A symmetry-driven approach toward the total synthesis of dodecahedrane.

Herein, we describe our progress toward the total synthesis of dodecahedrane, a complex and highly symmetrical hydrocarbon that bears twelve fused rings arranged in a cage-like architecture. Central to our approach is a late-stage [2+2+2+2+2] polyene cyclization cascade, which is expected to construct five new bonds and ten new rings in a single transformation. Toward this end, we describe efforts to synthesize key monomeric fragments, along with successful dimerization studies using a pinacol coupling approach. Subsequent studies include an attempted olefin metathesis rearrangement cascade in addition to a successful intramolecular photochemical [2+2] reaction. Although attempts to elaborate the photocycloaddition product were unsuccessful, our studies provide access to complex dimeric scaffolds and are expected to help guide our future total synthesis studies.

Facile synthesis of 2-aza-9,10-diphenylanthracene and the effect of precise nitrogen atom incorporation on OLED emitters performance.

Polycyclic aromatic hydrocarbons (PAHs) are important compounds in materials chemistry, particularly for optoelectronic applications. One strategy for tuning PAH properties involves the net exchange of carbon atoms for heteroatoms, such as nitrogen. We report a comparative study of the well-known fluorophore 9,10-diphenylanthracene with an aza analog. The latter compound is accessed using a short sequence involving the use of two strained cyclic alkynes, benzyne and a 3,4-piperidyne, in Diels-Alder cycloaddition sequences. Comparative studies of 9,10-diphenylanthracene and the aza-analog show how the addition of a single nitrogen atom impacts electrochemical and optical properties. Organic light-emitting diode (OLED) devices were prepared using both compounds, which showed that nitrogen substitution leads to an unexpected red shift in electroluminescence, likely due to exciplex formation between the active layer and the 4,4'-N,N'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPB) hole-transport layer. These studies highlight a unique approach to accessing heteroatom-containing PAHs, while underscoring the impact of heteroatoms on OLED device performance.

Reagent-Controlled α-Selective Dehydrative Glycosylation of 2,6-Dideoxy Sugars: Construction of the Arugomycin Tetrasaccharide.

The first synthesis of the tetrasaccharide fragment of the anthracycline natural product Arugomycin is described. A reagent controlled dehydrative glycosylation method involving cyclopropenium activation was utilized to synthesize the α-linkages with complete anomeric selectivity. The synthesis was completed in 20 total steps, and in 2.5% overall yield with a longest linear sequence of 15 steps.