A5008499728- Catalytic C–H Functionalization Methods
- Synthesis and Catalytic Reactions
- Crystallization and Solubility Studies
- X-ray Diffraction in Crystallography
- Asymmetric Hydrogenation and Catalysis
- Catalytic Cross-Coupling Reactions
- Coordination Chemistry and Organometallics
- Synthetic Organic Chemistry Methods
- Oxidative Organic Chemistry Reactions
- Asymmetric Synthesis and Catalysis
- Cyclopropane Reaction Mechanisms
- Synthesis of heterocyclic compounds
- Crystallography and molecular interactions
- Catalytic Alkyne Reactions
- Sulfur-Based Synthesis Techniques
- Organoboron and organosilicon chemistry
- Chemical Synthesis and Reactions
- N-Heterocyclic Carbenes in Organic and Inorganic Chemistry
- Radical Photochemical Reactions
- Organic Chemistry Synthesis Methods
- Spine and Intervertebral Disc Pathology
- Synthesis and Reactivity of Sulfur-Containing Compounds
- Carbon dioxide utilization in catalysis
- Synthesis of Indole Derivatives
- Synthesis and pharmacology of benzodiazepine derivatives
First Affiliated Hospital of GuangXi Medical University
2024-2025
Guangxi Medical University
2024-2025
Beijing National Laboratory for Molecular Sciences
2015-2024
Chinese Academy of Sciences
2015-2024
University of Chinese Academy of Sciences
2017-2024
Anhui Jianzhu University
2021-2023
Henan University
2023
Institute of Chemistry
2004-2022
Second Affiliated Hospital of Nanjing Medical University
2017-2021
Molecular Sciences Institute
2020-2021
A novel protocol for the palladium-catalyzed intramolecular direct arylation of benzoic acids is reported, which combines decarboxylation and C−H activation into one efficient process. With optimized catalyst system palladium trifluoroacetate, silver carbonate, proper solvent mixture (5% DMSO/dioxane), dibenzofuran derivatives are formed in excellent yield selectivity.
Described herein is a manganese-catalyzed dehydrogenative [4+2] annulation of NH imines and alkynes, reaction providing highly atom-economical access to diverse isoquinolines. This transformation represents the first example CH activation imines; stoichiometric variant cyclomanganation was reported in 1971. The redox neutral produces H2 as major byproduct eliminates need for any oxidants, external ligands, or additives, thus standing out from known isoquinoline synthesis by...
The first manganese-catalyzed aromatic C-H alkenylation with terminal alkynes is described. procedure features an operationally simple catalyst system containing commercially available MnBr(CO)(5) and dicyclohexylamine (Cy(2)NH). reaction occurs readily in a highly chemo-, regio-, stereoselective manner delivering anti-Markovnikov E-configured olefins high yields. Experimental study DFT calculations reveal that (1) the initiated by activation step via cooperation of manganese base; (2)...
A novel protocol for palladium-catalyzed intermolecular formal [4 + 2] annulation of 2-phenylbenzoic acids with alkynes is described. Acridine shown to be essential the high reaction efficiency. Phenanthrene derivatives are formed in moderate good yields without coupling (pseudo)halides or organometallic species.
ConspectusTraditional organic synthesis relies heavily on the transformations of various preinstalled functional groups, such as cross-coupling reactions using organohalides and organometallic reagents. The strategy C–H activation enables direct formation C–C/C–X (X = heteroatom) bonds from inert bonds, which can enhance atom- step-economy synthesis. To date, precious metals have overwhelmingly dominated field; however, rarity high cost these necessitate development more sustainable...
Herein, a manganese-catalyzed nucleophilic addition of inert C(sp(2))-H bonds to aldehydes and nitriles is disclosed by virtue dual activation strategy. The reactions feature mild reaction conditions, excellent regio- stereoselectivity, wide substrate scope, which includes both aromatic olefinic C-H bonds, as well large variety nitriles. Moreover, mechanistic studies shed light on possible catalytic cycles.
Glycine is a nonessential amino acid that plays vital role in various biological activities. However, the conventional synthesis of glycine requires sophisticated procedures or toxic feedstocks. Herein, we report an electrochemical pathway for via reductive coupling oxalic and nitrate nitrogen oxides over atomically dispersed Fe–N–C catalysts. A selectivity 70.7% achieved Fe–N–C-700 at −1.0 V versus RHE. Synergy between FeN3C structure pyrrolic facilitates reduction to glyoxylic acid, which...
C–H activation is an emerging powerful strategy to functionalize organic molecules alternative traditional synthetic tools. Despite being cheap and abundant in the earth's crust, manganese far less studied within realm of activation, particular for C–C bond formation, compared 'noble' transition metals. Herein, we provide a state-of-the-art review on Mn-mediated bond-forming reactions, both stoichiometric catalytic, via activation.
