Synthesis of Phenalenyl-Fused Pyrylium Cations: Divergent C-H Activation/Annulation Reaction Sequence of Naphthalene Aldehydes with Alkynes.

Described herein is the synthesis of stable oxonium-doped polycyclic aromatic hydrocarbons (PAHs) by the rhodium-catalyzed C-H activation/annulations of naphthalene-type aldehydes with internal alkynes. This protocol provides four divergent reaction types, including two unexpected annulations with an oxygen transposition process, which lead to diverse types of phenalenyl-fused pyrylium cations comprising a four-, five-, or six-ring-fused π-conjugated core. The annulations exhibit an exquisite regioselectivity and a high tolerance of sensitive functional groups.

Copper(ii)-promoted oxidative C-H/C-H cross-coupling for rapid access to aza-BODIPY-indole derivatives with broad optical absorption.

The direct C-H activation of electron-deficient aza-BODIPYs has been effectively achieved via a concise and inexpensive Cu(ii)-promoted oxidative C-H/C-H coupling approach. The resulting indole-aza-BODIPY 6b covers a broad spectrum of 429-900 nm with a FWHM of 294 nm in solution and covers a UV-vis-NIR region up to 1100 nm in film.

Cu-catalyzed controllable C-H mono-/di-/triarylations of imidazolium salts for ionic functional materials.

Herein the Cu-catalyzed direct C-H mono-, di- and triarylations of imidazolium salts with aryl iodides/bromides are accomplished for the first time. The unprecedented alkenylation and alkynylation are also realized using alkenyl and alkynyl iodides, respectively. Moreover, triarylated imidazolium salts with different substituents can be accessed in a modular and one-pot manner.

Palladium-Catalyzed Annulation of Internal Alkynes: Direct Access to π-Conjugated Ullazines.

A palladium-catalyzed cyclization reaction of 1-(2,6-dibromophenyl)-1H-pyrroles with alkynes has been developed to construct various π-conjugated indolizino[6,5,4,3-ija]quinolones (ullazines) with a reactive functional group tolerance. As illustrative examples, three new ullazine-based sensitizers are synthesized, and the performance of these dyes is examined in DSSC devices, which demonstrates the potential of direct C-H functionalization in the construction of organic optoelectronic materials.

Rapid Access to 2,2'-Bithiazole-Based Copolymers via Sequential Palladium-Catalyzed C-H/C-X and C-H/C-H Coupling Reactions.

A rapid access to 2,2'-bithiazole-based copolymers has been developed on the basis of the sequential palladium-catalyzed CH/CX and CH/CH coupling reactions. To assemble a "copolymer" through homopolymerization, a type of symmetric A-B-A-type building block is designed as the monomer and prepared via the regioselective C5H arylation of thiazole. A PdCl2 /CuCl-cocatalyzed oxidative CH/CH homopolymerization has been established to afford the 2,2'-bithiazole-based copolymers with high Mn (up to 69400).