity. However, its potential as an antifungal agent has not been fully explored.

Co-Immobilization of ADH and GDH on Metal-Organic-Framework: An Effective Biocatalyst for Asymmetric Reduction of Ketones.

Chiral alcohols are not only important building blocks of various bioactive natural compounds and pharmaceuticals, but can serve as synthetic precursors for other valuable organic chemicals, thus the synthesis of these products is of great importance. Bio-catalysis represents one effective way to obtain these molecules, however, the weak stability and high cost of enzymes often hinder its broad application. In this work, we designed a biological nanoreactor by embedding alcohol dehydrogenase (ADH) and glucose dehydrogenase (GDH) in metal-organic-framework ZIF-8.

Directed Evolution and Immobilization of Lactobacillus brevis Alcohol Dehydrogenase for Chemo-Enzymatic Synthesis of Rivastigmine.

Rivastigmine is one of the several pharmaceuticals widely prescribed for the treatment of Alzheimer's disease. However, its practical synthesis still faces many issues, such as the involvement of toxic metals and harsh reaction conditions. Herein, we report a chemo-enzymatic synthesis of Rivastigmine.

Covalent Organic Frameworks Based Photoenzymatic Nano-reactor for Asymmetric Dynamic Kinetic Resolution of Secondary Amines.

Bio-catalysis represents a highly efficient and stereoselective method for the synthesis of valuable chiral compounds, however, the poor stability and limited reaction types of free enzymes restrict their wide application in industrial production. In this work, to overcome these problems, a multifunctional photoenzymatic nanoreactor CALB@COF-Ir was developed through the encapsulation of Candida antarctica lipase B (CALB) in a photosensitive covalent organic framework COF-Ir. This bio-nanocluster serves as efficient catalysts in asymmetric dynamic kinetic resolution (DKR) of secondary amines to give a series of chiral amines in high yields (up to 99 %) and enantioselectivities (up to 99 % ee).

Identification of propranolol and derivatives that are chemical inhibitors of phosphatidate phosphatase as potential broad-spectrum fungicides.

Plant diseases cause enormous economic losses in agriculture and threaten global food security, and application of agrochemicals is an important method of crop disease control. Exploration of disease-resistance mechanisms and synthesis of highly bioactive agrochemicals are thus important research objectives. Here, we show that propranolol, a phosphatidate phosphatase (Pah) inhibitor, effectively suppresses fungal growth, sporulation, sexual reproduction, and infection of diverse plants.

Melatonin targets MoIcl1 and works synergistically with fungicide isoprothiolane in rice blast control.

Melatonina natural harmless molecule-displays versatile roles in human health and crop disease control such as for rice blast. Rice blast, caused by the filamentous fungus Magnaporthe oryzae, is one devastating disease of rice. Application of fungicides is one of the major measures in the control of various crop diseases.

Enantio- and diastereodivergent synthesis of fused indolizines enabled by synergistic Cu/Ir catalysis.

Highly diastereo-/enantioselective assembly of 2,3-fused indolizine derivatives could be easily available through a cascade allylation/Friedel-Crafts type reaction enabled by a synergistic Cu/Ir catalysis. This designed protocol provides an unprecedented and facile route to enantioenriched indolizines bearing three stereogenic centers in moderate to high yields with excellent stereoselective control, which also featured broad substrate generality. Remarkably, four stereoisomers of the 2,3-fused indolizine products could be efficiently constructed in a predictable manner through the pairwise combination of copper and iridium catalysts.

Designed polymeric conjugation motivates tunable activation of molecular oxygen in heterogeneous organic photosynthesis.

Photocatalytic oxidative organic reactions are important synthetic transformations, and research on reaction selectivity by reactive oxygen species (ROS) is significant. To date, however, there has rarely been any focus on the directed generation of ROSs. Herein, we report the first identification of tunable molecular oxygen activation induced by polymeric conjugation in nonmetallic conjugated microporous polymers (CMP).

Pyrene-Based D-A Molecules as Efficient Heterogeneous Catalysts for Visible-Light-Induced Aerobic Organic Transformations.