Transition-metal-catalyzed isoquinoline synthesis that profits from the strategy of chelation-assisted C−H activation has flourished over past decade. By virtue directed bond cleavage imines, amines, amidines, oximes, hydroximoyl halides, hydrazones, or azines, diverse derivatives have been accessed alkynes, conjugated dienes, diazo compounds under catalysis rhodium, ruthenium, palladium, nickel, manganese. This digest summarizes annulation reactions via leading to isoquinolines,...
Since 1987, the stoichiometric two-step C-H conjugate addition reactions have been developed. Herein we describe first manganese-catalyzed one-step direct aromatic to α,β-unsaturated carbonyls, which is accelerated by a catalytic amount of dicyclohexylamine. Experimental and computational studies substantiated validity proposed cycle.
Herein, we disclose the first manganese-catalyzed hydrosilylation of alkynes featuring diverse selectivities. The highly selective formation E-products was achieved by using mononuclear MnBr(CO)5 with arsenic ligand, AsPh3 . Whereas dinuclear catalyst Mn2 (CO)10 and LPO (dilauroyl peroxide) enabled reversed generation Z-products in good to excellent stereo- regioselectivity. Such a way controlling reaction stereoselectivity is unprecedented. Mechanistic experiments revealed dichotomy...
Abstract Described herein is a manganese‐catalyzed dehydrogenative [4+2] annulation of NH imines and alkynes, reaction providing highly atom‐economical access to diverse isoquinolines. This transformation represents the first example CH activation imines; stoichiometric variant cyclomanganation was reported in 1971. The redox neutral produces H 2 as major byproduct eliminates need for any oxidants, external ligands, or additives, thus standing out from known isoquinoline synthesis by...
Abstract So far, the direct C−H alkenylation of aromatic nitriles with alkynes has not been achieved. Herein, we discribe first manganese‐catalyzed N−H imidates to access mono ‐alkenylated nitriles. The reaction is accelerated by presence a catalytic amount sodium pivalate. This protocol also highlighted simple system, good compatibility functional groups, and excellent mono‐/dialkenylation selectivity as well E / Z stereoselectivity. magnified image
Rhenium-catalyzed oxyalkylation of alkenes is described, where hypervalent iodine(III) reagents derived from widely occurring aliphatic carboxylic acids were used as, for the first time, not only an oxygenation source but also alkylation via decarboxylation. The reaction features a wide substrate scope, totally regiospecific difunctionalization, mild conditions, and ready availability both substrates. Mechanistic studies revealed decarboxylation/radical-addition/cation-trapping cascade...
The first Re-catalyzed [4 + 1] annulation of azobenzenes with aldehydes was developed to furnish 2H-indazoles via isolable and characterized cyclic ReI-complexes. For the time, acetate-acceleration effect is showcased in C–H activation reactions. Remarkably, mechanistic studies revealed an irreversible aldehyde-insertion step, which sharp contrast those previous Rh- Co-systems.
Selectivity control of varied C-H bonds in a complex molecule is long-standing goal and still great challenge activation field. Most often, such selectivity achieved by the innate reactivity different bonds. In this context, classic Mannich reaction acetophenone derivatives imines ascribed to more reactive C(sp3)-H α carbonyl, with much less aromatic C(sp2)-H remaining intact. Herein we report an addition ketones enabled manganese catalysis, which totally reverses carbonyl those on ring....
An expedient Mn-catalyzed three-component synthesis of 1,5-amino/keto alcohols from Grignard reagents, imines/nitriles, and tetrahydrofuran (THF) is described, which deviates the classic addition to imines/nitriles in THF solvent. split "sewn" an unprecedented manner reaction, leading formation two geminal C-C bonds via C-H C-O cleavage. Mechanistic experiments DFT calculations reveal radical organo-Mn intermediates catalytic cycle α-arylative ring-opening as key reaction step.
Stoichiometric C-H bond activation of arenes mediated by iron carbonyls was reported Pauson as early in 1965, yet the catalytic transformations have not been developed. Herein, an iron-catalyzed annulation N-H imines and internal alkynes to furnish cis-3,4-dihydroisoquinolines is described, represents first iron-carbonyl-catalyzed reaction arenes. Remarkablely, this also redox-neutral [4+2] proceeding activation. The features only cis stereoselectivity excellent atom economy neither base,...
A versatile and modular one-pot method for the preparation of differently substituted symmetrical unsymmetrical imidazolium salts is reported, 19 examples are given. In key step, readily available formamidines alpha-halo ketones coupled to give imidazolinium 3, followed by salt formation acylation-induced elimination. For many substitution patterns products, this efficient strategy compares favorably with well-known processes in terms yield, ease synthesis, robustness.
One, two or three? The utilization of sterically hindered alkyl substrates represents a major challenge the present cross-coupling methodology. nickel-catalyzed Kumada cross- coupling tertiary Grignard reagents with aryl bromides allows this difficult reaction numerous different substrates. Optimal results were obtained using demanding, bifunctional N-heterocyclic carbene ligands.