The bio-based substrate and target product 2,5-bishydroxymethylfuran (BHMF) demonstrated to influence the reaction kinetics in the homogeneous reduction of 5-hydroxymethylfurfural (HMF) catalyzed by the Ru-based Shvo's catalyst. A combined experimental and computational study supports an important role of the -CH2OH moiety which may be involved in the catalytic cycle toward the formation of different intermediates from HMF and BHMF. The reaction is selective and leads to quantitative formation of BHMF working under mild conditions. Furthermore, an optimized recycling procedure which avoids the use of water, allows recover and reuse of the catalyst without loss of activity. The mechanistic insights from this work may be extended to provide a general description of the chemistry of the Shvo's catalyst feeding further bio-based molecules.

The first example of a catalytic asymmetric vinylogous Povarov reaction is presented. 1-N-Acylamino-1,3-butadienes react selectively at their terminal double bond in the presence of a chiral phosphoric acid catalyst, delivering highly enantioenriched 1,2,3,4-tetrahydroquinolines bearing a synthetically versatile enecarbamate group at the 4-position.

The first enantioselective Friedel-Crafts alkylation-acetalization-cascade of naphthols with α,β-unsaturated cyclic ketones and 1H-inden-1-ones was realized. 9-Amino(9-deoxy)epi-quinine A was the catalyst of choice for the realization of polycyclic structures with high enantiocontrol.

4-Aryl-3-bromo-N-benzylmaleimides and 3,4-biaryl-N-benzylmaleimides have been synthesized by a modified Suzuki cross-coupling reaction from 3,4-dibromo-N-benzylmaleimide. The conformational studies by dynamic NMR and DFT calculations showed that the interconversion barrier between the two available skewed conformations is under steric control. When the aryl group was a 2-methylnaphthyl, thermally stable atropisomers were isolated by enantioselective HPLC and their absolute configurations were assigned by TD-DFT simulations of the ECD spectra.

The stereodynamic behavior of a series of pyrazolo[3,4-b]pyridines was studied. The restricted rotations of the aryl substituent in position 4 of the heteroaromatic ring and of the benzoyl group in position 5 generated conformational enantiomers or conformational diastereoisomers depending on the local symmetry of the aryl substituent, with very high rotational barriers despite the absence of ortho-substituents. The energy barriers for the rotation of the 5-benzoyl group and the 4-aromatic ring were measured by dynamic NMR and rationalized by DFT calculations. When the aryl substituent at position 4 was 1-naphthyl, the resulting atropisomeric pair was resolved by means of enantioselective HPLC and the absolute configuration was determined by TD-DFT simulations of electronic circular dichroism spectra.