An efficiently aerobic dehydrazination of arylhydrazines promoted by potassium tert-butoxide (tBuOK) is detailed in this study. This method smoothly produces aromatics analogues from arylhydrazines using catalytic amount of tBuOK under practical conditions, exhibiting excellent functional group tolerance and a broad substrate scope. The application potential of this approach is further demonstrated through the preparation of deuterated, iodinated and brominated aromatics. Moreover, it shows that this aerobic base-mediated dehydrazination could be utilized to prepare unsymmetrical aryl sulfides ..read more

4,16-para-substituted [2.2]paracylophane with naphthalene (PCP⎼NAP), anthracene (PCP⎼ANTH), and tetraphenylethylene (PCP⎼TPE), as new through-space conjugated dimers, were prepared by the Suzuki–Miyaura cross-coupling reaction of 4,16-diboryl[2.2]paracyclophane and the corresponding bromo derivative using Pd(PPh3)4 as a catalyst and KOH as a base. The synthesized compounds were fully characterized by NMR and HR-MS, and their photophysical and electrochemical properties were studied. The photoluminescence quantum yield of PCP⎼NAP, PCP⎼ANTH were determined to be 0.21, 0.50 and for PCP⎼TPE in agg ..read more

We report the construction of C5-indole unnatural amino acid derivatives via the diastereoselective Pd(II)-catalyzed prochiral β-C(sp3)-H arylation of racemic (DL), and enantiopure L- and D-carboxamides of amino acids with 5-iodoindoles. Independently, indole-based compounds and amino acid motifs are important small molecules in organic synthesis and drug discovery research. This report aimed to contribute to enriching the library of indole-based unnatural amino acid derivatives. The synthesis of examples of C5-indole motif-installed amino acid derivatives comprising norvaline, phenylalanine ..read more

A direct diastereoselective aldol reaction of cyclic or acyclic α-azido ketones with α-trifluoromethyl (CF3) pyruvate catalysed by DABCO is developed, which allowed the facile access of CF3-containing multifunctional organoazides with vicinal tetrasubstituted carbons in good to high yields and diastereoselectivities. Moreover, phenylethynyl trifluoro- and difluoromethyl ketones are also viable substrates. Up to 50% enantioselectivity could be obtained in the initial exploration of the catalytic asymmetric variant ..read more

This review aims to highlight the role that computational chemistry has played in advancing the supramolecular chemistry field. We demonstrated recent uses of computational methodologies to elucidate noncovalent interactions in various processes occurring in supramolecular systems. We also emphasized the contributions of these techniques to studying reactions within confined space, showing how computational methodologies help clarify the effects of reactivity and conformational locking. Furthermore, we underscore the utilization of Molecular Dynamics (MD) in elucidating dynamical processes, un ..read more

The Daphniphyllum alkaloids represent a particularly diverse class of complex diterpene alkaloids, which are characterized by their enormous structural diversity. The daphnicyclidins, a subgroup of these alkaloids, stand out due to their unique pentafulvene structural motif. This review article gives an overview of the compounds that have been isolated so far and can be assigned to this subgroup. Furthermore, all synthesis approaches and total syntheses published to date are presented ..read more

The Pt-cathode hydrogen evolution reaction (Pt-HER) of acetone cyanohydrin provides an alternative method for introducing the cyano group onto electrophilic carbons of imines and chalcones. The synthesis of α-aminonitriles and β-cyano ketones has been achieved smoothly with a small excess of cyanating agent (2 equivalent), catalytic amount of supporting electrolyte and low electricity consumption (0.02 F/mol). Besides demonstrating a general atom economy, the high Faradaic efficiency, allows for a scale-up with low-demanding electrochemical design and short electrolysis times ..read more

An electrochemical decarboxylative addition of N-substituted glycines to enaminones has been developed and conducted under oxidant-, catalyst-, and light-free conditions in acetonitrile at room temperature by using electron as the traceless oxidant, which provided a green approach to C3-aminomethyl chromones. The resulting products were formed through radical addition/oxidation/cyclization or electrophilic addition/cyclization pathway and could act as valuable building blocks to construct polysubstituted pyrimidine derivatives ..read more

The presence of alkene moieties in fatty acids of (phospho)lipids and cholesterol derivatives makes them highly susceptible to damage by nitrate radicals (NO3•), potentially formed through simultaneous exposure to the environmental air pollutants nitrogen dioxide (NO2•) and ozone (O3). Absolute rate coefficients derived from reactions with simplified model systems range from 4 to 8 × 109 M−1 s−1 in acetonitrile, ranking among the highest determined for NO3• reactions with biomolecules in solution to date. Alkenes featuring an electron-withdrawing carbonyl substituent also display notable react ..read more

The successful mono- and diprotonation of DAMN showed the first site of protonation to be an amino group, while the second protonation occurs at a nitrile group. The prepared salts were characterized by vibrational spectroscopy and single crystal X-ray crystallography. Under strong superacidic conditions and with sufficient time cyclization of two (di)protonated molecules of DAMN is observed, yielding a tetracationic pyrazine species. Quantum chemical calculations are employed to explain reactivity and properties of compounds shown in the manuscript ..read more