scholarly journals Site-selective Amide Functionalization by Catalytic Azoline Engrafting

2021 ◽  
Author(s):  
Wyatt Powell ◽  
Garrett Evenson ◽  
Maciej Walczak
Keyword(s):  
Natural Products ◽  
Catalytic System ◽  
High Selectivity ◽  
High Efficiency ◽  
Unmet Need ◽  
Direct Conversion ◽  
Amide Group ◽  
Site Selective ◽  
Selection Of ◽  
General Method

Amide activation is a challenging transformation due to the stabilizing effect of the amide group. While enzymes can be considered as prototypical systems that have evolved to achieve high selectivity and specificity, small-molecule catalysts that functionalize the amide group may accommodate a much larger selection of substrates but currently re-main scarce. Here, by combining the desired features from both catalytic regimes we designed an artificial cyclodehy-dratase, a catalytic system for site-selective modification of peptides and natural products by engrafting heterocyclic into their scaffolds. The catalytic system features molybdenum(VI) center that was decorated with a sterically congest-ed tripod ligand. The optimized catalyst can introduce azolines into small molecules, natural products, and oligopeptides with high efficiency and minimal waste. We further demonstrate the utility of the new protocol in direct func-tionalization of a single amide group in the presence of up to seven other chemically similar positions, and direct conversion into amines and thioamides. This new mechanistic paradigm may address an unmet need for a general method for selective and sustainable functionalization of peptides and natural products.

scholarly journals Bifunctional Ligand-Assisted Cu-Catalyzed Intermolecular Cyclo-hexenone γ‑C(sp3)-H Amination: Controlled Synthesis of p-Aminophenols

2021 ◽  
Author(s):  
Xin Zhao ◽  
Fang Yang ◽  
Qian-Qian Zhou ◽  
Zou Shaoyu ◽  
Zi-Sheng Chen ◽  
...  
Keyword(s):  
Catalytic System ◽  
Amide Group ◽  
Practical Approach ◽  
Controlled Synthesis ◽  
Bifunctional Ligand ◽  
Environmental Friendly ◽  
Bifunctional Ligands ◽  
Site Selective

Abstract A 1,10-phenanthroline-type bifunctional ligand has been developed for Cu catalyzed direct γ-C(sp3)-H amination with intermolecular anilines. Stabilizing N-centered radicals via amide group installed on the bifunctional ligands, a new catalytic system for site-selective γ-C(sp3)-H amination to synthesize p-aminophenols was established. The economical and practical approach by using oxygen as the terminal oxidant was mild and environmental friendly.

Cobalt/Lewis Acid Catalysis for Hydrocarbofunctionalization of Alkynes via Cooperative C–H Activation

2020 ◽  
Author(s):  
Chang-Sheng Wang ◽  
Sabrina Monaco ◽  
Anh Ngoc Thai ◽  
Md. Shafiqur Rahman ◽  
Chen Wang ◽  
...  
Keyword(s):  
Catalytic System ◽  
Lewis Acid ◽  
Hydrogen Transfer ◽  
Acid Catalysis ◽  
Rate Limiting Step ◽  
Site Selectivity ◽  
Set Up ◽  
Site Selective ◽  
First Time ◽  
Rate Limiting

A catalytic system comprised of a cobalt-diphosphine complex and a Lewis acid (LA) such as AlMe3 has been found to promote hydrocarbofunctionalization reactions of alkynes with Lewis basic and electron-deficient substrates such as formamides, pyridones, pyridines, and azole derivatives through site-selective C-H activation. Compared with known Ni/LA catalytic system for analogous transformations, the present catalytic system not only feature convenient set up using inexpensive and bench-stable precatalyst and ligand such as Co(acac)3 and 1,3-bis(diphenylphosphino)propane (dppp), but also display distinct site-selectivity toward C-H activation of pyridone and pyridine derivatives. In particular, a completely C4-selective alkenylation of pyridine has been achieved for the first time. Mechanistic stidies including DFT calculations on the Co/Al-catalyzed addition of formamide to alkyne have suggested that the reaction involves cleavage of the carbamoyl C-H bond as the rate-limiting step, which proceeds through a ligand-to-ligand hydrogen transfer (LLHT) mechanism leading to an alkyl(carbamoyl)cobalt intermediate.

