We report an Orthogonal Tandem Catalysis (OTC) involving Au(I)-hydroacyloxylation and Rh(I)-hydroformylation highlighting their compatibility when these metals are employed in a reaction of homogeneous catalysis. Moreover, this OTC allows the...

Starting from commercially available 2-chloro-3-hydroxypyridine, a new route leading to the first protypical pentaarylpyridine bearing five different substituents is reported. This strategy involves set of sequential but fully regiocontrolled Suzuki-Miyaura reactions and highlights 2-OBn pyridine protecting group as key intermediate. The played double role: (i) it allowed additional bromination at position 5 (ii) could afford reactive OTf species for last C-arylation step less hindered 2...

To fill the need for environmentally sensitive fluorescent unnatural amino acids able to operate in red region of spectrum, we have designed and synthesized Alared, a solvatochromic fluorogenic acid derived from Nile Red chromophore. The new can be easily integrated into bioactive peptides using classical solid-phase peptide synthesis. fluorescence quantum yield emission maximum Alared-labeled vary broad range depending on peptide's environment, making Alared powerful reporter biomolecular...

Abstract A simple, sustainable, efficient, mild, and low‐cost protocol was developed for d ‐glucose‐assisted Cu‐catalyzed Ullmann reactions in water amides, carbamates, nitrogen‐containing heterocycles. The reaction compatible with diverse aryl/heteroaryl iodides, giving highly substituted pyridine, indole, or indazole rings. This method offers an attractive alternative to existing protocols, because the proceeds aqueous media, occurs at near ambient temperature, provides N‐arylated products...

Through the development of a new class unnatural ornithine derivatives as bioisosteres arginine, we have designed an orally active peptidomimetic antagonist neuropeptide FF receptors (NPFFR). Systemic low-dose administration this compound to rats blocked opioid-induced hyperalgesia, without any apparent side-effects. Interestingly, also observed that potentiated analgesia. This derivative provides novel therapeutic approach for both improving analgesia and reducing hyperalgesia induced by...

The rhodium-catalyzed hydroformylation of ynamides is described and gives selective access to 2- or 3-aminoacrolein derivatives. regioselectivity this carbonylation can be completely controlled at will thanks the nature ligand used. This represents first example regiodivergent alkyne hydroformylation. influence substituents on different positions ynamide has been investigated, it appears that reaction tolerant a wide range functional groups.

The synthesis of diversely substituted 2,3-dihydro-benzo[c]siloles through an unprecedented palladium-catalyzed domino sequence is reported, involving a cyclocarbopalladation internal silylalkyne. This reaction proceeds with complete stereoselectivity to lead fully exocyclic C=C double bond. Notably, the overall appears be crucial obtain desired cyclic vinylsilanes.

We report herein the synthesis of complex molecules containing furopyran cores through a gold(I)-catalyzed hetero-Diels–Alder cascade reaction. During this process, diene and dienophile are produced concomitantly by action single catalyst from starting material. Moreover, six bonds, four heterocycles, controlled stereogenic centers formed in one-step operation. DFT calculations provide mechanistic basis unprecedented

The synthesis of unprecedented benzimidazole‐fused thiazocines, thiazonines, and thiazecines having an exocyclic double bond is reported. process proceeds through 8‐, 9‐, or 10‐ exo ‐dig cyclocarbopalladation followed by reduction. scope limitations were established showed the importance precursor structure for success reaction. A competition between endo cyclization was observed two substrates bearing N ‐homopropargyl chain, ‐cyclization leading to rarely encountered 11‐membered N,S...

A Pd cross-coupling approach for the synthesis of <italic>N</italic>-aryl-oxetanylamines has been developed.

A new tandem palladium-catalyzed reaction involving a Suzuki–Miyaura coupling, desulfenylative and hydrothiolation of triple bond is reported. Notably, the coupling occurs without copper(I) assistance totally regioselective stereoselective. The overall process results in double incorporation boronic acid reincorporation sulfenyl moiety into product structure. Starting from 2-(bromobenzylsulfenyl)-1-propargyl benzimidazoles, transformation led to variously substituted benzimidazoles bearing...

