A5040961372- Asymmetric Synthesis and Catalysis
- Chemical Synthesis and Analysis
- Enzyme Catalysis and Immobilization
- Asymmetric Hydrogenation and Catalysis
- Synthesis and Catalytic Reactions
- Catalytic C–H Functionalization Methods
- Oxidative Organic Chemistry Reactions
- Cyclopropane Reaction Mechanisms
- Chemical Synthesis and Reactions
- Synthetic Organic Chemistry Methods
- Microbial Natural Products and Biosynthesis
- Click Chemistry and Applications
- Synthesis of Indole Derivatives
- Nanomaterials for catalytic reactions
- Axial and Atropisomeric Chirality Synthesis
- Carbohydrate Chemistry and Synthesis
- Hepatitis Viruses Studies and Epidemiology
- Phenothiazines and Benzothiazines Synthesis and Activities
- Political Philosophy and Ethics
- Circadian rhythm and melatonin
- Cellular transport and secretion
- Bioactive Compounds and Antitumor Agents
- Genomics, phytochemicals, and oxidative stress
- Automated Road and Building Extraction
- Plant tissue culture and regeneration
Jiangnan University
2022-2025
University of Groningen
2020-2022
Shenzhen University
2022
First Affiliated Hospital of Wannan Medical College
2021
Sichuan University
2012-2019
State Key Laboratory of Biotherapy
2012-2017
Université de Caen Normandie
2016
École Nationale Supérieure d'Ingénieurs de Caen
2016
Centre National de la Recherche Scientifique
2016
Institute of Molecular and Cell Biology
2007
Newly framed: The δ,ε CC bond of an interrupted cyclic 2,5-dienone induces the formation a linear trienamine in presence chiral primary amine, thus enabling δ,ε-CC to participate highly asymmetric inverse-electron-demand aza-Diels–Alder (DA) reaction with electron-deficient 1-azadienes. DA can be coupled Michael addition produce polycyclic framework complete stereocontrol. As service our authors and readers, this journal provides supporting information supplied by authors. Such materials...
Switchable reaction patterns of β-substituted cyclic enones via amine-based dienamine activation are reported. While γ-regioselective vinylogous Michael addition was observed with alkylidenemalononitriles, a completely different [4 + 2] cycloaddition obtained allylidene- or alkynylidenemalononitrile substrates, affording densely substituted bicyclo[2.2.2]octanes analogous architectures moderate to excellent diastereo- and enantioselectivity by the catalysis primary amines from natural...
The molecular mechanism governing the regulated secretion of most exocrine tissues remains elusive, although VAMP8/endobrevin has recently been shown to be major vesicular SNARE (v-SNARE) zymogen granules pancreatic acinar cells. In this article, we have characterized role VAMP8 in entire system. Immunohistochemical studies showed that is expressed all examined such as salivary glands, lacrimal (tear) sweat sebaceous mammary and prostate. Severe anomalies were observed glands VAMP8-null...
Here we report that cyclic 2,5-dienones can act as bisvinylogous precursors through in situ generation of linear trienamine species with a cinchona-derived primary amine, and exclusively remote ε-regioselective 1,4-additions to nitroalkenes were accomplished moderate high enantioselectivity. Moreover, diversity complex spirocyclic frameworks could be efficiently constructed an enantioenriched manner from these multifunctional 1,4-adducts via subsequent vinylogous iminium even cascade...
We present an artificial metalloenzyme based on the transcriptional regulator LmrR that exhibits dynamics involving positioning of its abiological metal cofactor. The position cofactor, in turn, was found to be related preferred catalytic reactivity, which is either enantioselective Friedel-Crafts alkylation indoles with β-substituted enones or tandem alkylation/enantioselective protonation α-substituted enones. could specialized for one these reactions introducing a single mutation protein....
The construction and engineering of artificial enzymes consisting abiological catalytic moieties incorporated into protein scaffolds is a promising strategy to realize non-natural mechanisms in biocatalysis. Here, we show that incorporation the noncanonical amino acid para-aminophenylalanine (pAF) nonenzymatic scaffold LmrR creates proficient stereoselective enzyme (LmrR_pAF) for vinylogous Friedel–Crafts alkylation between α,β-unsaturated aldehydes indoles. pAF acts as residue, activating...
As the chip of synthetic biology, enzymes play a vital role in bio-manufacturing industry. The development diverse functional can provide rich toolbox for biology. This article reports construction an artificial enzyme with introduction non-natural cofactor. By introducing 4-dimethylaminopyridine (DMAP) cofactor into optimal protein skeleton via covalent bonds based on click-chemistry strategy, we successfully constructed novel DMAP as catalytic center. catalyzed unnatural asymmetric...
Vision-language models (VLMs), such as CLIP, have demonstrated exceptional generalization capabilities and can quickly adapt to downstream tasks through prompt fine-tuning. Unfortunately, in classification involving non-training classes, known open-vocabulary setting, fine-tuned VLMs often overfit train resulting a misalignment between confidence scores actual accuracy on unseen which significantly undermines their reliability real-world deployments. Existing calibration methods typically...
Asymmetric α,γ-regioselective [3 + 3] formal cycloadditions of α,β-unsaturated aldehydes and 2-nitroallylic acetates have been developed for the first time. These reactions proceeded through a domino Michael addition–Michael addition sequence via an unusual cascade dienamine–dienamine catalysis chiral secondary amine, multifunctional cyclohexene derivatives were generally constructed in moderate yields with excellent stereoselectivity after simple treatment K2CO3.