Differentiation and Functionalization of Adjacent, Remote C–H Bonds

2019 ◽  
Author(s):  
Hang Shi ◽  
Lu Yi ◽  
Jiang Weng ◽  
Katherine Bay ◽  
Xiangyang Chen ◽  
...  
Keyword(s):  
Catalytic System ◽  
Functional Group ◽  
Hydrocinnamic Acid ◽  
Molecular Architectures ◽  
Site Selective ◽  
Developing Strategies

<p>Site-selective functionalizations of C–H bonds will ultimately afford chemists transformative tools for editing and constructing complex molecular architectures<sup>1-4</sup>. Towards this goal, developing strategies to activate C–H bonds that are distal from a functional group is essential<sup>4-6</sup>. In this context, distinguishing remote C–H bonds on adjacent carbon atoms is an extraordinary challenge due to the lack of electronic or steric bias between the two positions. Herein, we report the design of a catalytic system leveraging a remote directing template and a transient norbornene mediator to selectively activate a previously inaccessible remote C–H bond that is one bond further away. The generality of this approach has been demonstrated with a range of heterocycles, including a complex anti-leukemia agent, and hydrocinnamic acid substrates.</p>

Synthesis of Conjugated Triynes via Alkyne Metathesis

2019 ◽  
Author(s):  
Idriss Curbet ◽  
Sophie Colombel-Rouen ◽  
Romane Manguin ◽  
Anthony Clermont ◽  
Alexandre Quelhas ◽  
...  
Keyword(s):  
Steric Hindrance ◽  
High Selectivity ◽  
Alkyne Metathesis ◽  
Cross Metathesis ◽  
Synthetic Strategy ◽  
Sterically Hindered ◽  
Site Selective

<div> <div> <div> <div> <p>The synthesis of conjugated triynes by molybdenum-catalyzed alkyne metathesis is reported. Strategic to the success of this approach is the utilization of sterically-hindered diynes that allowed for the site- selective alkyne metathesis to produce the desired con- jugated triyne products. The steric hindrance of alkyne moiety was found to be crucial in preventing the for- mation of diyne byproducts. This novel synthetic strategy was amenable to self- and cross-metathesis providing straightforward access to the corresponding symmetrical and dissymmetrical triynes with high selectivity. </p> </div> </div> </div> </div>

One-step Separation and Purification of Four Phenolic Acids from Stenoloma chusanum (L.) Ching by Medium-pressure Liquid Chromatography and High-speed Counter-current Chromatography

2019 ◽  
Vol 9 (2) ◽  
pp. 138-143
Author(s):  
Tianyun Li ◽  
Xiling Dai ◽  
Yichen Li ◽  
Guozheng Huang ◽  
Jianguo Cao
Keyword(s):  
Natural Products ◽  
Liquid Chromatography ◽  
Phenolic Acids ◽  
High Speed ◽  
High Efficiency ◽  
Total Phenolic ◽  
Medium Pressure ◽  
Medium Pressure Liquid Chromatography ◽  
One Step ◽  
Counter Current

Background:Stenoloma chusanum (L.) Ching is a Chinese traditional medicinal fern with high total flavonoid and total phenolic content. Traditionally, phenolic compounds were separated by using column chromatography, which is relatively inefficient. </P><P> Objective: This study aims to use an efficient method to separate natural products from S. chusanum by Medium-Pressure Liquid Chromatography (MPLC) and High-Speed Counter-Current Chromatography (HSCCC).Methods:In the present research, firstly, a sample (2.5 g) from the dichloromethane extract of S. chusanum was separated by MPLC. Next, fraction P5 was purified by HSCCC with a two-phase solvent system composed of hexane-ethyl acetate-methanol-water (HEMWat) at a volume ratio of 2:4:1:4 (v/v/v/v). </P><P> Result: Four phenolic acids were obtained and their structures were identified by means of NMR and ESI-mass analysis. They were identified as: 1) protocatechuic acid (34 mg, purity 90.1%), 2) syringic acid (66 mg, purity 99.0%), 3) p-hydroxybenzoic acid (5 mg, purity 91.2%) and 4) vanillic acid (6 mg, purity 99.3%).Conclusion:The combination of MPLC and HSCCC is a high-efficiency separation method for natural products. This is the first report with regard to the separation of four phenolic acids in one step by MPLC and HSCCC from S. chusanum (L.) Ching.

