Design, Synthesis and Self-Assembly of Functional Amphiphilic Metallodendrimers.

A new family of alkynylated, amphiphilic dendrimers consisting of amidoamine linkers connected to 5,5'-functionalized 2,2'-bipyridine cores has been developed and evaluated in the formation of metallodendrimers of different generations and in self-assembly protocols. A convergent synthetic strategy was applied to provide dumbbell-shaped amphiphilic dendrimers, where the 2,2'-bipyridine cores could be coordinated to Fe centers to afford corresponding metallodendrimers. The ability of the metallic- and non-metallic dendritic structures to self-assemble into functional supramolecular aggregates were furthermore evaluated in aqueous solution.

Glycosyl dithiocarbamates: β-selective couplings without auxiliary groups.

In this article, we evaluate glycosyl dithiocarbamates (DTCs) with unprotected C2 hydroxyls as donors in β-linked oligosaccharide synthesis. We report a mild, one-pot conversion of glycals into β-glycosyl DTCs via DMDO oxidation with subsequent ring opening by DTC salts, which can be generated in situ from secondary amines and CS2. Glycosyl DTCs are readily activated with Cu(I) or Cu(II) triflate at low temperatures and are amenable to reiterative synthesis strategies, as demonstrated by the efficient construction of a tri-β-1,6-linked tetrasaccharide.

Calixarene-Mediated Synthesis of Cobalt Nanoparticles: An Accretion Model for Separate Control over Nucleation and Growth.

The nucleation and growth of crystalline cobalt nanoparticles (Co NPs) under solvothermal conditions can be separated into distinct stages by using (i) polynuclear clusters with multivalent capping ligands to initiate nucleation, and (ii) thermolabile organometallic complexes with low autonucleation potential to promote crystalline growth. Both nucleation and growth take place within an amorphous accretion, formed in the presence of polyvalent surfactants. At the pre-nucleation stage, a calixarene complex with multiple Co-alkyne ligands (Co-calixarene ) undergoes thermal decomposition above 130 °C to form "capped cluster" intermediates that coalesce into well-defined Co nanoclusters, but are resistant to further aggregation.

Glycal assembly by the in situ generation of glycosyl dithiocarbamates.

Glycal assembly offers an expedient entry into β-linked oligosaccharides, but epoxyglycal donors can be capricious in their reactivities. Treatment with Et(2)NH and CS(2) enables their in situ conversion into glycosyl dithiocarbamates, which can be activated by copper triflate for coupling with complex or sterically congested acceptors. The coupling efficiency can be further enhanced by in situ benzoylation, as illustrated in an 11-step synthesis of a branched hexasaccharide from glucals in 28% isolated yield and just four chromatographic purifications.

Stereoelectronic factors in the stereoselective epoxidation of glycals and 4-deoxypentenosides.

Glycals and 4-deoxypentenosides (4-DPs), unsaturated pyranosides with similar structures and reactivity profiles, can exhibit a high degree of stereoselectivity upon epoxidation with dimethyldioxirane (DMDO). In most cases, the glycals and their corresponding 4-DP isosteres share the same facioselectivity, implying that the pyran substituents are largely responsible for the stereodirecting effect. Fully substituted dihydropyrans are subject to a "majority rule", in which the epoxidation is directed toward the face opposite to two of the three groups.