Saturated bioisosteres of ortho-substituted benzenes are significant interest due to their enhanced pharmacokinetic properties, such as improved metabolic stability and reduced toxicity, making them valuable in drug design development. However, efficient synthesis remains a challenge organic chemistry. Herein, we report the biocatalytic saturated using engineered artificial photoenzymes. The photoenzyme, incorporating genetically encoded unnatural amino acids with benzophenone...
Abstract Exploring the promiscuity of native enzymes presents a promising strategy for expanding their synthetic applications, particularly catalyzing challenging reactions in non-native contexts. In this study, we explore promiscuous potential old yellow (OYEs) to facilitate Morita-Baylis-Hillman reaction (MBH reaction), leveraging substrate similarities between MBH and reduction reaction. Using mass spectrometry spectroscopic techniques, confirm Gk OYE both reactions. By blocking H - +...
Neu eingerahmt: Die δ,ε-CC-Bindung eines unterbrochenen cyclischen 2,5-Dienons induziert die Bildung linearen Trienamins in Gegenwart chiralen primären Amins und ist damit der Lage, an einer hoch asymmetrischen Aza-Diels-Alder(DA)-Reaktion mit elektronenarmen 1-Azadienen teilzunehmen. DA-Reaktion wurde Michael-Addition gekoppelt, um eine polycyclische Struktur vollständiger Stereokontrolle aufzubauen.
Abstract Endo ‐type cross‐conjugated trienamines between highly congested α′‐alkylidene 2‐cyclohexenones and a chiral primary amine catalyst serve as HOMO‐raised dienophiles in inverse‐electron‐demand aza‐Diels–Alder cycloadditions with number of 1‐azadiene substrates. The reactions exhibit exclusive β,γ‐regioselectivity, multifunctional products high molecular complexity are efficiently constructed excellent diastereo‐ enantioselectivity (>19:1 d.r., up to 99 % ee ).
A double catalytic system combining 2-mercaptobenzoic acid and a chiral phase transfer substance was disclosed for the intermolecular cross Rauhut–Currier reaction of 2-cyclopentenone isatin-based alkylidene malononitriles. The resulting adducts were sequentially assembled with diverse electron-deficient olefins to furnish highly enantioenriched cyclohexane derivatives (up 96:4 er, >19:1 dr). similar quinine further developed α-cyano chalcones 96.5:3.5 er).
Enantioselective protonation is conceptually one of the most attractive methods to generate an α-chiral center. However, enantioselective presents major challenges, especially in water. Herein, we report a tandem Michael addition/enantioselective reaction catalyzed by artificial enzyme employing two abiological catalytic sites synergistic fashion: genetically encoded noncanonical p-aminophenylalanine residue and Lewis acid Cu(II) complex. The exquisite stereocontrol achieved transient...
Abstract An asymmetric four‐component [5+1+1+1] formal cycloaddition reaction of 3‐substituted 2‐cyclopentenones, activated methylene nucleophiles and two molecules aldehydes is developed under chiral primary aminocatalysis, producing a diversity highly enantioenriched fused spirocyclic frameworks with high molecular complexity. Mechanism studies indicate that the current proceeds in challenging cascade quintuple Knoevenagel condensation/Michael addition/retro‐Michael addition/Michael...
Artificial enzymes utilizing the genetically encoded non-proteinogenic amino acid p-aminophenylalanine (pAF) as a catalytic residue are able to react with carbonyl compounds through an iminium ion mechanism promote reactions that have no equivalent in nature. Herein, we report vivo biocatalytic cascade is augmented such artificial enzyme-catalysed new-to-nature reaction. The enzyme this study pAF-containing evolved variant of lactococcal multidrug-resistance regulator, designated...
Abstract An asymmetric direct ϵ‐regioselective bisvinylogous 1,6‐addition reaction of β‐allyl‐2‐cyclohexenone to β‐substituted α,α‐dicyanodienes was developed through trienamine catalysis a bifunctional primary amine–thiourea compound. Excellent enantioselectivity (up 97 % ee ) obtained even such remote mode. In addition, more complex cyclic frameworks could be efficiently constructed with high stereoselectivity.
Cooperative catalysis has contributed greatly to the progress of asymmetric synthesis. However, double-activation been less explored, especially for covalently tethered species. Here, we present a strategy α'-alkylidene cyclic enone substrates that uses chiral primary amine and 2-mercaptobenzoic acid promote regio- chemoselective addition generate complex interrupted iminium ion Significantly enhanced reactivity enantioselectivity were observed β-regioselective Michael Friedel-Crafts...
Consistent introduction of novel enzymes is required for developing efficient biocatalysts challenging biotransformations. Absorbing catalytic modes from organocatalysis may be fruitful designing new-to-nature with functions. Herein we report a newly designed artificial enzyme harboring pyrrolidine residue that catalyzes the asymmetric Michael addition cyclic ketones to nitroolefins through enamine activation high efficiency. Diverse chiral γ-nitro two stereocenters were efficiently prepared...
Abstract Artificial enzymes utilizing the genetically encoded non‐proteinogenic amino acid p‐ aminophenylalanine (pAF) as a catalytic residue are able to react with carbonyl compounds through an iminium ion mechanism promote reactions that have no equivalent in nature. Herein, we report vivo biocatalytic cascade is augmented such artificial enzyme‐catalysed new‐to‐nature reaction. The enzyme this study pAF‐containing evolved variant of lactococcal multidrug‐resistance regulator, designated...