scholarly journals Rational Generation of Lasso Peptides Based on Biosynthetic Gene Mutations and Site-Selective Chemical Modifications

2021 ◽  
Author(s):  
Tan Liu ◽  
Xiaojie Ma ◽  
Jiahui Yu ◽  
Wensheng Yang ◽  
guiyang wang ◽  
...  
Keyword(s):  
Natural Products ◽  
Gene Mutations ◽  
Proteolytic Degradation ◽  
Biosynthetic Gene ◽  
Chemical Modifications ◽  
Lasso Peptides ◽  
Selective Chemical ◽  
Site Selective

Lasso peptides are a unique family of natural products whose structures feature a specific threaded fold, which confers these peptides the resistance to thermal and proteolytic degradation. This stability gives...

Selection of high-quality sperm with thousands of parallel channels

Lab on a Chip ◽  
2021 ◽  
Author(s):  
Mohammad Simchi ◽  
Jason Riordon ◽  
Jae Bem You ◽  
Yihe Wang ◽  
Sa Xiao ◽  
...  
Keyword(s):  
Clinical Practice ◽  
High Selectivity ◽  
High Yield ◽  
Sperm Selection ◽  
High Quality ◽  
Parallel Channels ◽  
Selection Of

A 3D-structured sperm selection device is presented that achieves both high selectivity and high yield via thousands of parallel channels. The device significantly outperforms the best clinical practice by selecting ∼100 000 of higher-quality sperm.

scholarly journals Ring-Opening Copolymerization of Cyclohexene Oxide and Cyclic Anhydrides Catalyzed by Bimetallic Scorpionate Zinc Catalysts

Polymers ◽  
2021 ◽  
Vol 13 (10) ◽  
pp. 1651
Author(s):  
Felipe de la Cruz-Martínez ◽  
Marc Martínez de Sarasa Buchaca ◽  
Almudena del Campo-Balguerías ◽  
Juan Fernández-Baeza ◽  
Luis F. Sánchez-Barba ◽  
...  
Keyword(s):  
Catalytic Activity ◽  
Reaction Mechanism ◽  
Catalytic System ◽  
Phthalic Anhydride ◽  
Ring Opening ◽  
High Selectivity ◽  
Zinc Complexes ◽  
Cyclohexene Oxide ◽  
Reaction Conditions ◽  
Cyclic Anhydrides

The catalytic activity and high selectivity reported by bimetallic heteroscorpionate acetate zinc complexes in ring-opening copolymerization (ROCOP) reactions involving CO2 as substrate encouraged us to expand their use as catalysts for ROCOP of cyclohexene oxide (CHO) and cyclic anhydrides. Among the catalysts tested for the ROCOP of CHO and phthalic anhydride at different reaction conditions, the most active catalytic system was the combination of complex 3 with bis(triphenylphosphine)iminium as cocatalyst in toluene at 80 °C. Once the optimal catalytic system was determined, the scope in terms of other cyclic anhydrides was broadened. The catalytic system was capable of copolymerizing selectively and efficiently CHO with phthalic, maleic, succinic and naphthalic anhydrides to afford the corresponding polyester materials. The polyesters obtained were characterized by spectroscopic, spectrometric, and calorimetric techniques. Finally, the reaction mechanism of the catalytic system was proposed based on stoichiometric reactions.

Hot off the press

2021 ◽  
Vol 38 (4) ◽  
pp. 677-681
Author(s):  
Robert A. Hill ◽  
Andrew Sutherland
Keyword(s):  
Natural Products ◽  
Bioorganic Chemistry ◽  
The Press ◽  
Selection Of

A personal selection of 32 recent papers is presented covering various aspects of current developments in bioorganic chemistry and novel natural products such as eurysoloid A from Eurysolen gracilis.

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