In this work, an efficient visible light promoted aerobic dehydro-coupling of amines, oxidation of thioethers and hydroxylation of arylboronic acids under benign conditions by using pyrene-based donor-acceptor (D-A) conjugated organic molecules was described. Donor-acceptor structure influences their π-conjugation and band gap a lot, and thereby enhances their visible light absorption ability, single electron transfer and oxidative behaviors. Alkynyl units in PS-IV play a crucial role in the catalyst which could serve as electron transferring bridge to strengthen electron delocalization, thus facilitating the single electron transfer from photosensitizer to substrates, and making it an efficient ⋅O generator.

Synthesis of remote fluoroalkenyl ketones by photo-induced ring-opening addition of cyclic alkoxy radicals to fluorinated alkenes.

Fluoroalkenyl moieties are often used as carbonyl mimics in medicine preparation, and thus the development of facile routes for the synthesis of such compounds is of great importance. In this work, we report a photocatalytic ring-opening addition of cyclic alcohols to α-(trifluoromethyl)styrenes, which underwent a proton-coupled electron transfer and β-scission process, delivering a great variety of remote -difluoroalkenyl ketone derivatives. This methodology can also be applied in the reaction of -difluorostyrenes and 1,1,2-trifluorostyrenes to access monofluoro- and 1,2-difluoroalkenyl ketones.

Melatonin functions as a broad-spectrum antifungal by targeting a conserved pathogen protein kinase.

Melatonin is a low-cost natural small indole molecule with versatile biological functions. However, melatonin's fungicidal potential has not been fully exploited, and the mechanism remains elusive. Here, we report that melatonin broadly inhibited 13 plant pathogens.

Efficient Synthesis of Diaryl Quaternary Centers by Rh(II)/Xantphos Catalyzed Relay C-H Functionalization and Allylic Alkylation.

A three-component reaction of N, N-disubstituted aniline, α-diazo ester, and an allylic electrophile has been realized by [Rh(II)] /Xantphos catalysis, providing a direct access to various aniline derivatives bearing diaryl allylic quaternary centers in good yields. The synthetic utility of this protocol was demonstrated by facile derivatization of the products for preparation of biologically relevant molecules and structural scaffolds, which offers a high potential for increasing the molecular diversity. Mechanistic studies identified α, α-diarylacetate species as an active intermediate, thereby revealing the presence of a C(sp )-H functionalization of aniline derivatives/allylic alkylation cascade in this attractive catalytic transformation.

Synthesis of bioactive fluoropyrrolidines copper(i)-catalysed asymmetric 1,3-dipolar cycloaddition of azomethine ylides.

Chiral pyrrolidinyl units are important building blocks in biologically active natural products and drugs, and the development of efficient methods for the synthesis of diverse structured pyrrolidine derivatives is of great importance. Meanwhile, incorporating fluorine containing groups into small molecules often changes their activities to a great extent due to the special physicochemical properties of fluorine atoms. Herein, we report an efficient route to obtain enantioenriched 3,3-difluoro- and 3,3,4-trifluoropyrrolidinyl derivatives by Cu(i)-catalysed enantioselective 1,3-dipolar cycloaddition of azomethine ylides with less active 1,1-difluoro- and 1,1,2-trifluorostyrenes.

A coumarin-based fluorescent probe for NIR imaging-guided photodynamic therapy against -induced infection in mouse models.

A coumarin-based viscosity-responsive fluorescent probe (HZAU800) was designed and synthesized. The probe, containing a strong electron-donating and rigid group on the 7-position of coumarin and a rhodamine derivative containing an oxonium ion on 3-position, could not only shift the emission wavelength to near-infrared region (NIR, = 800 nm) but also deliver a good PDT effect due to its high rigid planarity. The NIR fluorescence of HZAU800 can be lighted up in the -infected region due to its high viscous environment.

Rare-Earth-Catalyzed C-H Silylation of Aromatic Heterocycles with Hydrosilanes.

The catalytic C-H silylation of a variety of aromatic heterocycles such as furan, pyrrole and thiophene derivatives with secondary hydrosilanes has been achieved by using an yttrium metallocene complex. This protocol provides an efficient and straightforward way for the synthesis of a series of silylated heteroaromatic compounds containing tertiary silane moieties without the need for an additive or H acceptor.