We report an efficient synthesis of furopyrans through a gold(I)-catalyzed domino reaction. By starting from the same source and changing solvent reaction, two classes are accessible. During this one-step process, which takes place in DMF, bonds heterocycles formed. DFT calculations furnish mechanistic understanding transformation. The sequence includes 5-endo-dig cyclization, regioselective 8-endo-dig retro 8π 6π electrocyclization.

Abstract From electronic waste to Pd‐catalyzed reaction! The straightforward valuation of palladium recovered from is reported here. Following a classical leaching stage, selectively extracted complex aqueous mixture metallic cations into an organic phase. Afterwards, the judicious choice surfactant enables stabilization during back extraction cycles, and direct preparation micellar solution, which can be employed in model Suzuki−Miyaura cross‐coupling reaction. Clean phase separation...

The HDA reaction of dithioesters was developed as a new click-reaction compatible with the indirect 18F-labelling peptides. It involves dithioester-peptides and radiofluorinated diene novel prosthetic group. method applied to PSMA-ligand for in vivo detection LNCap tumors xenografted mice.

Mitogen- and Stress-Activated Kinase 1 (MSK1) is a nuclear kinase, taking part in the activation pathway of pro-inflammatory transcription factor NF-kB demonstrating therapeutic target potential inflammatory diseases such as asthma, psoriasis atherosclerosis. To date, few MSK1 inhibitors were reported. In order to identify new inhibitors, screening library low molecular weight compounds was performed, results highlighted 6-phenylpyridin-2-yl guanidine (compound 1a, IC50~18 µM) starting hit...

We report an efficient Buchwald–Hartwig cross-coupling reaction in alcoholic solvent, which a low catalyst loading showed excellent performance for coupling aryl halides (I, Br, and Cl) with broad set of amines, amides, ureas, carbamates under mild conditions. Mechanistically speaking, protic polar medium, extremely bulky biarylphosphine ligands interact the dimeric precatalyst [Pd(π-(R)-allyl)Cl]2 to form corresponding cationic complexes [Pd(π-(R)-allyl)(L)]Cl situ spontaneously. The...

We report herein an efficient synthesis of furopyran derivatives through a gold(I)-catalyzed domino reaction. The cascade reaction starts with two regioselective cyclizations, 5-endo-dig and 8-endo-dig, followed Grob-type fragmentation hetero Diels–Alder. obtained contain fused spiro-heterocycles. During this one-pot process, four bonds controlled stereogenic centers including quaternary center are formed.

Abstract 2‐aryl‐1,2,3‐triazoles are important compounds that find applications in Medicinal chemistry, diagnostics, catalysis and others. However, only few methodologies for their preparation is found the literature. The development of a post cycloaddition N 2 selective arylation towards these would benefit from more convergent strategy. In present communication, new tryptophan‐based ligand allowed ‐position 1,2,3‐triazoles using recyclable CuFe O 4 nanoparticles. This method was efficient...

Abstract A series of 1,4‐thiazepanes were synthesized using gold‐catalysis from 1,3‐aminothioethers having two or three carbon stereocenters. The process consists in a 7‐ exo ‐dig cyclization with C−S bond formation and concomitant allyl S‐to‐C migration, which occurs intramolecularly as demonstrated by cross‐over experiment. X‐ray crystal‐structure analysis one product confirmed the expected stereochemistry. Two examples reactions, azide‐alkyne cycloaddition (CuAAC) N ‐alkylation,...

Herein, we describe a catalyst-free thia-Diels–Alder cycloaddition for the chemoselective labeling of fully deprotected phosphonodithioester–peptides in solution with fluorophores functionalized an exocyclic diene. The reaction was optimized on model tripeptide 1 containing lysine residue, which enabled its rapid and straightforward three different (fluorescein, lissamine rhodamine B, squaraine) very mild conditions (H2O/iPrOH, 37 °C, h). then successfully applied to apelin-13 squaraine dye....