Pyrene-Fused [7]Helicenes Connected Via Hexagonal and Heptagonal Rings: Stereospecific Synthesis and Chiroptical Properties.

In this manuscript, we portrayed a stereospecific synthesis of - and -symmetric pyrene-fused [7]helicene compounds and , respectively. Compounds and were synthesized via a one-pot Suzuki coupling-C-H activation and two-step Suzuki coupling-Scholl reaction, respectively, with complete retention of configuration. The synthesized molecules differ in the fusing mode of [7]helicene units with pyrene via six- and seven-membered rings for and , respectively.

- and -Symmetric Configurationally Stable Pyrene-Fused [5]Helicenes Connected via Hexagonal and Heptagonal Rings.

In this paper, we describe the stereospecific synthesis and functional properties of - and -symmetric pyrene-fused [5]helicene molecules and connected via hexagonal and heptagonal rings, respectively. Both molecules showed high configurational stability and distinct functional properties, which were attributed to the fusing mode of [5]helicene with the pyrene and molecular symmetry. The estimated Gibbs activation energy for enantiomerization of is one of the highest reported values for any π-conjugated molecules incorporating [5]helicene moiety.

A K-arylacetylide complex for catalytic terminal alkyne functionalization using KOBu as a precatalyst.

Herein we report a transition metal free catalytic terminal alkyne functionalization across the C-X triple bond (X = CH and N) with E-selective homo (alkyne-alkyne) and head-to-tail selective hetero (alkyne-nitrile) dimerization. A series of stoichiometric reactions enabled us to crystallize a reactive organometallic intermediate K-arylacetylide complex which was characterized by X-ray crystallography, indicating that an ionic mechanism is operative.

Transition-Metal-Free Catalytic Carboalkoxylation of Styrenes at Room Temperature.

Herein, we describe the first transition-metal-free catalytic carboalkoxylation of styrenes with aryl diazonium salts by Meerwein addition in the presence of a phenalenyl ligand at room temperature without requiring any light stimulation. This three-component reaction allows facile difunctionalization of styrene derivatives with various alcohols (such as 1, 2, and 3°) as the source of alkoxy group during this transformation. The key intermediates and the transition states involved in this reaction path were unraveled by a series of control experiments coupled with density functional theory calculations.