Enantioselective Construction of Silicon-Stereogenic Silanes by Scandium-Catalyzed Intermolecular Alkene Hydrosilylation.

The catalytic asymmetric construction of silicon-stereogenic silanes is of great interest and significance, but has met with only limited success to date. We herein report the enantioselective hydrosilylation of alkenes with dihydrosilanes by a chiral half-sandwich scandium catalyst, which constitutes an efficient and general route for the synthesis of a wide range of enantioenriched silicon-stereogenic silanes from easily accessible starting materials. This reaction features a broad substrate scope, high yields, and high enantioselectivity.

Diastereodivergent Asymmetric Carboamination/Annulation of Cyclopropenes with Aminoalkenes by Chiral Lanthanum Catalysts.

Stereodivergent asymmetric catalysis is an important technology that can allow efficient access to various stereoisomers of a given product with multiple stereocenters from the same set of starting materials, but its application to the synthesis of a highly strained cyclopropane compound has remained unexplored to date. We report here the first diastereodivergent enantioselective synthesis of bicyclic aminocyclopropanes by lanthanum-catalyzed asymmetric carboamination/annulation of cyclopropenes with aminoalkenes. This protocol features 100% atom efficiency, good yield (up to 90%), and high chemo- (up to >20:1) and stereoselectivity (up to >20:1 dr and 99% ee), constituting a unique route for the efficient synthesis of two different diastereoisomers of a given chiral bicyclic aminocyclopropane compound.

Asymmetric Yttrium-Catalyzed C(sp )-H Addition of 2-Methyl Azaarenes to Cyclopropenes.

An enantioselective C-H addition to a C=C bond represents the most atom-efficient route for the construction of chiral carbon-carbon skeletons, a central research topic in organic synthesis. We herein report the enantioselective yttrium-catalyzed C(sp )-H bond addition of 2-methyl azaarenes, such as 2-methyl pyridines, to various substituted cyclopropenes and norbornenes. This process efficiently afforded a new family of chiral pyridylmethyl-functionalized cyclopropane and norbornane derivatives in high yields and high enantioselectivities (up to 97 % ee).

Synthesis of Chiral Aminocyclopropanes by Rare-Earth-Metal-Catalyzed Cyclopropene Hydroamination.

The search for efficient and selective routes for the synthesis of chiral aminocyclopropane derivatives is of great interest and importance as these structures are important components of biologically active natural products and pharmaceuticals. We herein report the enantioselective intermolecular hydroamination of substituted cyclopropenes with various amines catalyzed by chiral half-sandwich rare-earth-metal complexes. This method constitutes a 100 % atom-efficient route for the synthesis of a variety of chiral α-aminocyclopropane derivatives in high yields (up to 96 %) and excellent stereoselectivity (up to >20:1 d.

Et3N-catalyzed tandem formal [4 + 3] annulation/decarboxylation/isomerization of methyl coumalate with imine esters: access to functionalized azepine derivatives.

An unprecedented catalytic tandem formal [4 + 3] cycloaddition/decarboxylation/isomerization of methyl coumalate and imine esters is successfully developed. This tandem reaction only requires Et3N as the mild base affording a series of highly functionalized seven-membered heterocyclic azepine derivatives in good yields with excellent regioselectivities.

Cu(I)-catalyzed regio- and stereoselective [6 + 3] cycloaddition of azomethine ylides with tropone: an efficient asymmetric access to bridged azabicyclo[4.3.1]decadienes.

An unprecedented Cu(I)-catalyzed asymmetric [6 + 3] cycloaddition of tropone with azomethine ylides was reported, which performs well over a broad scope of substrates and offers a unique and facile access to the synthetically useful bridged azabicyclo[4.3.1]decadiene derivatives in good yields with high levels of diastereoselectivities and enantioselectivities under mild conditions.

Silver-catalyzed enantioselective desymmetrization: facile access to spirolactone-pyrrolidines containing a spiro quaternary stereogenic center.

An unprecedented Ag(I)-catalyzed asymmetric desymmetrization of spiro cyclohexadienone lactones has been developed successfully, which performs well over a broad scope of substrates and provides a facile access to optically active spirolactone-pyrrolidines in high yields with excellent levels of diastereo-/enantioselectivities.