Nitroepoxide ring opening with thionucleophiles in water: synthesis of α-xanthyl ketones, ß-keto sulfones and ß-keto sulfonic acids.

Nitroepoxide ring opening with thionucleophiles such as potassium xanthates, sodium aryl sulfinates and sodium bisulfite in water is investigated. It provides a direct and green route for the synthesis of α-xanthyl-α-aryl-2-propanones (P2P-xanthate derivatives), ß-keto sulfones and ß-keto sulfonic acids. High to excellent yields, performing the reaction in water under catalyst-free conditions, and easy work-up are the main advantages of this protocol.

Development and synthesis of a novel salen-type ligand based on phenylalanine for Mizoroki-Heck, and S-arylation cross-coupling reactions.

In this article, we introduced a novel salen-type ligand precursor and applied it in the Pd-catalyzed Mizoroki-Heck and Cu-catalyzed S-arylation cross-coupling reactions. For the preparation of this structure, (DL)-phenyl alanine was employed as a starting material. These ligand precursor and related catalytic system can be readily synthesised. Various aryl halides (-I, -Br) and alkenes were applied successfully in this protocol to give the corresponding Mizoroki-Heck cross-coupling and S-arylated products in high to excellent yields.

Catalyst free one pot three components synthesis of 2-iminothiazoles from nitroepoxides and thiourea.

Nitroepoxides were introduced as efficient substrates for the one-pot three-component synthesis of 2-iminothiazoles under catalyst-free conditions. Reaction of amines, isothiocyanates, and nitroepoxides in THF at 10-15 °C afforded corresponding 2-iminothiazoles in high to excellent yields. The reaction proceeds via the in situ formation of thiourea from an amine and an isothiocyanate, followed by nitroepoxide ring opening with the sulfur of thiourea, cyclization reaction, and dehydration cascade. The structures of products were confirmed by IR, NMR, HRMS analyses and X-ray crystallography.

Cellulose-Supported Heterogeneous Gold-Catalyzed Cycloisomerization Reactions of Alkynoic Acids and Allenynamides.

Herein, we describe efficient nanogold-catalyzed cycloisomerization reactions of alkynoic acids and allenynamides to enol lactones and dihydropyrroles, respectively (the latter via an Alder-ene reaction). The gold nanoparticles were immobilized on thiol-functionalized microcrystalline cellulose and characterized by electron microscopy (HAADF-STEM) and by XPS. The thiol-stabilized gold nanoparticles (Au0) were obtained in the size range 1.5-6 nm at the cellulose surface. The robust and sustainable cellulose-supported gold nanocatalyst can be recycled for multiple cycles without losing activity.

Layered dermal reconstitution through epigallocatechin 3-gallate loaded chitosan nanoparticle within enzymatically crosslinked polyvinyl alcohol/collagen fibrous mat.

Biocompatible electrospun fiber comprising bioactive substrates has potential to implant into the wound site as a reliable therapeutic approach in tissue regeneration. Here, electrospun polyvinyl alcohol conjugated tyramine (PVA-Tyr) and collagen (Col) fibrous mat containing chitosan nanoparticle loaded with epigallocatechin 3-gallate (NCs-EGCG) developed and the composite was applied to evaluate in vivo wound healing ability of fabricated wound patch. The synthesized PVA-Tyr and Col were electrospun and crosslinked through peroxidase reaction in presence of vaporized H2O2 as an electron donor which covalently proceeded conjugation of phenolic groups and could develop hybrid fibrous mat in stable structure and uniform shapes. The EGCG as anti-oxidative/inflammatory substrate was encapsulated efficiently in NCs and released in a sustained manner. The hybrid fibers seeded with adipose-derived stem cells presented appropriate biocompatibility from biophysical and biochemical viewpoints and in following wound healing ability in a full-thickness excisional animal model. Fourier transform infrared spectroscopy (FTIR) confirmed all typical absorption characteristics of PVA-Tyr and Col as well as NCs and EGCG. The results showed the perfect hydrophilic/hydrophobic ratio and good mechanical and structural characteristics including shape uniformity and porosity. Interestingly, cellular attachment and proliferation on the PVA-Tyr/Col fibers containing NCs-EGCG were higher than control samples. The histological analysis of hybrid fibrous patch could be suggested the applicability of this structure as suitable skin substitutes to repair injured skin.

Hyaluronic acid/gelatin microcapsule functionalized with carbon nanotube through laccase-catalyzed crosslinking for fabrication of cardiac microtissue.

Carbon nanotube (CNT) and gelatin (Gela) molecules are effective substrates in promoting engineered cardiac tissue functions. This study developed a microfluidic-based encapsulation process for biomimetic hydrogel microcapsule fabrication. The hydrogel microcapsule was produced through a coaxial double orifice microfluidic technique and a water-in-oil emulsion system in two sequential processes. The phenol (Ph) substituted Gela (Gela-Ph) and CNT (CNT-Ph), respectively as cell-adhesive and electrically conductive substrates were incorporated in hyaluronic acid (HA)-based hydrogel through laccase-mediated crosslinking. The Cardiomyocyte-enclosing microcapsule fabricated and cellular survival, function, and possible difference in the biological activity of encapsulated cells within micro vehicles were investigated. The coaxial microfluidic method and Lac-mediated crosslinking reaction resulted in spherical vehicle production in 183 µm diameter at 500 capsules/min speed. The encapsulation process did not affect cellular viability and harvested cells from microcapsule proliferated well likewise subcultured cells in tissue culture plate. The biophysical properties of the designed hydrogel, including mechanical strength, swelling, biodegradability and electroconductivity upregulated significantly for hydrogels decorated covalently with Gela-Ph and CNT-Ph. The tendency of the microcapsule for the spheroid formation of cardiomyocytes inside the proposed microcapsule occurred 3 days after encapsulation. Interestingly, immobilized Gela-Ph and CNT-Ph promote cellular growth and specific cardiac markers. Overall, the microfluidic-based encapsulation technology and synthesized biomimetic substrates with electroconductive properties demonstrate desirable cellular adhesion, proliferation, and cardiac functions for engineering cardiac tissue.

DABCO bond cleavage for the synthesis of piperazine derivatives.

The applications of DABCO (1,4-diazabicyclo[2.2.2]octane) in the synthesis of piperazine derivatives including biologically active compounds via C-N bond cleavage are investigated in this review. Different reagents such as alkyl halides, aryl(heteroary) halides, carboxylic acids, diaryliodonium salts, tosyl halides, activated alkynes, benzynes etc. were applied for the preparation of the corresponding quaternary ammonium salts of DABCO, which are very good electrophiles for various nucleophiles such as phenols, thiophenols, thiols, alcohols, aliphatic and aromatic amines, sulfinates, phthalimide, indoles, NaN3, triazole and terazoles, NaCN, enols and enolates, halides, carboxylic acid salts etc. Besides preactivated DABCO salts, the in situ activation of DABCO in multicomponent reactions is also an efficient tactic in synthetic organic chemistry for the diversity oriented synthesis of drug-like piperazine derivatives.