The optimization of a Biginelli Multicomponent Reaction (MCR) protocol for obtaining a collection of 3,4-dihydropyrimidin-2(1H)-one/thione, with UV absorption and blue fluorescent properties, from synthetic coumarin beta-ketoester derivatives is described. This is the first report of Biginelli adducts bearing a coumarin nucleus in the β-ketoester moiety and their MCR mechanism seems to pass through a Knoevenagel intermediate, which was considered as unlikely before. A chemical library was obtained and the dihydropyrimidin-2(1H)-one nucleus formation confirmed by X-ray diffraction. Photophysical analyses of representative compounds in different solvents show good Stokes shifts in water that are associated to a postulated ICT process and pK_a determination make these compounds a good start point for new chemical and biological probes as well as useful pH indicators.

The synthesis, crystal structures and magnetic properties of two families of heterospin complexes containing lanthanide ions and a bis(imino nitroxide) biradical (IPhIN = 1-iodo-3,5-bis(4′,4′,5′,5′-tetramethyl-4′,5′-dihydro-1H-imidazole-1′-oxyl)benzene) are reported: in [Ln₂(hfac)₆(IPhIN)(H₂O)₂] compounds, two lanthanide ions [Ln = Gd^III (1) and Dy^III (2)] are coordinated to the biradical, and in [Ln(hfac)₃(IPhIN)(H₂O)] compounds, one lanthanide ion (Ln = Tb^III (3), Gd^III (4) or Dy^III (5)) is coordinated to the biradical. Ferromagnetic intramolecular magnetic interactions between Gd^III and the biradical were found for 1 and 4, while intramolecular magnetic interactions between the radicals were ferro- and antiferromagnetic, respectively. Compound 2 shows a field induced slow relaxation of magnetization, which (under an external applied field of 2 kOe) exhibits an activation energy barrier of ΔE/k_B = 27 K and a pre-exponential factor of 1.4 × 10⁻⁸ s. To support the magnetic characterization of compound 3ab initio calculations were also performed.

The highly diastereoselective synthesis of P-stereogenic phosphinic amides via directed ortho lithiation (DoLi) of (S_C)-P,P-diphenylphosphinic amides with t-BuLi followed by electrophilic quench reactions is described. Functionalised derivatives containing a wide variety of ortho substituents (Cl, Br, I, OH, N₃, SiMe₃, SnMe₃, P(O)Ph₂, Me, allyl, ^tBuOCO) have been prepared in high yields with diastereomeric ratios up to 98 : 2. The X-ray diffraction structure of the ortho-stannylated and ortho-iodo compounds showed that the pro-S P-phenyl ring was stereoselectively ortho-deprotonated by the organolithium base. The usefulness of the method is supported by two key transformations, the synthesis of P-stereogenic methyl phosphinates through replacement of the chiral auxiliary by a methoxy group and the first example of the insertion of benzyne into the P–N bond of a P-stereogenic phosphinic amide. A DFT study of this reaction showed that the insertion proceeds through a [2 + 2] cycloaddition and a subsequent ring-opening with retention of the P-configuration. Explorative coordination chemistry of the new P-stereogenic ligands provided access to a chiral phosphinic amide-phosphine oxide Zn(II) complex, the crystal structure of which is reported.