Titanocene-catalyzed cascade cyclization of epoxypolyprenes: straightforward synthesis of terpenoids by free-radical chemistry

The titanocene-catalyzed cascade cyclization of epoxypolyenes, which are easily prepared from commercially available polyprenoids, has proven to be a useful procedure for the synthesis of C(10), C(15), C(20), and C(30) terpenoids, including monocyclic, bicyclic, and tricyclic natural products. Both theoretical and experimental evidence suggests that this cyclization takes place in a nonconcerted fashion via discrete carbon-centered radicals. Nevertheless, the termination step of the process seems to be subjected to a kind of water-dependent control, which is unusual in free-radical chemistry. The catalytic cycle is based on the use of the novel combination Me(3)SiCl/2,4,6-collidine to regenerate the titanocene catalyst. In practice this procedure has several advantages: it takes place at room temperature under mild conditions compatible with different functional groups, uses inexpensive reagents, and its end step can easily be controlled to give exocyclic double bonds by simply excluding water from the medium.     

Freezing Capture of Polymorphic Aggregates of Bolaamphiphilic L‐Valine‐Based Molecular Hydrogelators

Nanostructured xerogels have been prepared by the freeze‐drying of hydrogels and aggregates formed by bolaamphiphilic L ‐valine derivatives after aging under different environmental conditions. A wide variety of shapes and sizes has been achieved by a simple methodology. These nanostructures have been studied by SEM and WAXD and a dramatic influence of structural flexibility on the kinetics of aggregation has been observed. Such flexibility and a modulation of the hydrophobic effect have shown a profound influence in the packing of these compounds and revealed a high degree of polymorphism.     

Evaluation of viscoelastic constants of metallic materials by laser-ultrasonics at elevating temperature

The main objective of this study is the determination of elastic moduli and viscosity coefficients of metals at elevating temperature up to melting point. More specifically, it involves the analysis of the propagation of acoustic waves generated and detected simultaneously by laser-ultrasonic for the measurement of longitudinal and shear velocities. This preliminary work primarily concerns Tin (Sn) metal known for its low melting point and attenuation coefficient.     

Bassianolone: an antimicrobial precursor of cephalosporolides E and F from the entomoparasitic fungus Beauveria bassiana

We have established the chemical structure of (+)-bassianolone (3), the antimicrobial compound precursor of cephalosporolides E and F, and that of the furan metabolite 4 from the entomopathogenic fungus Beauveria bassiana.     

Unprecedented hydrogen transfer from water to alkenes and alkynes mediated by TiIII and late transition metals

We describe how alkenes and alkynes can be hydrogenated under mild conditions by hydrogen transfer from water mediated by titanocene(III) and a substoichiometric quantity of one of the late transition metals usually employed as hydrogenation catalysts. This process proceeds presumably by H-atom transfer from TiIII-coordinated water to the late transition metal partner (depicted in the drawing above), a mechanism in support of which we provide theoretical and experimental evidence.     

Ti-catalyzed homolytic opening of ozonides: a sustainable C-C bond-forming reaction

The unprecedented homolytic opening of ozonides promoted and catalyzed by titanocene(III) is reported. This novel reaction proceeds at room temperature under neutral, mild conditions compatible with many functional groups and provides carbon radicals suitable to form C-C bonds via both homocoupling and cross-coupling processes. The procedure has been advantageously exploited for the straightforward synthesis of the natural product brittonin A.     

CpTiCl2-Catalyzed Cross-Coupling between Internal Alkynes and Ketones: A Novel Concept in the Synthesis of Halogenated,Conjugated Dienes

A novel concept for the synthesis of halogenated, conjugated dienes is disclosed: the CpTiCl₂-catalyzed coupling of keto-alkynes, in the presence of Me₃SiBr/Et₃N ⋅ HBr. This reaction provided five-, six-, and seven-membered carbocycles, nitrogenated heterocycles, as well as six-membered oxygenated heterocycles leading to a brominated conjugate diene. These products showed high reactivity in the Diels–Alder, Suzuki, and Sonogashira reactions, giving complex chemical structures in only three steps from the corresponding acyclic keto-alkyne. Hopefully, this strategy will pave the way towards the synthesis of bioactive natural products and new materials.