Multinuclear mesoionic 1,2,3-triazolylidene complexes: design, synthesis, and applications.

The chemistry of multinuclear metal complexes bearing by N-heterocyclic carbene (NHC) ligands, is an area of fast growing interest in modern organometallic chemistry. In particular, complexes supported by mesoionic (MIC) 1,2,3-triazolylidenes are attracting a great deal attention due to their postulated superior donor capacity compared to classical NHC ligands. Despite the readily available synthetic routes to MIC-based ligand platforms featuring several substitution levels, most of the coordination chemistry of triazolylidenes is still dominated by mononuclear complexes. In this short review article, recent progress on the design and synthesis of multinuclear triazolylidene complexes (ranging from di- to tetranuclear species) is discussed. Special emphasis is placed on their structural features, electronic properties and catalytic applications.

Stereoselective C-glycosidation of D-fucose derivatives directed by the protective groups.

Stereoselectivity in the C-glycosidation of lactones derived from D-fucose by following Kishi's method, which involves the addition of a nucleophile onto a carbohydrate-derived lactone and subsequent reduction of the lactol, was found to be reliant on the nature of the C2 and C3 protective groups. Lactones bearing TBDMS protecting groups selectively afford 1,3-trans products (α anomer), in which the stereoselective outcome is in apparent concordance with Woerpel's model. On the other hand, their benzylated congeners produce the 1,3-cis products (ß anomer) as the major diastereoisomers. The latter results suggest an abnormal behavior during the stereoselective nucleophilic substitution at the anomeric position of the benzylated lactones.